BE416669A - - Google Patents

Description

       

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    Improvements in the manufacture of artificial structures.



   The manufacture of shaped structures from viscose by means of coagulating or alkaline precipitating baths is first described in British Patent No. 323,747 by the same inventor, in which a hot or very hot alkali solution is proposed as a coagulating bath.



   Practical experience with the method set forth in the above patent has, however, shown that the coagulation is much too slow for any practical use.



   In fact, it has been found impossible to coagulate viscose using a very hot or hot caustic alkali solution in the rapid and complete manner required.

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 in the manufacture on an industrial scale of shaped strac- ters of all kinds, such as artificial silk, artificial horsehair, artificial straw, film, ribbons, tapes, plates, coverings, coatings and impregnations of all kinds, finishes, materials for finishing or filling fabrics, canvas for bookbinding, substances for sizing threads, for printing fabrics, etc.



   In the process described in British Patent No. 323,747 by the same inventor, the coagulation is carried out with such a slowness that this process was to remain a mere laboratory method. However, in view of the slowness of coagulation, the inventor was not able to produce artificial threads by means of a solution of caustic alkali or of a solution of alkali sulphide hot or very hot even at laboratory, and this is the reason why the examples contained in Patent No. 323,747 are confined to the manufacture of films.

   However, the time required to effect by means of a very hot caustic alkali solution, the complete coagulation of a viscose layer having a thickness customary in the film industry is much too long to allow the manufacture of. films on an industrial scale. This is true even when the caustic alkali solution or sodium sulfide solution is used at a very high temperature, for example at about 140 ° C.



  For, apart from the fact that solutions of caustic alkali or of alkali sulphide having the desired concentration, when they are employed at temperatures appreciably exceeding 100 ° C., have an unfavorable effect on the properties of the film and in particular on tensile strength, they do not coagulate viscose at the speed required in the film industry.

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   Even if we use a viscose which, thanks to a prolonged setting or full. that a small proportion of carbon disulphide has been used for its preparation, contains a greatly reduced proportion of OSS, for example no more than one CSS group for 6 or for a greater number of units C6H1005 molecules of cellulose, it is impossible to produce on a commercial scale from this viscose artificial yarns or film according to the process described in UK Patent No. 323,747.



     The same is true for other shaped structures, such as, for example, coverings, layers and prints of all kinds, dressings, fillings and finishings of textiles, sizing of threads, printing of fabrics, etc.



   Generally speaking, the present invention is based on the inventive principle that shaped structures and useful articles having valuable properties can be obtained by coagulating solutions of cellulose ether xanthates by means of alkaline coagulation baths. lins when an agent which contains at least an alkaline carbonate is employed as a coagulating agent.



   The eminently important part of the present invention, however, is the conception that cellulose ether xanthates prepared using a proportion of carbon disulphides of less than 20%, preferably less than 15%, or even more preferably less than 10% calculated on the weight of the corresponding cellulose is particularly suitable as a starting material for the manufacture of shaped structures or other useful articles by means of coagulant baths containing at least one alkali carbonate.



   The inventoura further obhorved that, for or who uonuur not the cellulose ether xanthates prepared in. average of a proportion of carbon sulide which is not less than or is greater than 20% of carbon disulfide calculated on the weight of the corresponding cellulose ether, xanthates

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 of such cellulose ether which are particularly suitable for the present invention are those which have reached a degree of maturity substantially exceeding the C2.4 stage and preferably exceeding the C36 'stage.
In other words, the present invention includes in particular the idea of forming the cellulose ether xanthate in the form of a conformal structure and of coagulating the conforming solution of cellulose ether xanthate by means of a cellulose ether xanthate. solution of one or more alkaline carbonates.



   The inventor was able to prove that, when suitable working conditions are observed, despite their alkalinity, the alkali carbonates coagulate the shaped solutions of cellulose ether xanthate with the rapidity and completeness required in the process. 'Conforming Structures' industry, t that conforming structures produced in accordance with the invention have valuable properties.



   This discovery is all the more unexpected, since it would not have been possible to suppose that a solution of a xanthet of cellulose ether in a solution of caustic alkali could be coagulated by means of solutions of carbonates. alkaline, that is to say those with an alkaline reaction. However, this is the least we could do, the conagulation being expected to occur with rapidity and. a complete sufficient for the production of conformed structures.

   It was also unlikely that alkaline reacting salt solutions would be able to precipitate conformal solutions of cellulose ether xanthate in the form of cohesive structures strong enough to withstand all the operations involved in production and ( or) sequencing the conformed structures and to ensure the minimum resistance that the conformed structures must possess.



   This is why, until now, we have generally used

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 for the coagulation of shaped solutions of cellulose ether xanthates, coagulating agents which are able to neutralize aloali present in the solutions.



   A particularly remarkable advantage of the invention over methods in which acidic coagulating agents are used to make shaped structures from cellulose ether xanthates is that, unlike these methods, the present method makes it possible to recover at least a part of the caustic alkali contained in the solutions of the cellulose ether xanthates and, consequently, to reintroduce the caustic alkali in the operation following a cyclic circuit.

   This advantage should not be underestimated, considering that the proportions of caustic alkali present in the solutions of cellulose ether xanthates are rather large and considering that, in the relative processes known heretofore in in which the coagulation bath used consists mainly of extended sulfuric acid not containing or containing sodium sulphate and / or another sulphate, the caustic soda contained in the solutions of xanthates of ether of cellulose is transformed into sodium sulphate which is more or less worthless, ie it is simply lost.



   From the foregoing it therefore emerges that not only the solvent, that is to say the caustic alkali, but also the coagulating agent, that is to say the sulfuric acid, is completely lost. in the methods known hitherto.



   . Accordingly, another advantage of the present invention over the methods known heretofore is the possibility of reusing, in the process, at least part of the alkaline carbonate contained in the coagulating agent. As in all cases in which a solution of one or more alkaline carbonates without any other additional substance serves as a pre-coagulation, even after having served as a layer.

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 a longer or shorter period of time, apart from the water, the coagulating agent contains practically one or more alkaline carbonates and a little caustic alkali, the alkali carbonate (s) can be separated caustic alkali as usual,

     for example by crystallization or by evaporation of water, heating the residue to the melting point of the caustic alkali or to a temperature between the melting point of the caustic alkali and the melting point of the alkali carbonate, then separating the molten caustic alkali from the alkaline carbonate. Alternatively, the alkali carbonate can be converted into the corresponding caustic alkali by caustification, i.e. by treating the coagulation bath with lime, as known in the caustic alkali industry. .



   In either case the alkali carbonate is reused in the operation following a cyclic circuit; in the form of alkali carbonate (in the first case) for the preparation of the coagulation bath, and in the form of caustic soda (in the second case) for the production of cellulose ether xanthate and (or) for prepare the. cellulose ether xantiiate solution.



   If desired, buildup, i.e. the presence of a large proportion of caustic alkali or the presence of any caustic alkali in the coagulation bath, can be avoided, for example by introducing Carbo- anhydride
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 nique ftfnn la b Ln do ao; ; ^ a7..t.on, oontinuolloRont or üo tumpo to another, and thus transforming, according to the quantity of CO2 which is introduced, the caustic alkali present in the bath or a part of this alkali into carbonate or bicarbonate of sodium.

   Thus, in some cases, the adverse influence of the caustic alkali introduced into the bath from the conformal solution of cellulose ether xanthate may be. to have

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 on the freshly coagulated shaped structure or on the coagulating power of the alkali carbonate solution or on the mechanical strength and therefore on the conductivity of the freshly coagulated material through the spinning or film-making machine , or some of that influence can be neutralized.



   If the CO2 is prepared by heating calcium carbonate and if the recovery of the caustic soda is envisaged by causticizing the sodium carbonate, the remaining calcium oxide can be used for the caustification,
Another favorable feature of the present invention is the high price of aloaline carbonates, in particular sodium carbonates which fall into the category of the least expensive chemicals known.



   However, the present invention is marked by another very important technical progress. To understand it, you have to be aware of the following:
When preparing solutions of cellulose ether xanthates using a proportion of carbon disulphide of less than 20% and preferably less than 15% or more preferably less than 10% by weight of the cellulose ether. corresponding cellulose ether and transforming these solutions into shaped structures by means of acid coagulant baths, shaped structures such as strands or film are obtained having extensibility and, in some cases, also toughness. wet condition which are not sufficient for all practical purposes.



   In contrast to this, it is possible, in accordance with that part of the present invention in which, for the production of the cellulose ether xanthates, sulfide proportions of. carbon less than 20% and preferably less than 15% or, even better, less than 10% of the weight of the corresponding cellulose ether, -to produce (Ion

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 conformed structures which have sufficient extensibility for all practical uses.



   Therefore, the present invention can be regarded as the solution of the following three problems:
I. Regeneration of at least part of the caustic alkali contained in the cellulose ether xanthate solution.



   II. Reuse of at least part of the clotting agent.



   III. Use of amounts of carbon disulphide which are less than the amounts heretofore employed in the cellulose ether xanthates industry without adversely affecting the properties of shaped structures.



   Another technical advance provided by the present invention is in the valuable properties of shaped structures and other useful articles produced by this process.



  Thus, in some cases, the dynamometric properties, i.e. tensile strength, particularly in the wet state and (or.) The extensibility of shaped structures produced in accordance with the present invention at. from a solution of cellulose ether xanthate are superior to the dynamometric properties of shaped structures of the same type prepared from the same solution by means of the coagulating agents known heretofore in the manufacturing industry. shaped structures from cellulose ether xanthates.



   That part of the present invention which relates to the production of shaped structures from cellulose ether xanthates prepared using proportions of carbon disulphide of less than 20% and preferably less than 15% or, even better, less. to 10% of the weight of the corresponding cellulose ether, is also accompanied by the advantage that, thanks to the fact that the proportions of sodium sulphide, sodium hydrosulphide and sodium trithiocarbonate con-

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 Tons af3no bed solution of cellulose ether are considerably smaller than in the solutions of cellulose ether xanthates prepared in. using the usual proportions of carbon disulphide, the coagulant baths are less contaminated and (or)

   decolourised than in the case of cellulose ether xanthates prepared using the amounts of carbon disulfide customary in the art.



   But, ohose more important, like, or with regard to the alcali-
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 nitÓ don bf.tis, actnrj la pï'6auji.t pm'uo64.J, t1 no se aevonc pi <J of sulfur or. only reduced amounts are deposited in the shaped structures and, like the alkali carbonates acting as a desulfurizing agent in many cases, the desulphurization and / or bleaching of the shaped structures (operations which are necessary in finishing of shaped structures produced from ordinary cellulose ether xanthates using acid baths) may be omitted or applied in a limited manner.

   This is particularly true for the part of the present process in which less than 20% and preferably less than 15% or even more preferably less than 10% of carbon disulphide, calculated on the weight of the corresponding cellulose ether xanthates are used.



   An object of the invention is therefore to create the possibility of recovering at. minus a substantial portion of the caustic alkali contained in the solution which is shaped and another object of the invention is to reuse the coagulating agent in the process of manufacturing shaped structures. cellulose ether xanthates.



   A third object is to make the desulfurization and bleaching of shaped structures unnecessary or at least to make these operations much cheaper.



   Accordingly, one of the objects of the invention is considerable economy when the production of shaped structures and other useful articles from ether xanthates.

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 cellulose.



   Other objects of the invention will emerge from the description which follows.



   It should be understood that the invention is not limited to this description and to the examples of the actual carrying out of the process.



   The practice of the invention is to form a solution of a cellulose ether xanthate into a shaped structure and to cause the shaped solution to act with an agent containing at least one alkali carbonate.



   Then, optionally after having treated it pure a solution of an acid or a neutral or acidic salt, or of an acid and a neutral or acidic salt, or after having subjected it to a subsequent treatment by a solution of an alkali salt, for example of an alkali carbonate or of an alkali borate of an alkali, or of an alkali silicate of an alkali, or of a phosphate or acetate, or sulphide or analogue salt, the structure is washed
 EMI10.1
 conformed coagulated and l. dry, fcaltat2ve: ie nt + near the see treated with an acidic agent or any other agent indicated above and washed again.
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  Lm ue which reads conl'orfibes not including support, such as artificial threads, artificial horsehair, artificial straw, films, ribbons, bands, etc. the cellulose ether xanthate solution can be shaped and coagulated through appropriately shaped openings in a bath containing at least one alkali carbonate. According to the invention, also shaped structures without support, such as films or tapes etc., can also be produced by spreading the cellulose ether xanthate solution on a smooth surface which is at least partially immersed in the bath. coagulation, then removing the coagulated shaped structure from this surface and finishing it as shown in

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 the previous paragraph.

   In the case of shaped structures combined with a rigid or flexible support, such as coverings, layers and impregnations of all kinds, fabric preparations for printing on textile materials, bookbinding fabrics , tracing cloths, materials for gluing yarns or paper, for coating the pepier, etc., the shaping and coagulation can be effected by taking a rigid or flexible support and covering or covering it. impregnating or imprinting or coating it with the cellulose ether xanthate solution or incorporating it into the support in any other way, wholly or partially and, with or without intermediate drying, treating the material with an agent containing at least one alkaline carbonate,

   that is, by introducing the material into a bath containing at least one alkali carbonate, or by spraying it with an agent containing at least one alkali carbonate, or by passing the material through a mist containing at least one alkaline carbonate, or by any other method of applying a liquid or a paste on a rigid or flexible support.



   The cellulose ether xanthates which can be employed in the present invention can be prepared by any process or method, for example by the processes described in Belgian Patents Nos. 368,617, 407,052, 378,205, 382,218 and 389.619 by the same inventor and in his patent
 EMI11.1
 English vat nez0 or following lou proo (5dùu dCuri, l, rJ dc..riu loo English patents nos 9762/35, 9763/35, 9764/35, 9765,35,9766 / 35, 9767/35. 9768/35, 9769/35, 9770/35, 9771/35, 9772/35, 9773/35, 9774/35, 9775/35, 9776/35, 9777/35, 9778/35 and 12184/35, to the same inventor or according to n any other process or method suitable for the production of cellulose ether xanthates.



   It is obvious that in the present invention instead of solutions of cellulose ether xanthates, it is possible to employ

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 mixtures of solutions of xanthates of cellulose ether xenthates with cellulose or their solutions (viscose).



   In addition, it is evident that in the present invention, instead of xanthates of cellulose ethers, the products which are obtained by bringing together alkali-soluble cellulose etners in solid form can be used. or in solution with cellulose xanthates or their lutiens (viscose), for example the products described in British patent applications Nos. 11.343 / 1935 and 14.488 / 1935, by the same inventor.



   Likewise, the products obtained when the viscose is put into contaot with etherifying or esterifying agents, for example the products described in Belgian patents 368. 619, 371.965, 378.202, 389.591 and 389.619 of the same inventor and in his xx / UK Patent 362,437, may be employed in the present invention in place of or in admixture with cellulose ether xanthates or solutions thereof.



   Any suitable softening agents such as glycerin or a glucol or a sugar, such as glucose or a soap or madder oil, a drying or non-drying oil, in short any substance known in the art. that viscose as an addition to viscose can be added to the cellulose ether xanthate solution before its transformation into artificial structures was in accordance with the present invention.



   Carbonates of all alkali metals can be employed in the present invention, and the carines can be primary or secondary. The latter can also be used in the form of bicarbonates when the temperature of the coagulation bath is such as to cause decomposition of at least part of the bicarbonate employed.



   The proportions of alkaline carbonates contained in the cooling baths can vary in small quantities.

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 for example from 5 to 36% of alkaline carbonate calculated in
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 Na2co3 or from 3 to 1410 calculated as NaHCO.



   The temperature of the coagulation baths can vary between wide limits, for example from 5 ° C. to the boiling point. Thus, the coagulation bath can be used at room temperature or below room temperature, for example at 8-10 ° C or above room temperature, for example at room temperature. from 30 to 45 C or to 60 0 or to 90
Other salts having an alkaline reaction, for example an alkaline dibasic or tribasic phosphate or an alkaline borate, for example borax or an alkali silicate or an alkaline thiosulphate (hyposulphite) or an alkali salt of a weak organic acid, such as an alkali salt of a fatty acid,

   for example an alkali acetate or the like.



   One or more neutral salts such as an alkaline sulfate (for example sodium sulfate) or an alkali chloride can also be incorporated into the solutions of alkaline carbonate.
 EMI13.2
 , - ,, - <lln (ri-r uxelIt1, pl.c; du. oix.o; uxe du oo <1.t.u.m) or. an Mol i. ,, n <.izouuw.



   As far as is compatible with alkali carbonates, any organic substance known in the viscose industry to serve as an addition to coagulation baths may be added, in accordance with the present invention, to the conditioning agents. coagulation containing one or more carbonates, alkalis, for example glycerin or a sugar, such as glucose, madder oil, etc.



   Coagulation can be carried out in a bath or. in two consecutive baths. In other words: the shaped solution or paste of a cellulose ether xanthate can first be introduced into a solution or otherwise treated with a solution of a salt such as sulfate. ammonium or ammonium chloride or sodium silicate, in parti- ku

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   culier of the acid type, or. sodium bisulfite or an acid bath, for example a bath containing acetic acid or sulfuric acid, this bath possibly containing, or not, one or more neutral salts, or acids, or by methanol or by ethanol is an analogous product; after which she can;

   be brought into contact with a solution containing one or more alkaline carbonates. If an acid bath is used as the first bath, the shaped structure can be passed, if desired, before entering the bath containing the alkali carbonate (s), through water or a medium. alkaline bath, for example an extended ammonia solution or 1 :: otherwise treat with water or such an alkaline bath and then contact it with a solution containing one or more alkaline carbonates ,
On leaving the coagulation bath containing one or more alkaline carbonates, the freshly coagulated shaped structure can be washed directly with water and then dried;

   or it can be washed with water, thick; ted by a bath, through which it is passed for example, containing an acid or a neutral or acidic or alkaline salt, or an acid and a neutral salt and (or) an acid salt, or a coagulation bath or of any precipitation known to the viscose industry or to the art of making structures shaped from other alkali soluble cellulose derivatives, then washed and dried.

   Or, on leaving the coagulation bath containing one or more alkaline carbonates, the freshly coagulated shaped structure can be introduced directly, without being washed, into a medium through which it is passed, for example, containing an acid. or a neutral or acidic or alkaline salt, or an acid and a neutral salt and / or an acidic salt or any coagulation or precipitation bath known in the viscose industry or in the art of making shaped structures at

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 from other cellulose derivatives soluble in an alkali, then leavened and dried,
For example, on leaving the coagulation bath containing one or more alkaline carbonates,

   the freshly coagulated shaped structure can be treated for a relatively short time (eg a few seconds up to a few minutes) or for a relatively long time (eg a few minutes up to, several hours) with a cold or lukewarm solution or hot of one or more alkaline carbonates (for example a solution of sodium carbonate with a concentration of 10 to 30%), this solution possibly containing or not one or more other salts having an alkaline or neutral reaction, after which is washed the shaped structure or, optionally after having washed it for a more or less long time, it is treated with an acid (that is to say cold or hot,

   by a bath containing an acid or an acid salt or an acid / and one or more neutral or acidic salts) and washed.



   The process can also be carried out in such a way that, directly on leaving the coagulating bath containing one or more alkali carbonates, the freshly coagulated shaped structure is treated for a shorter time, for example a few seconds to a few minutes) or for a longer time (for example a few minutes to several hours) with a cold or warm or hot solution of one or more alkaline carbonates (for example a solution of sodium carbonate with a concentration of 10 to 30%), this solution which may or may not contain one or more other salts having an alkaline or neutral reaction, after which the shaped structure is washed or, optionally after having washed it for a longer or shorter time, it is treated with a acidic (i.e. cold or hot,

   by a bath containing an ucid or an acid salt or an acid and one or more neutral or acid salts) / and washing. This way of proceeding is suitable for

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 example in cases where, having regard, for example, to the insufficient maturation of the solutions of cell ether xanthates
 EMI16.1
 1000, or. to litlcr c7ori1pCld.I: l.Ori or a tO!, lp6rc.tu.: r'o l.nf'l) proiJr 1.6613 of the coagulating agent, the shaped structures freshly coagulated by an agent containing one or more alkaline carbonates are not washable directly, that is, they show a tendency to swell strongly or even to dissolve in water.



   According to the present invention, artificial structures which are not without interest are obtained when the freshly coagulated shaped structures are introduced directly, on leaving the coagulation bath containing one or more alkali carbonates, in an acid bath (for example.
 EMI16.2
 ple in extended sulfuric acid or any other acid bath known in the viscose industry), then washed.



  This variant of the process makes it possible to obtain structures
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 conformed such as threads or films or coatings or. layers, or impregnations of all kinds, in some cases containing empty spaces.



   Desulfurization and bleaching of artificial structures produced in accordance with the invention can be carried out by any method or process known in the viscose industry for desulfurization and (or) structure bleaching: artificial, such as as wires, films or the like.



   Shaped structures produced in accordance with the invention may, at any stage of their production, be treated with any softening or lubricating agent known in the viscose industry.



   Achievement of the ability of the object to be processed into shaped structures according to the invention depends on, among other things: (1) the proportion of carbon disulphide employed for the preparation of the viscose,

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 (2) the composition and temperature of the coagulant bath,
 EMI17.1
 (; 3) due oond.tionu of '1jJ:.' O.val1 fiul are ObcH): t'v6o (J during the production of conformed structures and (4) of the composition of the solution to be conformed.



   Ad 1) The inventor has found that the lower the proportion of carbon disulphide employed in the preparation of the cellulose ether xanthate, the faster is achieved the ability of the xanthate solution or paste to be transformed into structure. conformed such as threads, films, coverings, layers and impregnations of all kinds.

   For example: when the proportion of carbon disulphide is less or not appreciably greater than 10% (calculated on the weight of the correspon- ding cellulose), the viscose can be transformed into artificial structures in 12 to 48 hours. about (time calculated from the time of the end point of the sulfurization operation or the completion of the preparation of the cellulose ether xanthate) such that the structure. freshly coagulated conformal is introduced directly on leaving the coagulating bath, in water and is washed with water for any desired time.

   When the proportion of carbon disulphide is not more than or less than 10%, in many cases the suitability to be transformed into artificial materials is established even before 12 hours have elapsed.



   When the proportion of carbon disulphide is approximately equal but not appreciably more than 20% in certain isolated cases, the transformation of the. viscose into shaped structures can be made, for example, in 48 to 240 hours as described above. However, in many other cases, the freshly coagulated shaped structures are not yet washable indefinitely. In this case, if you want to wash the

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 EMI18.1
 structures oonfûrmebs tl'u101H'IllklU t ùoue: ulúol1, 'l 7 fnnu for a longer time, - the cellulose ether xanthate solution can be stored until it reaches infinite washability with water immediately after coagulation.

   Or, (a) the freshly coagulated shaped structure can be washed for a short time (eg 30 seconds to 15 minutes) only and then treated with acid and washed again.



  Or, (b) it can be introduced into an acid bath directly after leaving the coagulant bath and then be washed. Or, on leaving the coagulating bath, the freshly coagulated shaped structure can be treated at or below room temperature, or at a higher temperature (eg 4Q-80 C) with an agont containing an or more alkali carbonates and (or) one or more other alkali salts and (or) one or more neutral salts until washability is achieved.

   The duration of the treatment varies according to the composition of the cellulose ether xanthate solution and its age, so that it may require a relatively short time (eg, 5 to 15 minutes) or a short time. longer (for example, 15 minutes to 12 hours).



  Then the shaped structure is washed.



   If desired, the washing operation can be preceded or followed by an acid treatment. In the latter case the shaped structure is washed again after the treatment - the acid.



   In cases where the freshly coagulated conformal structure cannot be washed even for a very short time, only methods (b) or () should be considered.



   It goes without saying that methods (a) or (b) or (e) can also be employed in cases where the freshly coagulated shaped structures are washable indefinitely.



  When the proportion of carbon disulphide is very

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 large, it happens in some cases that for 48 or even 240 hours or longer (time calculated from the time of finishing the cellulose ether xanthate), the cellulose ether xanthate solution does not coagulate fast enough with or in an agent containing one or more alkaline carbonates. In this case none of the methods described above under (a) to (c) can be applied, and the cellulose ether xanthate solution must be kept in reserve or heated, for example at 50 C until that it achieves the desired coagulability.



   Ad 2). The higher the proportion of the alkaline carbonate (s) contained in the coagulating bath and the higher the temperature of the latter, the faster and more complete the coagulation of the shaped structure. As a result, in some cases, the water-availability of freshly coagulated shaped structures is established earlier with concentrated and hot baths (for example, with baths which are saturated with one or more. 'sieurs aloaline carbonates or of one or more carbonates and one or more other salts and having a temperature of, for example, 70-95 C) with or in coagulant baths extended or moderately concentrated and (or ) cold or moderately hot.



     Ad 3). As stated above, if it is not desired to wash the shaped structure with water immediately after leaving the coagulating bath, the maturation of the solutions of cellulose ether xanthates which do not reach the washability in a vaulu time in particular, can be omitted or considerably shortened by the use of one of the working methods described above under (b) or (c).



   However, if the freshly coagulated conformal structure can be washed for a fairly short time (e.g.

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 eg 30 seconds or several minutes, eg 1-15) without strongly swelling or becoming unduly friable, the process can be carried out according to the method set out above under (a).



   As discussed above, this method can also be applied in cases where the freshly coagulated shaped structures are washable indefinitely.



   It should be expressly emphasized that the aptitude point, i.e. coagulability and (or)
 EMI20.1
 la lflvubl1l tú de # structureu fra2c; heni.nC coagul <3 <a #, i> cut be achieved not only by storing at room temperature or below room temperature, but also by weakly or strongly heating the solution of the cellulose ether xanthate.



  The inventor has frequently observed that it suffices to heat a solution weakly or strongly to, for example, 40-50 C and to maintain it, by kneading it, stirring it and stirring it in another way, at this temperature for 15 minutes to 1 hour and a half or 2 hours to impart to the cellulose ether xanthate solution the desired degree of ability to be transformed into a shaped structure according to the method envisaged for the particular case considered.

   
 EMI20.2
 f) fllU'1 all Ion On oh, for una or uutro ralmoti, special importance is attached to accelerating the establishment of the desired maturity of a solution of cellulose ether xanthate, this acceleration can also be effected by adding to the cellulose ether xanthate solution one or more of the substances known in the viscose industry as ripening accelerators.

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   If the time is right for establishing the suitability of a type of cellulose ether xanthate solution, i.e., its coagulability with agents containing one or more alkali carbonates and (or) the washability of freshly coagulated conformal structures, pre-
 EMI21.1
 , ax6ar QOu.ro; t'116m (Hlt to l.'1Ulft, uUcm from the vubba uolu- tion, is unknown, it is essential to determine this point or these points by preliminary experiments carried out at suitable intervals.

   These experiments can, for example, be carried out in such a way that the cellulose ether xanthate solution studied is spread on a glass plate which is then immersed in the coagulating bath intended for the production of the shaped structure. , for example, in a 20-28% sodium carbonate solution or in a solution containing 19-23% sodium carbonate, said solution may or may not contain a little glucose or glycerin and (or) 10-13% sodium sulphate or in a solution containing 19-20% sodium carbonate, 12-13% sodium sulphate and 8-9% glucose or glycerin.

   Depending on the desiderata of the case contemplated, the solution can be employed at the temperature or at a higher temperature, for example at 40.4b, 50, 60, 70 ° C or more. After the film has remained in the coagulating bath for a time corresponding to that during which the intended shaped structure is to remain in the coagulating bath, the film is transferred to water. If, after remaining in water for a longer period of time, the film does not swell, swell excessively, or disintegrate or dissolve, it can be assumed that the establishment of convertibility to the intended conformal structure cellulose ether xanthate solution in question by any desired method within the scope of the invention has occurred.

   Accordingly, the

  <Desc / Clms Page number 22>

 production of the shaped structure can be undertaken even if it is desired to conduct the manufacture of the shaped structure so that it is washed indefinitely on leaving the coagulating bath.

   If, however, it is intended to produce the shaped structure in such a way that, on leaving the coagulating bath, it is only washed for a short time and then treated with acid in the water. means of a solution containing an acid or an acid salt or an acid or an acid salt and one or more
 EMI22.1
 but noutroa or else it is treated in a bath containing one or more alkali and (or) neutral salts, the preliminary experiment must be carried out in such a way that the film coagulated in the allotted time is not washed with water only for as long a time as envisaged for the intermediate washing to be carried out between the coagulating bath and the acid bath.

   If the film resists washing during this time without excessively swelling or disintegrating or dissolving, the cellulose ether xanthate solution is ready to be made into a conformal structure.



   If it is intended to produce the shaped structure in such a way that, on leaving the coagulating bath, it is treated directly with an acidic agent or with a
 EMI22.2
 agont cold, ti? 3dr ait ahrmù pontnncrnt a nu :, 1110 i "'Ir: -. (' 1> 1'- alkali metal bonates and (or) one or more other alkaline or neutral salts, just find by experiences
 EMI22.3
 The point at which the coaglability of the solution of cellulose ether xanthate is established in a bath containing one or more alkaline carbonates.



   It is advisable to carry out the same preliminary tests or similar tests also in cases where it is desired to achieve the suitability of the cellulose ether xanthate solution by heating it slightly.

  <Desc / Clms Page number 23>

 or strongly and (or) by incorporating therein one or more of the accelerators known in the viscose industry.



  It goes without saying that in such a case the preliminary experiments should be carried out in much shorter intervals, for example 5 in 5 or 10 in 10 minutes when heating the tank.
 EMI23.1
 iLu halter of a cxbotmtd elutx7lu tiii 1'0 ub am.v:!,!;) y 101 'another alkali salt of a weak inorganic or organic acid, that is to say another salt having a reaction alkaline, such as a bibasic or tribasic alkali phosphate or an alkali borate, for example borax or an alkali silicate of the type, alkaline or an alkali salt of a weak organic acid, such as a salt alkaline of a fatty acid,
 EMI23.2
 by uxmn4lc: an alkaline acetata or equivalent LUI ;.



   With regard to the practice of the present invention.), It is impossible to indicate all the conditions of success in each particular case and it goes without saying that preliminary experiments cannot be. avoided to prove what are the conditions necessary for success, when employing a particular species of cellulose, a particular method for cellulose ether xanthate preparations, a particular method of shaping the xanthate solution, etc. etc.



   The specific examples which follow are given to explain the nature of the present invention.



   It is obvious that the invention not being limited to
 EMI23.3
 these examples, to the exact proportions of the ingredients, to the times, to the temperatures and to the series of operations exposed; parts are given by weight.



   A solution containing 7 to 9% of caustic soda and 6 to 8% of a cellulose ether xanthate prepared according to any one of the examples of the English patent application No. 11242/35 of the same inventor as a 'they remember

  <Desc / Clms Page number 24>

 carried to cellulose ether xanthate prepared by means of a proportion of carbon disulphide not exceeding 10% calculated on the weight of the initial cellulose ether, is left to mature at 15 to 18 C for 6 at 36 hours and, after having been during this time filtered and freed from gas bubbles, it is transformed into conformed structures under the following working conditions which, for reasons of brevity,

   were chosen at random from the working conditions which were used in many series of tests and which, therefore, can undergo almost endless variations in the mode of conformation or application. of the solution of the cellulose ether xanthate, the composition and temperature of the coagulation bath, the subsequent treatment of artificial structures coming out of the coagulation baths, etc., etc.



   Artificial threads
1. At a rate of about 4.8 to 5 ccm per minute, the cellulose ether xanthate solution is extruded through a die nozzle having 54 perforatians 0.08 to 1 mm in diameter in it. '' one of the following coagulation baths: a) sodium carbonate solution with a concentration of 36% at 90 C, or b) sodium carbonate solution with a concentration of 32% at 60 C or 70 C or 80 C or 90 C, or c) sodium carbonate solution with a concentration of 38%, at 60 C of 70 C or 80 C or 90 C, or d) sodium carbonate solution with a concentration of 28 % at a temperature of 45-50 C, or e) sodium carbonate solution with a concentration of 21% at 45-50 C or 60 C or 70-800C, or 90 C, or f)

   sodium carbonate solution of one concentration

  <Desc / Clms Page number 25>

 15% at 45-50 C or at 60 C or at 70 C-80 C or at 90 C, or
 EMI25.1
 ) duluLlutt do UtirbulluLo du Clud lUll d'utm tà <> iiu <-iii, 1: <tion of 10% at 45-50 C or at 60 C or at 70 C-80 C or at 90 C, or h) a bath containing 23 to 24% sodium carbonate and 15 to 16% sodium sulfate at 50 C, or i) a bath containing 28% sodium carbonate and 10% sodium sulfate at 50-60 C or 70-90 C, or
 EMI25.2
 le) a bath c mt 1 e ttttt L; 46 / do a c;

   ul I utm t, vod1 uln v 10% glucose or glycerol at 50-60 C or 70-90 C, or
1) a bath containing 21% sodium carbonate and 1E)% sodium sulfate at 50-60 C or 70-90 C, or m) a bath containing 21% sodium carbonate and 13.5 parts sodium sulfate sodium at 50-60 C or at 70-90 C, or n) a benzine containing 21% sodium oarbonate, 13.5 parts of sodium sulfate and 10% glucose or glycerol at 50-60 C or at 70 -90 C, or o) a bath containing 19% sodium carbonate, 12 to 13% sodium sulfate and 8% glucose at 50- or 60 or 70 C, or p) a bath containing 28% sodium carbonate sodium and
 EMI25.3
 8% of the borax (Mai4U7.1U 112 0) at 50-ôo 1 or at 70-9000, or r)

   a bath containing 80% sodium carbonate and 25% borax (Na 2 B 4 0 7. 10 H20) at 50-60 C or 70-90 C, or s) a bath containing 28% sodium carbonate and 8% sodium sulfite crystallized at 50-60 0 or 70-90 C, or t) a bath containing 20% sodium carbonate and 17% sodium sulfite crystallized at 50-60 C or 70-90 C , or u) a bath containing 26% sodium carbonate and 12% sodium bicarbonate at 45-50 C, or v) a bath containing 29% sodium carbonate and 8% sodium bicarbonate at 45-50 C , or Ó

  <Desc / Clms Page number 26>

 
 EMI26.1
 w) a bath containing bzz of sodl carbonate:

  i 12% sodium bicarbonate at 45-50 C, or x) a bath containing 25% sodium carbonate and 3 to 5% caustic soda at 45-50 C, or 60-70 C, or y) a bath containing 19 to 21% sodium carbonate, 12 to 13% sodium sulphate and 3 5% caustic soda at 45-50 C or 60-70 C, or z) sodium bicarbonate solution of a concentration of 12% at 45-50 C, or zl) a sodium bicarbonate solution of a concentration of 12% at 60 C, or z2) a bath containing 12% of sodium bicarbonate and 10% glucose at 45 C, or z3) a bath containing 12% sodium bicarbonate,
 EMI26.2
 13 of sodium sulfate and 10 115 dr;

   glucasu, (1 40-4G C or z4) a bath containing 20% sodium carbonate at 20-25 C, or z5) a bath containing 27% sodium carbonate at 25-30 C, or z6) a bath containing 34% sodium carbonate at
 EMI26.3
 : 0-: 3f3 C, or z7) a bath containing 31% sodium carbonate at 40 C.



   The immersion length of the wire in the coagulation bath is about 40 to 80 cm. 50 to 160 cm of the yarn is then allowed to pass through air and wind it on a spool which produces a spinning speed of about 30 meters per minute and which may or may not turn in water.



   The threads are then washed and finished in any known manner. They can be twisted or milled in the wet state, for example before, during or after washing or in the dry state.



   (2) The process is carried out as in (1), but with

  <Desc / Clms Page number 27>

 the difference being that the spinning is carried out in a centrifugal spinning machine, all details of the procedure and handling will be apparent from (1) to those skilled in the art.



   (3) Procedure as in (1) or (2), but with the difference that the spinning is carried out with additional drawing, which can be carried out, for example, by introducing into the path followed by the yarn from the die to 'to the spool or to the centrifugal box, one or more brakes such as buckets, differential rollers, rods arranged to form a comb or two or more glass or metal rods between they an angle and above which the wires are led and are thus subjected to additional stretching or tension. If desired, glass or metal tubes can be slid over one or more of the glass or metal rods.

   In this case, the wires do not come into contact with the rods themselves, but with the tubes which must be quite easily movable around the rods so that they turn quickly when the wires slide over them.



   Artificial yarns can be treated either during their manufacture or in the finished state with a hardening agent, such as formaldehyde or the like.



   It goes without saying that films or yarns having a low gloss or entirely dull can also be produced from viscose by the present process with the aid of any method known in the industry. sorts artificial silk.



   (4) The process is carried out as in (1) or (2) or (3), except that instead of being 30 m, the spinning speed is 40 m per minute.



   (5) The process is carried out as in (1) or (2) or

  <Desc / Clms Page number 28>

 (3), except that instead of 30 m, the spinning speed is 60 m per minute, the quantity of the solution of the cellulose ether xanthatte delivered per minute being about double or triples the quantity delivered in (1).



   (6) The process is carried out as in any one of the operating formulas (1) to (5), but with the difference that the solution of the cellulose ether xanthate does not enter directly into the bath. coagulation containing sodium carbonate, but is extruded into one of the following baths:

   a) a xxxxx solution of sodium sulphate with a concentration of 25% having a temperature of 45 to 70 C, b) a solution of sodium chloride with a concentration of 25% having a temperature of 45 to 70 C, or c) an ammonium sulphate solution of 25 to 30% carcinization having a temperature of 16 to 25 C, or d) an ammonium sulphate solution of a concentration of 25 at 30% having a temperature of 30 to 50 C, or e) an ammonium chloride solution of a concentration of 25 to 30% having a temperature of 16 to 25 C or f) a chloride solution of ammonium of a concentration
 EMI28.1
 tration of 25 to 30 days having a temperature of;

  0 to 500C, or g) Laui, bain da aoajulaLion 001111U dmii l '1 IIdut! Trl of the solution of the cellulose ether xanthate, for example a bath containing 2 to 10% H2S04 or 2 to 10%
 EMI28.2
 of Hs0 and 10-24% Na2SO4 and (or) 12-16% gSO4 at 30-55C.



   On leaving this bath, the completely or incompletely coagulated wire is introduced into one of the baths indicated

  <Desc / Clms Page number 29>

 at µ 1 under a) to z7).



   (7) The process is carried out as in any of the operative formulas (1) to (6), but with the difference that the yarn is washed on the spool for about 15 minutes, is then twisted and processed. into a skein or skein and is then treated for a short time (for example 1 to 20 minutes) with 2 to 10% sulfuric acid, 1 to 1 hydrochloric acid. up to 5% or by a bath containing 2 to 10% sulfuric acid and 10 to 16% sodium sulphate and (or) 12 to 16% magnesium sulphate, at temperature at room temperature or at 40 to 50 C or by sulfuric acid with a concentration of 30 to 70%, at room temperature, at 5 C, at 0 C or at minus 5 C or by the any of the baths indicated above in (1)

   under (a) to (z7) and is then washed and finished in the ordinary manner. If the spinning is carried out in an oentrifuge spinning machine, the first wash is carried out with the cake and the separate twisting is omitted.



   (8) Procedure as in (7), but with the difference that before the acid treatment or the subsequent treatment with one of the baths mentioned above in (1) under (a) to (z7), the yarn is washed on the spool or in the cake for about 2 to 3 minutes instead of 15 minutes or not washed before the acid treatment, (9) Procedure as in (7), but with the different rence that before being treated with acid or subsequently treated with one of the baths indicated above in (1) under (a) to (Z7), the yarn is washed on the spool or in the gâ - water for half an hour to an hour or more (for example, for 2 to 6 hours), instead of 15 minutes).



   (10) Procedure as in (7), (8) or (9), except that the first wash and the acid treatment or treatment

  <Desc / Clms Page number 30>

 Subsequently by one of the baths stated in (1) under (a) to (z7) above is carried out on the spool or cake, after which the thread is lifted and finished.



   In the case of spool spinning, the twisting or milling of the yarn can be carried out either after the current treatment or the subsequent treatment by one of the baths indicated above in, (1) under (a) to (27), either after the washing following the acid treatment or the subsequent treatment with a bath containing one or more alkaline carbonates or after drying.



   (11) The process is carried out according to any of the working methods (1) to (6), but with the difference that the yarn is milled directly from the spool and is then made into a skein or skein (or , if the spinning takes place in a centrifugal machine, the cake is directly processed into a skein), after which the skein is washed for about 15 minutes
 EMI30.1
 ot is then treated for a short period of taap:., (for example for 1 to 20 minutes) with one of the acidic agents or mediums mentioned under (7) or with any of the baths indicated above (in ( 1) under (a) to (z7) and is
 EMI30.2
 then washed and finished in the oe, dinaire way.



   (12) Procedure as in '(11), but with the difference that, before being acid-treated or treated
 EMI30.3
 ultél'luu1 "ollml1t pure 1" Ur \ cloli1 hnj, z im'li '] 1és 1) lw:' hAut in (1) under (a) to (27), the skein is washed for approx. 2 to 5 minutes instead of 15 minutes.



   (13) Procedure as in (11), except that before being treated with acid or subsequently treated by one of the baths stated above in (1) under (a) to (z7), the skein is washed for half an hour to an hour
 EMI30.4
 or 11111; 1 1Ilnp; tomrr. (pnr eX'1m; 11n for z6 6 hours).



   (14) Procedure as in (11), but with the difference that when it is put in the form of a scale

  <Desc / Clms Page number 31>

 vette, that is to say without any intermediate washing, the yarn is treated with an acid or subjected to the subsequent treatment by one of the baths indicated above in (1) under (a) to (z7), as this is described in (11) and is then washed and finished.



   (15) Procedure according to any one of the working formulas (1) to (3), with the difference (except for the washing to which the yarn is subjected if the spool turns in water or if it turns in the water. (water, or if it is washed in the funnel or pot of the centrifugal spinning machine) the yarn is subjected, without being washed, to the acid treatment or to the subsequent treatment directly on the spool or in the cake by means of the '' any of the acidic agents indicated in (7) or any of the baths indicated above in (1) under (a) to (z7) respectively, after which (in the case of spool spinning, if it is desires, after washing and (or) milling), optionally after being / twirled into a skein,

   it is washed (if it has not been washed or has been incompletely washed on the spool or in the cake) and finished.



   (16) The process is carried out in accordance with any of the operating formulas (1) to (5), except that the wire collected on the spool or in the centrifuge box is treated with an agent containing an alkali carbonate, for example by any of the coagulating agents indicated in (1) under (a) to (z7), (for example, by a 25% sodium carbonate solution.

   at room temperature or at 45-50 C or with a 10% sodium carbonate solution, at room temperature or at 45-50- C or, with a solution containing 20% sodium carbonate and 12 to 13% sodium sulfate, at ardinal temperature or at 45-50 C) or with a solution of a neutral salt, for example with a 20-25% solution of sodium sulfate.

  <Desc / Clms Page number 32>

 dium or sodium chloride, at room temperature or at 40-50 C or higher.

   This treatment with the agent containing an alkali carbonate or with a solution of a salt can be carried out while the wire is being deposited on the spool or in the centrifugal box, for example by rotating the spool in a liquid containing a carbonate. sodium and (or) another salt, or by introducing this liquid into the centrifuge box during spinning, and (or)
 EMI32.1
 aprua spinning, processing the yarn on to bwbIn <or '-U.1H ::> the cake with one of the liquids indicated above, at / at room temperature or at 45-50 C, for example for 15 to 30 minutes or more, for example for one to 6 hours, then (in the case of spool spinning after twisting the yarn) putting the yarn into a skein, treating the skein with any of the acidic agents indicated
 EMI32.2
 on (r) al on 11w:

  1IlL uL tIttl.uttul, 1. ' Imvt, E, c:. Il7 / Procedure as in (16), except that after having been treated with the solution containing an alkali carbonate and (or) another salt and put in a skein, the yarn is washed and finished without having been subjected to the acid treatment. of.



   (lE) Procedure as in. (17), except that after being treated with the solution containing an alkali carbonate and (or) another salt, the yarn is completely washed without having been skeined and subjected to the acid treatment , after which it is skeined and finished.



   (19) Procedure as in (16), except that after having been treated with the solution containing an alkali carbonate and (or) another salt, the yarn is not put into a skein, but subjected xx xxx directly to the treatment acid on the spool or in the form of a cake and washed on the spool or in the form of a cake and finished or else (ground in the case of a spool) skein washed and finished.

  <Desc / Clms Page number 33>

 



   (20) Procedure as in (16), except that after having been skeined, the yarn is washed for two to three minutes, then subjected to the acid treatment.



   (21) Procedure as in (20) except that before being subjected to the acid treatment, the yarn is washed for about 15 minutes instead of 2 to 3 minutes.



   Examples for the manufacture of fibers in rovings automatically result from the above examples.



   - If desired, the extensibility of artificial yarns can be increased by treating them with shrinkage agents, for example by any of the processes described in Belgian Patents Nos. 342,831, 355,400, 361,387, 361,532 and 361,564 by the same inventor.



   (22) The process is carried out according to any one of the operating formulas (1) to (21), except that before spinning it into artificial threads, the solution of the cellulose ether xanthate at 15- is allowed to mature. 17 C for 36,48,60 Qu 72 hours.



   Desulphurization and (or) bleaching of ar-. tificials can be carried out by any or all of the methods known in the cellulose ether xanthate solution industry, including the methods described in Belgian Patents No. 371,966,
697,588 and 397,589 by the same inventor.



   Movies.



   1. Spread the cellulose ether xanthate solution uniformly in a known manner on the surface of the drum of a film making machine, based on the drum principle, with part of the drum immersed in any one of the baths. indicated in the chapter "artificial threads" of this example in 1) under (a) to (z7) or, when the two-bath system is adopted, the drum is / immersed in any one of the baths indicated in this phapter in
6) under (a) to (g), after which the freshly coagulated film

  <Desc / Clms Page number 34>

 is introduced into one of the baths indicated under the title "artificial threads" of this example under (a) to (z7).

   The diameter of the drum must be such that: when the drum rotates at the desired speed, the film is sufficiently solidified at the moment when it has to move away from the surface of the drum to undergo the subsequent treatment (s) envisaged .



   The solidified film is washed in a known manner with hot, lukewarm or cold water, then dried.



   Film casting and (or) film drying can be carried out without additional stretching or with more or less severe additional stretching.



   The film can be treated, before or after drying,
 EMI34.1
 .by ucia aqueous solution of glyerol (of a çO! 1Ú'lltl'é.l.tlún of 4 to 10% for example) or of glycol, to increase its flexibility.



   It goes without saying that the film can also be treated with any of the known agents or any of the known compositions resistant to humidity and water.



   The film may be treated during manufacture or when finished with a curing agent, such as formaldehyde or the like.



   Proceed as in (1), except that instead of being re-parted on a drum, the solution of the cellulose ether xanthate is applied by means of a suitable device on an endless tape having a smooth surface and immersed in one of the coagulation baths indicated in the chapter "artificial threads" of this example in (1) under (a) to (z7); or, when adopting the two-bath system, the endless ribbon is immersed in any one of the baths indicated in the chapter "artificial threads !! of this example in (6) under (a) to (g) , after which the freshly coagulated film is introduced into one of the baths indicated in this chapter in (1) under (a) to (z7).

  <Desc / Clms Page number 35>

 



   3. Proceed as under (1) or (2), except that instead of being spread over the surface of an endless drum or ribbon immersed at least partially in the coagulation bath, the xanthatc solution cellulose ether is extruded by extrusion through a suitable funnel or suitable slit into any of the baths given in the "artificial yarns" chapter of this example in (1) under (a) to (z7) or, when the two-bath system is adopted, the solution of the cellulose ether xanthate is extruded by extrusion in any of the baths indicated in the chapter "artificial threads" of this example in ( 6) under (a) to (g), after which the freshly coagulated film is introduced into one of the baths indicated in this chapter in (1) under (a) to (z7).



   4. Proceed as in any one of Examples (1) to (3), except that on leaving the coagulation bath or when operating by the two-bath process, on leaving the second bath, the film is subjected to to a further treatment at room temperature or at a higher temperature in a subsequent bath containing one or more alkali carbonates in which it has been coagulated or of any other bath containing at least one alkaline carbonate, for example one of the other baths indicated in (1) under (a) to (z7), after which the film thus treated is washed and finished or washed, acid treated, washed again and finished.



   5. Proceed as in (.1) or (2) or (3), except that when leaving the coagulation bath or, when using the two-bath process, when leaving the second bath, the film is washed. for 2 to 15 minutes, then treated for a short time (for example, for 20 minutes) with a bath containing 2 to 10% H2SO4 and 10 to 16% Na2SO4 and (or) 12 to 16% MgSO4, at room temperature

  <Desc / Clms Page number 36>

 te or at 40-50 C or par. of sulfuric acid in a concentration of 30 to 70% at room temperature or at 50 C or at 0 C or at minus 5 C, then washed and finished as habit.



   6. proceed as in (5), except that no 1 - # intermediary takes place between coagulation and the subsequent temt by an acidic agent.



   7. Proceed as in (4), except that instead of being treated with a bath containing one or more alkaline carpnates, the film emerging from the coagulation bath is treated, with or without intermediate washing, with a solution of a neutral salt, for example by a sol; ion at 20-25% sodium sulfate or sodium chloride at room temperature or at 40-50 0 or higher.



   It goes without saying that the threads or films having reduced gloss or being entirely matt can also be produced by the present process using any method known in the chardonnette industry (re nne).



   It is possible to obtain threads or films in which empty spaces are distributed, for example by incorporating into the solution of cellulose ether xanthate,: ¯ sodium carbonate, or another substance xxxx capat-, de- developing a gas during the spinning, and by incorporating the freshly coagulated threads or films coming out of the coagulation inlet directly into an acid bath, by e iple one of the acid baths indicated in the chapter "Artifical fs" of this example (under (7)) or in chapter II films "of this example under (5) or by dispersing air or another gas in the solution of xanthate '' cellulose ether and by coagulating the conforma solution of cellulose ether by any of the processes given in Chapter II, artificial yarns "under (1) to (22)

   

  <Desc / Clms Page number 37>

 
Finishing (priming) and printing of textiles.



   Finishing
1. Take a fabric, such as a cotton cloth, and fit it by means of a suitable machine, for example a post-filling machine or a tampon machine or a spreading machine, with one or more covers made of the solution of cellulose ether xanthate, to which can be added a filler such as talc or kaolin or zinc white or a colorant or pigment such as lacquer or carbon black or ocher or mioa and (or) a softening agent, for example an oxytrimethylene sulphide (see English bhevet n 25.246 / 1911 of the same inventor) or a soap or madder oil or a siccative oil or no, etc. etc.

   When the material is covered or impregnated or loaded, it is introduced directly or after drying and (or) intermediate steaming, in one of the coagulation baths or in one of the combinations of coagulation baths which are indicated in the chapter "artificial threads" of this example in (1) under (a) to (z7) and in (6) under (a) to (g), after which it is washed and dried.



   The textile material can be treated, before or after drying, with a softening agent, such as soap or madder oil, or glycol, etc .....



   2) Proceed as in 1), except that the solution of the cellulose ether xanthate is mixed with a solution of starch or starch, or dextrin, or any other colloid known in the finishing industry.



   3) Proceed as in 1) or 2), except that measures are taken to incorporate gas bubbles or screws into the regenerated cellulose deposited inside or Ci the surface of the fibers of the fabric or similar product. . One can obtain this result in any known way by dispersing n

  <Desc / Clms Page number 38>

 a gas such as air or hydrogen, or nitrogen, etc., or by distributing it in some other way in the solution of xamalt of cellulose ether, or by incorporating into the solution of the cellulose ether xanthate of sodiam carbonate or another substance capable of liberating a gas when brought into contact with an acidic medium., and (or) by directly introducing the impregnated fabric emerging from the bath of coagulation in an acid bath,

   for example in sulfuric acid with a concentration of 2 to 15% at a temperature of 4 to 8 C or at room temperature or a temperature of 35 to 45 C, or in a bath containing 10 to 16% H2SO4 and 20 to 25% Na2SO4, or in a bath containing 10 to 15% Na2SO4, 14 to 18% MgSO4 and 6 to 16% H2SO4 at room temperature or at a temperature of 35 to 45 C .



   4) Proceed as under 1) to 3), except that before applying the solution of the cellulose ether xanthate to the fabric or similar product, it is transformed into a kind of soapy foam by the method described in Belgian Patent No. 389,620 by the same inventor.



   Examples of sizing of yarns automatically follow from what is said under 1) to 4).



   5) Mix the solution of the cellulose ether xanthate with a dye or pigment, such as lacquer, ocher, carbon black or zinc white, or finely divided Mich or a bronze powder not containing aluminum, and apply it to a cotton cloth by printing on a roller or stencil printing machine.

   After printing and, if desired, after drying it, introduce the cotton fabric into one of the coagulation baths or one of the combinations of tains described in the chapter " artificial threads "of this example in 1) under (a) to (z7) and in (6) under (a) to (g)

  <Desc / Clms Page number 39>

 
What has been said in chapters II artificial yarns "and" films "of this example concerning the application, to the manufacture of yarns and films, of all the variants concerning the coagulation baths, their temperature and all details of further processing, also applies to finishing or sizing or printing of textiles.

   In other words: taking into account, as appropriate, the difference between the handling and the technique of making artificial yarns or films, on the one hand, and the sizing or finishing or filling or the printing or sizing of textiles, on the other hand, it will be easy and, as regards every detail, it will be quite appropriate for any person skilled in the art, to apply all the variants of the process in question described in the Chapter "artificial yarns II of this example under 1) to 22) for finishing, covering, sizing, filling or sizing or printing textiles.



   Cements and adhesives
The cellulose ether xanthate solution is used for bonding two or more sheets of paper or cardboard or cotton fabrics or veneer sheets, the bonded materials then being, after intermediate drying, if desired, introduced into one of the coagulation baths or into one of the combinations of coagulation baths which have been described in the chapter "artificial threads" of this example in 1) or (a) to ( z7) and in (6) under (a) to (g).
 EMI39.1
 



  E.2 .. (1} l, O.H.- ¯I '!.) j n l2 .: ":.



   Thick plates can be made by shaping the concentrated solutions or pastes of the cellulose ether xanthate to the desired shape and, optionally; after intermediate drying, by treating them with one of the precipitation baths or one of the combinations of baths which have been described in the chapter "artificial threads" of this example.

  <Desc / Clms Page number 40>

 ple in (1) under (a) to (z7) and in (6) under (a) to (g).



   All the variations concerning the coagulation baths, their temperature, as well as the age of the solution of the cellulose ether xanthate and all the details of the further processing indicated in chapter II artificial wires II of this example under (1) to (22) apply to the
 EMI40.1
 Inlaci nu prutifLUo do In> rnnnnto The invention for the use of: forming the solution of the cellulose ether xanthate to serve as an adhesive, or to produce thick plates or the like according to the invention. It goes without saying that handling and techniques must adapt to the mechanical and other processes and procedures in use in these industries.



   In the production of shaped structures or other articles of utility by the present procedure, which production is indicated in this example and the following ones, the bath or coagulation baths should be kept in constant circulation as usual.



   With respect to any one and all points of this example, the bath (s) should be kept in permanent circulation in the usual way and the carbonate;
 EMI40.2
 do .1ci (lititil tyitc: t3 citw: 1.m nou <1Q 01 \ 11 :; [.1'lUO l'n'IV "IIt. (^ It recovered as sodium carbonate or caustic soda (causticization of sodium carbonate) as described on page 7.



   As for the caustic soda entering the bath and coming from the shaped structures, it can be completely or partially transformed into sodium carbonate by introducing Co2 into the bath, either continuously or temporarily.



   Example II.



   The process is carried out as in Example I, except that the cellulose ether xanthate solution is a

  <Desc / Clms Page number 41>

 solution of a cellulose ether xanthate which has been prepared in accordance with British Patent Application No. 11242/35 by the same inventor, using xx 14 to 16% carbon disulphide, calculated on the weight of the ether cellulose initial. In some cases the cellulose ether xanthate solution of the example set does not achieve the suitability of providing conformable structures according to the present process which, on leaving the coagulation bath, can be washed indefinitely beforehand; 5-16 days calculated from the time of completion of the cellulose ether xanthate substitution preparation.

   Accordingly, if it is desired to transform the cellulose ether xanthate solution into shaped structures by washing the freshly coagulated shaped structures indefinitely, the cellulose ether xanthate solution must be matured.
 EMI41.1
 ù 1> - = V G ut, lu 11, aniòi, m;> llwn <i <: In uoLutiOu du x'tubhnt ') of cellulose ether in conformal structures should be delayed until such time as the preliminary experiments cited above show indefinite washability, or be carried out by a method which does not require undefined, for example according to one of the methods indicated in the chapters "artificial threads" of this example under (7) to (21).

   However, these or similar methods can also give good results where the cellulose ether xanthate solution has already reached the degree of suitability required to provide shaped structures leaving the coagulation bath or a combination. indefinitely washable coagulation baths.
 EMI41.2
 E: X; (tn;

  r.ln III.
The process is carried out as in Example I, except that the cellulose ether xanthate solution is a

  <Desc / Clms Page number 42>

 solution of a cellulose ether xanthate which has been prepared in accordance with any of the methods described in UK Patent Applications Nos. 9762/35, 9763/35, 9764/35, 9765/35, 9766 / 35, 9767/35 9768/35, 9769/35, 970/35, 9771/35, 9772/35, 9773/35, 9774/35, 9775/35., 9776/35, 9777/35, 9778/35 and 12184/35 by the same inventor, in that they describe the production of cellulose xenthates using proportions of carbon disulphide not exceeding 10% of carbon disulfide, calculated on the weight of the starting cellulose ether.



   Example IV
The process is carried out as in Example 1, except that the cellulose ether xanthate solution is a solution of a cellulose ether xanthate which has been prepared according to any of the processes described in the applications. British Patent Nos. 9762/35, 9763/35, 9764 / 35.9765 / 35, 9766/35, 9767/35 9768 / 35.9769 / 35, 9770/35 9771/35, 9772/35, 9773/35, 9774/35, 9775 / 35,9776 / 35, 9777 /
 EMI42.1
 35, 9778/35 and 12184/35 du m (Imp 3 nvr3ntcur on tant (lU 'l) 11 zou describe the production of cellulose xanthates by means of carbon disulphide proportions exceeding 10% but less than 20% of 'carbon, calculated on the weight of the starting cellulose ether.



   Example V.



   The process is carried out as in any of Examples I to IV, except that instead of cellulose ether xanthate, a product is employed resulting from contacting cellulose xanthate with one or more cellulose ethers. soluble in alkali, a product which
 EMI42.2
 does not contain p, 8. hands of 20 lez ', and preferably less than 15% or even less than 10% of CS2 (see, for example, Belgian Patents Nos. 407.262, 407.734, 406.950 by the same inventor and in his British patent application not

  <Desc / Clms Page number 43>

 11,242 / 35 (for example, the products of Example I or Examples VI to XIX) and in UK Patent Application No. 14,488 / 1935.



   In the coagulation baths employed in the preceding examples, the sodium carbonate can be totally or partially replaced by one or more other salts with an alkaline reaction, for example by sodium etraborate (borax) (for example, a borax solution with a concentration of 21%, at 50 C or at 60 C or at 70 C up to 90 C or at a concentration of 36%, at 70-90 C or at a concentration of 53% at 90 c or a solution of crystallized sodium sulphite with a concentration of 25% at 50 C or at 60-70 or at 80-90 neck with a concentration of 42%, at 70-80 C or a phosphate solution bibasic sodium with a concentration of 45%,

   at 50 or 70-80 C or 47% concentration at 60-80 C or tribasic sodium phosphate solution 20-40% concentration, 50 C or 60-70 or 80 VS
Example VI
A solution containing 7 to 9% of caustic soda and 6 to 8% of a xanthate of cellulose ether is prepared by means of 25 to 30% of carbon disulphide (calculated on the weight of the cellulose ether ) in accordance with any one of the processes described in Belgian patents 368,617, 407,052, 378,205, 382,218 and 389.

   619 by the same inventor and in his UK patent no.367.920 or based on his UK patent applications no.9762/35, 9763/35, 9764/35 9765/35, 9766/35, 9767/35, 9768/35, 9769/35, 9770/35, 9771/35, 9772/35, 9773/35, 974/35, 9775/35, 9776/36, 9777/35, 9778/35.



   In some cases the cellulose ether xanthate solution of this example does not achieve the ability to provide by the present process shaped structures which, upon leaving the coagulation bath, are unduly washable.

  <Desc / Clms Page number 44>

 finely before 10 to 21 days calculated from the time of completion of the preparation of the xanthate solution of cellulose ether.

   Accordingly, if it is desired to transform the cellulose ether xanthate solution into conformal structures by washing the freshly coagulated conformal structures indefinitely, it must be left to cure at 15-30 C or heat at 60 C and process into. conformed structures must be delayed until the preliminary tests cited above show indefinite washability, or must be carried out according to a method which does not require indefinite washability, for example, according to one of the methods given in the chapter "artificial threads" which will follow, under (7) to (21).

   However, these or similar methods can also be used successfully in cases where the cellulose ether xanthate solution has already reached shark fitness levels to provide conformal structures which exit the cellulose ether. coagulation bath or a combination of coagulation baths, in an indefinitely washable state.



   The cellulose ether xanthate solution is transformed into man-made structures under the following working conditions, which for brevity have been selected at random from working conditions which have been applied in many series, experiments and or! are therefore susceptible to almost innumerable variations in the method of shaping or applying the cellulose ether xanthate solution, in the composition and temperature of the coagulation bath, in the subsequent treatment of the structures artificial coming out of coagulation baths etc. etc.



     Artificial yarns "(1) The solution of cellulose ether xanthate is

  <Desc / Clms Page number 45>

 extruded at a rate of about 4.8 to 5 Qom per minute through a die having 54 perforations of 0.08 to 1 mm in one of the following coagulation baths:

   (a) sodium carbonate solution with a concentration of 36% at 90 C, or (b) sodium carbonate solution with a concentration of 32% at 60 C or 70 C or 80 c or 90 C, or (c) sodium carbonate solution with a concentration of 28% at 60 C or 70 C or 80 c or 90 C, or (d) sodium carbonate solution with a concentration of 28 % at 45-50 C, or (e) sodium carbonate solution with a concentration of 21% at 45-50 C or at 60 C or 70-80 0, or at 90 C, or (f) solution of sodium carbonate with a concentration of 15% at 45-50 C, or at 60 C or at 70-80 C or at 90 C, or (g) solution of sodium carbonate with a concentration of 10% at 45-50 C or at 60 C or at 70-80 C or at 90 C, or (h)

   a bath containing 23 to 24% sodium carbonate or 15 to 16% sodium au] fate at 50 C, or (i) a bath containing 28% sodium carbonate and 10% sodium sulphate at 50-60 C had at 70-90 C, or (k) a bath containing 26% sodium carbonate and 10% glucose or glycerol at 50-60 C or 70-90 C, or (1) a bath containing 21% sodium carbonate and 18% sodium sulfate at 50-60 C or 70-90, or (m) a bath containing 21% sodium carbonate and 13.5 parts sodium sulfate at 50-60 C or at 70-90 C, or (n) a bath containing 21% sodium carbonate, 13,

  5 parts of sodium sulfate and 10% of glucose or glycerol at 50-60 C or at 70-90 or

  <Desc / Clms Page number 46>

 (o) a bath containing 19% sodium carbonate, 12 to 13% sodium sulfate and 8% glucose at 50 or 60 or 70 C or (p) a bath containing 28% sodium carbonate and 8% borax (Na2B4O7, 10H2O) at 50-60 0 or at 70-90 0, or (r) a bath containing 20% sodium carbonate and 23% borax (Na2B4O7.

   10H2O) at 50-60 C or at 70-90 0, or (s) a bath containing 28% sodium carbonate and 8% sodium sulfate crystallized at 50-60 G or 70-90 C, or (t ) a bath containing 20% sodium carbonate and 17% crystalline sodium sulfite, at 50-60 or 70-90 C, or (u) a bath containing 26% sodium carbonate and 12% sodium bicarbonate at 45-50 G, or ((v) a bath containing 29% sodium carbonate and 8% sodium bicarbonate at 45-50 C, or (w) a bath containing 15% sodium carbonate and 12% sodium sodium bicarbonate at 45-50 C, or (x) a bath containing 25% sodium carbonate and 3 to 5% caustic soda at 45-50 C,

     or at 60-70 C or (y) a bath containing 19 to 21% sodium carbonate, 12 to 13% sodium sulphate and 3 to 5% caustic soda at 45-50 or 60-70 0 .



   (z) a sodium bicarbonate solution with a concentration of 12% at 45-50 C, or (zl) a sodium bicarbonate solution with a concentration of 12% at 60 C, or (z2) a bath containing 12% sodium bicarbonate and 10% glucose at 45 C, or (z3) a bath containing 12% sodium bicarbonate,

  <Desc / Clms Page number 47>

 13% sodium sulfate and 10% glucose, at 40-45 C, or (z4) a bath containing 20% sodium carbonate at 20-25 C, or (z5) a bath containing 27% sodium carbonate at 25-30 C, or (z6) a bath containing 34% sodium carbonate at 30-38 C or
 EMI47.1
 (7.7) a bath \ 10ntAnnnt 3l µ1 l onrhonntn c9n 1Jo (l''1H 1
40 C.



   The immersion length of the wire in the coagulation bath is about 40 to 80 cm. We then let pass
50 to 160 om of yarn in air and then wound onto a spool which produces a spinning speed @ of approx.
30 meters per minute and which may or may not turn in the water.



   The yarns are then washed and finished in any known manner. They can be milled in a wet state, for example before, during or after washing or in a dry state.



   (2) The process is carried out as in (1), but with the difference that the spinning is carried out in a centrifugal spinning machine, all the details of the procedure and of the handling resulting from (1) for the specialist.



   (3) Procedure as in (1 or (2), but with the difference that the spinning is carried out with additional drawing, which can be carried out, for example, by inserting into the path followed by the yarn from the die up to the spool or up to the centrifugal box, one or more brakes, such as buckets, rollers, differentials, rods arranged so as to form a comb or two or a greater number of glass rods or metal forming an angle between them and above the

  <Desc / Clms Page number 48>

 which the sons are led and are thus. ''. subjected to additional stretching or tension. If desired, glass or metal tubes can be slid over one or more of the glass or metal rods.

   In this case, the wires do not come. in contact with the rods themselves but with the tubes which must be able to move fairly easily around the rods so that they turn quickly when the threads slide on them.



   Artificial yarns can be treated during their manufacture or in the finished state, with a curing agent, such as formaldehyde or the like.



   It goes without saying that from the cellulose ether xanthate solution, films or threads having low gloss or entirely matt can also be produced by the present process with the help of any. method known in the artificial silk industry (rayon).



   (4) The process is carried out as in (1), (2) or (3), except that instead of being 30 m, the spinning speed is 40 m. n the minutn.



   (5) The process is carried out as in (1), (2) or (3), except that instead of being 30 m, the spinning speed is 60 m. per minute, the amount of the cellulose ether xanthate solution delivered per minute being about double or triple the amount delivered in (1) (6) The process is carried out as in any of the formulas operations (1) to (5), but with the difference that the cellulose ether xanthate solution does not enter directly into the coagulation bath containing sodium carbonate, but is extruded into one of the baths following:

   (a) a sodium sulphide solution of a 25% concentration having a temperature of 45 to 70 C, or

  <Desc / Clms Page number 49>

 (b) a sodium chloride solution of 25% concentration having a temperature of 45-70 ° C or (c) an ammonium sulfate solution of a concentration
 EMI49.1
 trD: tion of a5 to i30 'l having uno tuinperaturu da 10 to: Jt.5 0, or (d) a solution of ammonium sulphate of a concentration of 25 to 30% having a temperature of 30 to 50 c, or (e) a solution of ammonium chloride with a concentration of -25 to 30% having a temperature of 16 to 25 C, or
 EMI49.2
 (f) a solution of unI ammonium ohloride ;:

  ) 25 to 30% conformation having a temperature of 30 to 50 C, or (g) any coagulation bath known in the industry of the cellulose ether xanthate solution, for example a bath containing Z at 10% H2SO4 or 2 to 10% of
 EMI49.3
 H2SO4 and 10 to 24 days of Na2so4 and (or) 12 to 16% ligSO4 at 30-55 C, at the end of which the completely or incompletely coagulated wire is introduced into one of the baths indicated in (1) under (a) to (z7).



   (7) The process is carried out as in any of the working formulas (1) to (6), but with the difference that the yarn is washed on the spool for about 15 minutes, is then milled and processed. skein and is then treated for a short time (for example, for one to 20 minutes) with 2-10% sulfuric acid or with 1-5% hydrochloric acid or with a bath containing 2 to 10% sulfuric acid and 10 to 16% sodium sulphate and (or) 12 to 16% magnesium sulphate, at room temperature or at 40-50 C, or by sulfuric acid of a concentration of 30-70%, at room temperature, at 5 C, at 0 C or at minus 5 C or by any of the baths indicated above in (1) under

  <Desc / Clms Page number 50>

 (a) to (z7)

   and is then washed and finished in the ordinary manner. If the spinning is carried out in a centrifugal spinning machine, the first washing is carried out with the cake and the separate milling or twisting is omitted.



     (8) Procedure as in (7), know that before the acid treatment or the subsequent treatment with one of the baths indicated above in (1) under (a) to (27), the yarn is washed on the coil or in the cake for about 2 to 5 minutes instead of 15 minutes or not washed before the acid treatment.



     (9) Procedure as in (7), except that before being
 EMI50.1
 subject to trtiituitmiit. i.1.ûd.d6 or! 'u.ltUli10Ut u.lL6rlour pure one of the baths indicated above in (1) under (a) to (z7), the thread is washed on the spool or in the cake for half an hour to 1 hour or more (for example, 2 to 6 hours) instead of 15 minutes.



   (10) Procedure as in (7), (8) or (9), except that the first washing and the acid treatment and (or) the subsequent treatment by one of the baths indicated above in (1) under ( a) to (z7) is performed on the spool or cake, after which the thread is washed and finished.



   In the case of spool spinning, the twisting or milling of the yarn can be carried out either after the acid treatment or the subsequent treatment by one of the baths indicated above in (1) under (a) to ( z7), either after washing
 EMI50.2
 which follows the acid treatment or the treatment! .l ", nt subsequent i. = 1¯ a bath containing one or more alkaline carbonates or yesterday. after drying.



   (11) The process is carried out according to any of the working formulas (1) to (6), but with the difference that the yarn is twisted directly from the spool and is then made into a skein (or, if the spinning takes place in a centrifugal machine, the cake is

  <Desc / Clms Page number 51>

 directly made into a skein), after which the skein is washed for about 15 minutes and then treated for a short time (for example, for 1 to 20 minutes) with / from the indicated acidic agents or media under (7) or by any of the baths indicated above in (1) under (a) to (z7) and is then washed and finished in the ordinary manner.



   (12) Procedure as in (11), but with the difference that before being treated with acid or subsequently treated with one of the baths indicated above in (1) under (a) to (z7) , the skein is washed for about 2 to 5 minutes instead of 15 minutes.
 EMI51.1
 



  (15) Procedure as in (11), except that it can be treated with acid or subsequently treated by one of the baths indicated above in (1) under (a) to (z7), the bedside table is washed for half an hour to 1 hour or longer (eg, 2 to 6 hours).



   (14) Procedure as in (11), but with the difference that, when it is put in the form of a skein, that is to say without any intermediate washing, the yarn is treated with a acidic or subjected to further treatment by one of the baths indicated above in (1) under (a) to (g) (z7), as described in (11) and is then washed and finished.



   (15) Procedure according to any one of the working formulas (1) to (5) but with the difference that (except for the washing to which the yarn is subjected if the spool turns in water or if it turns in the water). water, or if it is washed in the funnel or pot of the centrifugal spinning machine), the yarn is subjected, without being washed, to the acid treatment or to the subsequent treatment directly on the spool or in the cake by means of the 'Any of the acidic agents or media indicated in (7) or any of the baths indicated above in (1) under (a) to

  <Desc / Clms Page number 52>

 
 EMI52.1
 (z7) respectively, after which (in the case of spool spinning, if desired, after having been washed and / or rewound), optionally after being made into a skein,

   it is washed (if it has not been washed or if it has been completely washed on the spool or in the cake) and finished.



   (16) The process is carried out in accordance with any of the operating formulas (1) to (5), except that the wire collected on the spool or in the centrifuge box is treated with an agent containing an alkali carbonate, for example for example by any of the coagulating agents given in (1) under (a) to (z7) (for example a 25% sodium carbonate solution, at room temperature or at 45-50 C or by a 10% sodium carbonate solution, at room temperature or at 45-50 C or with a solution containing 20% sodium carbonate and 12 to 13% sulfa-
 EMI52.2
 te of sodium, â the.

   ambient temperature or at 45-50 0) or by a solution of a neutral salt, for example by a 20-25% solution of sodium sulphate or sodium chloride, at / at room temperature or at 40-50 0 or more. This treatment with the agent containing an alkaline carbonate or with a solution of a salt can be carried out while the wire is being deposited on the spool or in the centrifugal box, -car
 EMI52.3
  <T! Tm.'p1 "nri Îf.imud. Tuurnur lu Ucùitm .;

   in the liquid containing sodium carbonate and (or) another salt, or by introducing this liquid into the centrifugal box during spinning, and (or) after spinning, by treating the yarn on the spool or in the cake by one of the liquids listed above, at room temperature or 45-50 C, for 15 to 30 minutes or more, for example for 1 to 6 hours, then (in the case of spool spinning after twisting of the yarn) by putting the yarn in a skein, treating the skein with any of the acidic agents indicated in (7) and washing and finishing the skein.

  <Desc / Clms Page number 53>

 



   (17) Procedure as in (16), except that after having been treated with the solution containing an alkali carbonate and (or) another salt and put in chévette, the thread is washed and finished without having been subjected to the acid treatment .



   (18) Procedure as in (17), except that after having been treated with the solution containing an alkali carbonate and (or) another salt, the yarn is, without being tied up and, without being subjected to the acid treatment , completely washed and then skeined and finished.



   (19) Procedure as in (16), except that after having been treated with the solution containing an alkali carbonate and (or) another salt, the yarn is, not put into a skein, but subjected directly to the acid treatment on the coil or cake and washed on the coil or cake and finished or (twisted, in the case of a coil) skeined, washed and finished.



     (20) Procedure as in (16), except that after being skeined, the yarn is washed for 3 or 3 minutes, then subjected to the acid treatment.



   (21) Procedure as in (20), except that before being subjected to the acid treatment, the yarn is washed for about 15 minutes instead of 2 to 3 minutes.



   Examples for the manufacture of fibers in rovings automatically result from the above examples.



   If desired, the stretchability of artificial yarns can be increased by treating them with shrinkage agents, for example by any of the methods described in Belgian Patents Nos. 342,831, 355,400, 361,387, 361,532 and 361,564 by the same inventor. .



   (22) The process is carried out according to any one of the operating formulas (1) to (21), except that before spinning it into artificial threads, the solution of the cellulose ether xanthate at 15- is allowed to mature. 17 C for 36, 48,60 or 72 hours.

  <Desc / Clms Page number 54>

 



   Desulfurization and / or bleaching of artificial yarns can be carried out by any of the methods described in Belgian Patents Nos. 371,966, 397,588 and 397,589 by the same inventor.



    ,,-Movies-,,
 EMI54.1
 (1) L 'nn1 \ ticïn ütz:, nnblmtn d'4ttimr t1n o <111.lo: "': n, ce.: T spread uniformly in a known manner on the surface of the drum of a film-making machine, based on the drum principle, part of the drum being immersed in one any of the baths indicated in the chapter "Artificial threads" of this example in (1) under (a) to (z7) or, when the two-bath system is adopted, the drum is
 EMI54.2
 dipped in one '1UO 100n'1.uo des bain' i ttrlirluc3z danr: one ohn- pitre in (6) under (a) to (g), after which the freshly coagulated film is introduced into one of the baths indicated in the chapter "Artificial threads" of this example in (1) under (a) to (z7).

   The diameter of the drum should be adjusted so that, when the drum rotates at the desired speed, the film is sufficiently solidified at the time it has to move away from the surface of the drum to undergo the subsequent treatment (s) envisaged.



   The solidified film is washed in a known manner with hot or lukewarm or cold water, then dried.



   Film casting and (or) film drying can be carried out without additional stretching or with more or less severe additional stretching.



   The film can be treated, before or after drying, with an aqueous solution of glycerol (with a concentration of 4 to 10% for example) or of glycol, in order to increase its flexibility.



   It goes without saying that the film can also be treated with any of the known agents or any of the known compositions resistant to moisture and water.



   The film can be processed during manufacture or during

  <Desc / Clms Page number 55>

 that it is finished by a hardening agent, such as formaldehyde or the like.



   (2) The process is carried out as in (1), except that instead of being distributed on a drum, the solution of the cellulose ether xanthate is applied by means of a suitable device on an endless belt having a smooth surface and immersed in one of the coagulation baths indicated in the chapter "Artificial threads" of this example in (1) under (a) to (27), or, when the two-bath system is adopted, the endless ribbon is dipped into any of the baths indicated in the chapter "Artificial threads" of this example in (6) under (a) to (g), after which the freshly coagulated film is introduced into the one of the baths indicated in said chapter in (1) under (a) to (z7).



  * (3) The process is carried out as in (1) or (2), except that instead of being spread on the surface of an endless drum or ribbon dipping with the hands partially into the coagulation bath , the solution of the cellulose ether xanthate is extruded through a suitable funnel or suitable slit into any of the baths shown in chapter II artificial threads "of this example in (1) under (a) to (z7 ) or, when the two-bath system is adopted, the solution of the cellulose ether xanthate is extruded into any one of the baths indicated in the chapter "Artificial threads" of this example in (6) under (a) to (g), after which the freshly coagulated film is introduced into one of the baths indicated in said chapter in (1) under (a) to (z7).



   (4) The process is carried out as in (1), (2), or (3), except that on leaving the coagulation bath or, when operating by the two-bath process, on leaving the second bath on film is treated at room temperature or at a higher temperature in a consecutive bath containing one or more alkaline carbonates, in the bath 11 was @ or by any other bath containing at least one carbonate.

  <Desc / Clms Page number 56>

 alkaline bonate, for example by one of the other baths indicated in (1) under (a) to (z7), after which the film thus treated is simply washed and finished or else washed, acid-treated, rewashed and finished .



   (5) The process is carried out as in (1), (2) or (3), except that when leaving the coagulation bath or, when operating by the two bath process, when leaving the second bath , the film is washed for two to 15 minutes, then treated for a short time (for example 1 to 20 minutes) with a bath containing 2 to 10% H2SO4 and 10 to 16% Na2So4 and ( or) 12 to 16% MgSO4, at room temperature or at 40-50 C, or by sulfuric acid at a concentration of 30-70%, at room temperature, at 5 C, at 0 c, or minus 5 C, then washed and finished as usual.



   (6) Procedure as in (5) except that no intermediate washing takes place between coagulation and subsequent treatment with an acidic agent.



   (7) Process carried out as in (4), except that instead of being treated with a bath containing one or more alkali carbonates, the film leaving the coagulation bath is treated, with or without intermediate washing, by a solution of a neutral salt, for example with a 20-25% solution of sodium sulphate or sodium chloride at room temperature or at 40-50 C or higher.



   It goes without saying that yarns or films having reduced gloss or being entirely matt can also be produced by the present process using any method known in the chardonnette (rayon) industry.



   Yarns or films can be obtained in which voids are distributed, for example by incorporating into the solution cellulose ether xanthate, sodium carbonate or other substance capable of developing a gas during spinning, and introducing freshly coagulated threads or films emerging from the direo- coagulation bath

  <Desc / Clms Page number 57>

 tement in an acid bath, for example one of the bailacids indicated in the chapter "Artificial threads II of this example (under (7)) or in the chapter" Films "(under (5))

     or by dispersing air or other gas in the solution of cellulose ether xanthate and coagulating the solution
 EMI57.1
 O'l.M <4o cetjc'-MK ether xanthate gueloongue cellulose ether xanthate any of the itidiquau ü.Ull :: J la ulLaiJl1rv "] J'11tJ l1l'Llflulci1." Do this example under ( 1) to (22).



   Finishing (priming) and printing of textiles.



   Finishing (1) A fabric, such as a cotton fabric is provided by means of a suitable machine, for example a post-filling machine or a tampon machine or a spreading machine, with one or more coverings made of the solution of cellulose ether xanthate, to which can be added a filler such as talc or kaolin or zinc white or a dye or. a pigment such as lacquer or carbon black or ocher or mica and (or) a softening agent, for example oxytrimethylene sulphide (see UK Patent No. 25.246 / 1911 by the same inventor)
 EMI57.2
 uu um xavun ùu from lmilC to <:; l: J.l.'t1UlJtj uu mia l1ul1tJ; l ...: ...: u.l.1.vo or nor, etc. etc.

   When the material is covered or impregnated or loaded, it is introduced directly or after drying and (or) intermediate steaming, in one of the coagulation baths or in one of the combinations of baths. coagulation which are indicated in the chapter "Artificial threads II of this example ep. (1) under (a) to (z7) and in (6) under (a) to (g), then it is washed and dried.



   The textile material can be treated, before or after drying, with a softening agent, such as soap or madder oil or glycol, etc.



   (2) Proceed as in (1), except that the solution of the cellulose ether xanthate is mixed with a solution of starch or starch, or dextrin, or

  <Desc / Clms Page number 58>

 any other colloid known in the finish industry.



   (3) proceed as in (1) or (2), except that steps are taken to incorporate gas bubbles or voids into the regenerated cellulose deposited within or on the surface of the fibers of the fabric. This can be achieved in any known way by dispersing a gas such as air or hydrogen or nitrogen, etc., or by ±:

     otherwise distributing cellulose ether xanthate in the solution, or incorporating therein sodium carbonate or another substance capable of liberating a gas when brought into contact with an acidic medium, and (or) by directly introducing the impregnated fabric emerging from the coagulation bath into an acid bath, for example in sulfuric acid with a concentration of 2 to 15% at a temperature of 4 to 8 C or at room temperature or at 35-45 C, or in a bath containing 10 to 16% H2SO4 and 20 to 25% Na2SO4 or in a bath containing 10 to 15% Na2SO4 14 to 18% MgSo4 and 6 to 16% H2SO4, at room time or at 35-45 0.



   (4) The method is carried out as in any of Examples (1) to (3), except that before being applied to the tissue, the solution of the cellulose ether xanthate is made into a kind of soapy foam by the process described in Belgian Patent No. 389,620 of the same inventor.



   Examples of sizing or sizing of yarns automatically result from what is said in (1) to (4).



   (5) The solution of cellulose ether xanthate is mixed with a colorant or with a pigment, such as lacquer, ocher, carbon black, zinc white, finely divided mi- ca or a bronze powder not containing aluminum, and it is applied to a cotton fabric by printing on a roller or stencil printing machine. After printing, and, if desired, after drying the fabric, it is introduced into one of the coagula baths

  <Desc / Clms Page number 59>

 tion or one of the bath combinations that have been described
 EMI59.1
 Cluiio la 0111.1.111 \ '1'0 "Fila arllrlulmiv" from 00 (> IZUIIII) Iti to (1) under (a) to (z7) and in (6) under (a) to (g).



   What has been said in chapters II Artificial yarns and "Films" of this example about the application, to the manufacture of yarns and films, of all the variants concerning the coagulation baths, their temperature and all the details concerning further processing, also applies to the finishing or sizing or printing of textiles.

   In other words: taking into account, as appropriate, the difference between the handling and the technique of making artificial threads or films, on the one hand, and the primer or the finishing or the filling or the printing or sizing of textiles, on the other hand, it will be easy and, with regard to every detail it will be appropriate for any person skilled in the art, to apply all the variants of the present process described in the chapter "Artificial threads "from this example in (1) to (22) to finishing, covering, sizing, filling, sizing or printing textiles.



     "Cements and adhesives
The cellulose ether xanthate solution is used for bonding two or more sheets of paper or cardboard or cotton fabrics or veneer sheets, the bonded materials then being, after intermediate drying. , if desired, introduced into one of the coagulation baths or into one of the combinations of coagulation baths which have been described in the chapter "artificial threads" of this example in (1) under (a ) to (z7) and in (6) under (a) to (g).



   Thick plates
Thick plates can be made by shaping concentrated solutions or pastes of the cellulose ether xanthate into the desired shape and, optionally after a,.

  <Desc / Clms Page number 60>

 intermediate drying, by treating them with one of the precipitation baths or one of the combinations of baths described in the chapter "Artificial threads" of this example in (1) under (a) to (z7) and in (6) under (a) to (g).



   All the variations concerning the coagulation baths their temperature, as well as the age of the cellulose ether xanthate solution and all the details of the subsequent treatment indicated in the chapter on artificial threads "in (1) (22) can be applied in the practice of the present invention for the use of a xanthatte solution of cellulose ether in adhesive, or to produce thick plates or the like according to the invention. It goes without saying that the handling and
 EMI60.1
 that: ;;: must be adapted to prooudoo and rJlo'1 ': J: .1 oà> Gr: atilr,> i mechanical and others in use in these industries.



   In the production of shaped structures or other articles useful by the present process, which production is indicated in this example and the following ones, the coagulation bath or baths should be kept in constant circulation in the usual manner.



   With respect to any and all of the points in this example, the coagulation bath (s) must be kept in permanent circulation in the usual manner and the sodium carbonate as well as the caustic soda can be recovered as (sodium carbonate). sodium or caustic soda (causticizing sodium carbonate) as described.



   As for the caustic soda entering the bath and coming from the shaped structures, it can be completely or partially transformed into sodium carbonate by introducing CO 2 into the bath, continuously or at a temperature.

  <Desc / Clms Page number 61>

 



   Example VII
The process is carried out as in Example (VI) except that the proportion of carbon disulphide employed for the preparation of cellulose ether xanthate amounts to 400-500 parts.



   In some cases the cellulose ether xanthate solution of this example does not achieve the ability to provide conformable structures according to the present process which, on leaving the coagulation bath, are washable indefinitely.
 EMI61.1
 It took 14 to 36 days calculated from the end of the preparation of the cellulose ether xanthate mixture.

   Accordingly, if it is desired to transform the cellulose ether xanthate solution into conformal structures by washing the freshly coagulated conformal structures indefinitely, the cellulose ether xanthate solution must be matured at 15. -30 C or heat it for example to 60 C and its transformation into conforming structures must be delayed until the moment when the preliminary experiments indicated above show indefinite washability, or else be carried out according to a process which does not require indefinite washability, for example according to one of the methods indicated in the chapter "Artificial yarns of example VI under (7) to (22).



   However, these or similar methods can also give good results in cases where the cellulose ether xanthate solution has already reached the degree of suitability required to provide conformal structures which leave the bath. coagulation or the combination of coagulation baths at. indefinitely washable condition.



   Example VIII
The procedure is carried out oommo in Example VI, but with the difference that instead of the solution of cellulose ether xanthate, a solution of a product is used.

  <Desc / Clms Page number 62>

 obtained by contacting cellulose xanthate and one or more alkali soluble cellulose ethers, which product contains not less than 20% CS2 (see, for example, Belgian Patents Nos. 407,262, 407,734, 406. 950 by the same inventor and his English patent applications 11242/1935 and 14488/1935).



   In the coagulation baths employed in the preceding examples, the sodium carbonate can be completely or partially replaced by one or more other
 EMI62.1
 1'11) 1: 1 l'6nr.t.inn qlcll] ino, pnr ox "'Jp1o, p! Ir du t57, r h'.rr.' -1 sodium (borax) (for example, by a borax solution of a
 EMI62.2
 concentration of 21 jo, at 50 0 or at 60 0 or 70-90 C or at a concentration of 36%, at 70-90 C or at a concentration of 53%, at 90 C or by a solution of sodium sulphite crystallized at a concentration of 25%, at 50 c or at 60-70 or at
 EMI62.3
 EO-900C or at a concentration of 42%, at 70-800C or by a bibasic sodium phosphate solution at a concentration of 45%, at 50 C, or at 70-80 0 or at a concentration 47%, at 60-80 C or with a tribasic sodium phosphate solution with a concentration of 20-40%,

   at 50 C or 60-70 or 80 C.



   If desired, the extensibility of shaped structures, such as yarns, films, coatings, can be increased.
 EMI62.4
 or similar structures produced by the present invention, by treating them during their manufacture, for example after coagulation and washing or alternatively in the finished state, dry or wet, with suitable shrinkage agents. , for example by some of the shrinkage agents mentioned in Belgian Patents Nos. 342,831, 355,400, 397,588, 397,587, 361,532, 361,564 and 371,966 by the same inventor.

  <Desc / Clms Page number 63>

 



   The term "cellulose" as employed in the specification and claims is, wherever the context permits, intended to include cellulose, such transformation and oxidation products, such as cellulose hydrate, I 'hydrocellulose, oxycellulose, acid-cellulose, and the like, in summary, any body of the cellulose group which has been proposed as a starting material for the preparation of cellulose derivatives or compounds of any kind, including including the cellulose ether xanthate solution.



   The term "alkali-cellulose" is intended to include, whenever the context permits, aloali-cellulose prepared in the usual manner, that is to say by soaking cellulose in a solution of caustic alkali and removing excess thereof by pressure, or by mixing cellulose with the amount of caustic alkali solution desired to be present in the final alkali cellulose.



   Whenever the context permits, the expressions "cellulose ether soluble in an alkali", cellulose ether which is soluble or at least partially soluble in a solution of caustic alkali II and "cellulose ether which is at least partially soluble in a caustic alkali solution ";

  are intended to include single and mixed cellulose ethers which are completely or almost completely soluble in a solution of caustic alkali at room temperature and at a lower temperature, for example at a temperature between room temperature and 0 C or a lower temperature and single and mixed cellulose ethers which are insoluble or incompletely soluble in caustic alkali solution at room temperature,

   but which can be made partially or completely soluble in this solution at room temperature by cooling their suspensions or incomplete solutions in an al- solution.

  <Desc / Clms Page number 64>

 caustic cali at a temperature between room temperature and 0 C, for example at minus 5 C or minus 10 C or lower and then allowing the temperature to rise to 0 C and 20 C, for example at a temperature comprised in 00 and 20 C and single or mixed cellulose ethers which are insoluble or incompletely soluble in a caustic alkali solution at room temperature or at a temperature between room temperature and 0 C and 0 VS,

   but which can be made partially or completely soluble in this solution at the temperature of the chamber and (or) at a temperature between room temperature and 0 C or at 0 C in re-
 EMI64.1
 .odacznt Inurs aunponsione or i.neomplat solutions:. ^, at a temperature below 0 c for example at minus 5 C or monk 10 c or lower, and then allowing the temperature to rise to 0 c or above 0 C, for example at room temperature.



   In the description and the claims, whenever the context permits, the expression "cellulose ether It is intended to include single cellulose ethers and mixed alichatic and aromatic cellulose ethers of any kind, it is i.e. any cellulose compound containing an alcohol radical coupled in the form of an ether to the cellulose molecule, whether or not the alcohol radical is replaced by any organic group or radical or by an inorganic element such as nitrogen or sulfur or a group containing an inorganic element such as a nitrogen-hydrogen group or a sulfur-hydrogen group, in short, any group or radical which is known as a substituent of alcohol radicals.



   The expression II alkaline carbonate "in the description
 EMI64.2
 and reveidications are, whenever cor-text allows, tines to include primary and secondary alkali carbonates.

  <Desc / Clms Page number 65>

 



   The expression "artificial structures" or "shaped structures" employed in the description and the claims is intended to include: artificial yarns, in particular artificial silk (rayon) and strand or roving fibers, horsehair artificial, artificial straw, films, bands and plates of all kinds, plastic masses of any description; adhesives and cements, finishes, coatings and layers of all kinds, particularly those applicable in the finishing, filling and sizing of textile fabrics, sizing of threads, thickeners or fixing for pigments in fabric printing and the like; paper like coatings, paper sizing materials;

   in the manufacture of artificial leather or canvas for bookbinding, or of
 EMI65.1
 canvas to copy, or from J?!: t.1Jior tr'8.118p!: tr0ul ;, or from 'transparent canvas and others.



   The term II Artificial yarns "includes artificial yarns and spun articles of all kinds, for example, artificial silk (rayon), artificial cotton, artificial wool, artificial rope, and straw. the artificial of any kind.



   The expression "textile materials" in the description and in the claims comprises, whenever the context permits, any spun or woven textile fibers, whether of animal or vegetable origin (for example linen, linen. flax, hemp, ramie, jute, wool and particularly cotton, as well as artificial fibers of all kinds in the form of yarns, rovings or fabrics made from, or containing, artificial fibers) in the form of single fabrics or of mixed fabrics or in the form of yarns in skeins or skeins, tassels or chains.


    

Claims (1)

CLAIMS. ---------------- 1. A process for making shaped structures as defined herein or other useful articles from cellulose derivatives, wherein a preferably liquid shaped mass comprising at least one cellulose ether xanthate is contacted with a medium contained at least one alaelin carbonate. EMI66.1 2. A method of making 0úl1l'c, 1 '.: 1' ':' e .... structures as defined herein, or other useful articles from cellulose derivatives, wherein a preferably liquid shaped mass comprising, in solution in a caustic alkali solution, in addition a cellulose ether xanthate which has been prepared by employing a proportion of carbon disulphide of less than 20% by weight of the ether of initial cellulose, is brought into contact with a medium containing at least one alkaline carbonate. 3. A process for making shaped structures as defined herein, or acre useful articles from cellulose derivatives, wherein a EMI66.2 mass conforming to a liquid preference comprising, in 801u- tion in a solution of caustic alkali, at least one xanthate of cellulose ether which has been prepared by employing a proportion of carbon disulphide of less than 15% by weight of the The initial cellulose ether is brought into contact with a medium containing at least one alkali carbonate. EMI66.3 4. A 1?!: 'C.H16tlú da rabrloùtlon dcz atruoturos conf'Ol'miÍn: 1 as defined herein, or other useful articles from cellulose derivatives, in which a shaped mass of preferably a liquid comprising, in solution in a caustic alkali solution, at least one xanthatte of cellulose ether which has been prepared by employing a proportion of carbon disulphide which is not greater than. <Desc / Clms Page number 67> re or is even less than 10% of the weight of the initial cellulose ether, is brought into contact with a medium EMI67.1 UU1ÜtHlllllL uu iuulm a ourbuttubu, loul1.ll. 5. A process for making shaped structures as defined herein, or other useful articles from cellulose derivatives, wherein a preferably liquid shaped mass comprising, in solution in a solution of caustic alkali , at least one cellulose ether xanthate which has been prepared using EMI67.2 urm proportion of the aul'Curo do ourbono 'which is not inf' "i- iure to 20% of the weight of the initial cellulose ether, is contacted with a medium containing at least one alkaline carbonate. 6. A method of fabricating shaped structures as defined herein, wherein a caustic alkali solution of at least one cellulose xanthate which has been prepared using a proportion of carbon disulphide which is not is not less than 20% of the weight of the initial cellulose ether, is brought into a suitable form and is then coagulated with an aqueous solution containing at least one alkali carbonate. 7. A process according to claim 5 or 6, wherein before being transformed into a shaped structure the cellulose ether xanthate reaches a degree of ripeness substantially exceeding the C24 stage and preferably substantially exceeding the C24 stage. stage C36 8. A process according to any preceding claim in which, instead of the caustic alkali solution of a cellulose ether xanthate, a caustic alkali solution of a product obtained when the xanthate of cellulose ether in dissolved, undissolved or half dissolved state is contacted with an ether of cellulose ether soluble in alkali, in dissolved, undissolved or half dissolved state, the proportion <Desc / Clms Page number 68> of carbon disulphide. contained in the final product not being less than 20%, calculated on the. sum of the weight of the cellulose contained in the cellulose ether xanthate and the weight of the alkali soluble ether. 9. A process according to any one of the preceding claims, in which, instead of the caustic alkali solution of a cellulose ether xanthate, a caustic alkali solution of cellulose ether is employed. a product obtained when the cellulose ether xanthate in the dissolved, undissolved or half-dissolved state is in contact with a cellulose ether soluble in an alkali, in the dissolved, undissolved or half-dissolved state, the proportion of carbon disulphide contained in the final product being less than 20% and preferably less than 15% or, even better, less than 10% calculated on the sum of the weight of the cellulose ether contained in the cellulose ether xanthate and the weight of the cellulose ether soluble in an alkali :. 10. A process according to any preceding claim, wherein the cellulose ether xanthate solution contains cellulose xanthate. 11. A process according to any preceding claim, wherein the cellulose ester xanthate is a xanthate of a dan-soluble cellulose ether. an alkali. 12. A process according to any one of claims 1 to 7, wherein instead of the xanthate solution of cellulose ether, a solution of a product obtained when an alkali-soluble cellulose ether is employed. , in the dissolved, undissolved or half-dissolved state is brought into contact with a cellulose xanthate in the dissolved, undissolved or half-dissolved state, the proportion <Desc / Clms Page number 69> of @ carbon disulphide contained in the final product being less than 20% and preferably less than 15% or even 10% or else not being less than 20%, calculated on the sum of the weight of the cellulose ether soluble in an alkali and the cellulose contained in the cellulose xanthate. 13. A method according to any preceding claim, wherein a caustic alkali solution of the cellulose ether xanthate of the end product referred to in any one of claims 8 to 12 , is put into a suitable form and is then coagulated with an aqueous solution containing at least one alkali carbonate. 14. A process according to any one of the preceding claims, wherein the cellulose ether xanthate or the other cellulose derivative is a substance during the preparation of which in particular however during its dissolution a temperature. less than plus 5 C, for example a temperature between plus 5 C and minus 10 C or a lower temperature, is employed at least temporarily. 15. A process according to any preceding claim, wherein the coagulation bath contains at least one secondary alkali carbonate. 16. A process according to any preceding claim, wherein the bath contains at least one sodium carbonate. 17. A process according to any preceding claim, wherein the coagulation bath contains secondary sodium carbonate. 18. A process according to any preceding claim, wherein, besides at least one alkali carbonate, the coagulation bath contains a further salt. <Desc / Clms Page number 70> inorganic or organic with alkaline reaction. 19. A method according to any one of the claims EMI70.1 In which case, 1: 1% alkaline uim ciiD-unate, the coagulation bath contains a neutral inorganic or organic salt. 20. A process according to any preceding claim, wherein the alkali carbonate solution contains at least one organic substance which is known in the viscose industry as an addition to a coagulation bath and which is compatible with. alkali carbonate. 21. A process according to any preceding claim, wherein the coagulation bath is at a temperature above 40 ° C. 22. A process according to any preceding claim, wherein the shaped solution is first introduced into a bath containing at least one neutral salt and then into a bath containing at least one alkaline carbonate. 23. A process according to any one of claims 1 to 21, wherein the shaped solution is first introduced into a bath containing an acid or an acid salt and then into a bath containing at least one alkali carbonate. 24. A process according to any one of the preceding claims, in which the shaped structure obtained by coagulation by means of a bath containing at least one alkali carbonate is washed directly with water. 25. A method according to any preceding claim, wherein the shaped structure obtains EMI70.2 nus j>; ir, '() ucc: ulut10n p] .1.ta au Muino C: f) It1j71.3tifl Elll laitySIi of a bath containing at least one alkaline carbonate, is treated by a bath known as a coagulation bath in the industry <Desc / Clms Page number 71> Sort of manufacture of shaped structures as defined herein from alkali soluble cellulose derivatives. 26. A process according to claim 20, wherein the second bath is a bath known as a coagulation bath, in the industry for manufacturing shaped structures as defined herein, from soluble cellulose ethers. an alkali: 27. A process according to claim 21, wherein the second bath is a bath known as a coagulation bath in the industry for manufacturing shaped structures as defined herein from viscose. 28. A process according to any one of claims 1 to 21, wherein the shaped solution is first introduced into a bath containing at least one alkali carbonate and then into a bath containing at least one neutral or alkali salt. 29. A process according to any one of claims 26, 27 or 28 wherein the second bath contains an acid, an acid salt or both. 30. A process according to any one of claims 1 to 21, in which the shaped structure obtained by more or less complete coagulation by means of a bath containing at least one alkali carbonate, is treated with a bath containing at least one. Alkaline carbonate alone or together with at least one of the additional substances mentioned in any one of claims 18, 19 or 20. 31. A process according to any one of claims 1 to 21, in which the shaped structure obtained by more or less complete coagulation by means of a bath containing at least one alkali carbonate, is treated with a bath containing at least one. sodium carbonate only where or <Desc / Clms Page number 72> together with at least one of the additional substances mentioned in any one of claims 18, 19 or 20. 32. A process according to any one of claims 25-31, wherein, prior to being treated by the second bath, the freshly coagulated shaped structure is washed. 33. A process according to any preceding claim in which the shaped structure is an alkylated solution of a cellalose xanthate. 54. A process according to any preceding claim in which the conforming solution is a solution of a hydroxy-alkyl cellulose xanthate. 35. A process according to any one of the preceding claims, wherein the conforming solution is a solution of an alkyl-hydroxy-alkylated cellulose xanthate. 36. A process according to any one of the preceding claims, wherein the solution of the cellulose ether anthate is formed on a rigid or flexible carrier, 37. A process according to claim 36, wherein the carrier is a textile material. 38. A manufacture of films by a process according to any one of the preceding claims, in which the solution of cellulose ether xanthate is spread over a surface, part of which is immersed in a bath containing at least one carbonate. alkaline. 39. A film manufacture according to claim 38, wherein the solution of the cellulose ether xanthate is spread over the surface of a drum or endless puban. 40. A process according to any one of the preceding claims, wherein the caustic alkali entering the coagulation bath containing at least one carbonate <Desc / Clms Page number 73> alkali is converted entirely or partially into alkali carbonate by the continuous or temporary introduction of carbon dioxide (CO2) into the bath. 41. A process according to claim 30, wherein the carbon dioxide is prepared in a known manner by heating calcium carbonate. 42. A process according to claim 30, wherein the carbon dioxide is obtained by heating calcium carbonate, and wherein the obtained calcium oxide is employed for the causticization of the alkali carbonate present in the coagulation bath. 43. A process according to any one of the preceding claims in which, instead of the alkali carbonate, an alkali reacting alkali salt of a weak inorganic or organic acid is used. 44. A manufacture of shaped structures as defined herein, substantially as described in any of the preceding examples. 45. Such shaped structures are defined herein which can be made by the process set out in any one of the preceding claims, whether so made or by any process which is a. obvious ahimic equivalent of each of these processes.