US2335126A - Process of finishing fibrous and textile materials - Google Patents

Description

Patented Nov. 23, 1 943 PROCESS OF FINISHING FIBROUS AND TEXTILE MATERIALS Leon Lilienfeld, deceased, late of Vienna, Germany, by Paul Abel, executor, Vienna, Germany; Antonie Lilienfeld, administratrix of said Leon Lilienfel'd, deceased, assi'gnor to Lilienfeld Patents Inc., Boston, Mass., a corporation of Massachusetts No Drawing. Application September 6, 1938, Serial7No. 228,714. In Great Britain September 7,

3 Claims. (Cl. 117-166) All arduous efforts which have been made with the object of providing a permanent and nevertheless perfectly soft finish or filling or the like which consists of a cellulosic body and which exhibits a soft feel having failed, the lack of a cellulosic material capable of giving a finishing, dressing, filling, impregnating, coating, weighting, printing, stencilling, sizing, etc. which is permanent, i. e. perfectly or at least in an appreciable degree fast to laundering and sufficiently resistant to wear and tear and which nevertheless has a feel to the touch that is not inferior or not substantially inferior to the feel of the fibrous materials, such as fabrics or yarn, to which it has been applied, is a long-felt want in the technology and in the industries of finishing textiles.

The present invention supplies this desideratum in the technology of treating fibrous materials, particularly in the finishing-art of textile materials, for example in the art of finishing textile materials particularly those containing natural vegetable fibers and those containing artificial fibers. For, it enables to produce finishes of any kind which are permanent, i. e. perfectly fast or at least in an appreciable degree fast to laundering and sufiiciently resistant to wear' and tear and which nevertheless have in many cases a high degree of softness.

In other words: According to the present invention it is possible to finish as herein defined, fibrous materials as herein defined, particularly textile materials as herein defined, with cellulosic bodies without impairing or considerably impairing their natural soft feel to the touch.

This novel effect of the present invention is the more surprising and important,

(1) Since the cellulosic bodies used as finishing materials in the present invention produce this eifect also in absence of softening agents or plasticizers, and

(2) Since the cellulosic bodies used as finishing materials in the present invention produce this effect even when they are introduced into the fibrous materials, do not or do not substantially deteriorate, and in many cases even improve the genuine textile appearance of thefibrous materials, particularly textiles.

A highly preeminent and astonishing technical advance of the present invention consists in the fact that, although perfectly textile in feel and appearance, the finishes produced according to the present invention, even when they do not contain mineral fillers, possess in many cases a covering power which is superior or at least not substantially inferior to the covering power of as China clay, calculated on the weight of the cellulose or near conversion product of the degraded cellulose contained in the dressing.

The present invention resides in the recognition that, when such water-insoluble degradation products of cellulose whose solutions or partial or incomplete solutions or dispersions or partial or incomplete dispersions or pastes or magmas or colloidal suspensions in caustic alkali solution as are incapable of yielding coherent films or films which do not disintegrate in the coagulating bath or in the washing water into which they are introduced. therefrom or on being dried, are dissolved or partially or incompletely dissolved or dispersed or partially or incompletely dispersed or colloidally suspended in caustic alkali solution and the thus obtained solutions or partial or incomplete solutions or dispersions or partial or incomplete dispersions or pastes or magmas or colloidal suspensions are applied as herein defined to fibrous materials of any kind as herein defined, they yield finishes as herein defined, i

(1) Which in most cases do'not impair or do not substantially impair the soft feel of the fibrous materials to which they are ap'plied,

(2) Which inmost cases are fast or at least in an appreciable degree fast to commercial laundering,

(3) Which have an excellent textile appearance,

(4) Which exhibit a greater fullness than the fibrous materials before treatment,

(5) Which possess a far greater covering power than the covering powerof finishes obtained with other celulosic bodies, such as cellulose or a near .conversion product of cellulose (deposited in the fibrous materials for instance of the fibrous materials obtained with other cellulosic bodies, such as cellulose, or a near conversion product of cellulose deposited in the fibrous materials, for instance from a cellulose solution or viscose) or alkali-soluble cellulose derivatives or the like and carrying large amounts of mineral fillers (e. g. 100 to 400 per cent. of a mineral filler, such as China clay, calculated on the weight of the cellulose or near conversion product of cellulose or the like).

A highly important feature of the present invention is the degree of degradation of the cellulosic materials asset forth in the last paragraph above, and for brevity, the term water-insoluble non-coherent-film-forming alkali-dispersible degraded cellulosic materia will be used hereinafter, in the claims, to set forth cellulosic materials of the degree of degradation indicated in said paragraph. And, it is important to note that such degraded cellulosic materials are insoluble (or substantially all insoluble) in water and in the usual detergent solutions, e. g. soap solutions, in order that the dressed fabrics should be fast or substantially fast, to laundering.

This novel effect of the present invention is highly important by itself and, in addition, by the fact that the dyeing properties of the fibrous materials as herein defined finished as herein defined with the cellulosic bodies characteristic of the present invention by themselves, 1. e. Without mineral fillers, are far better than the dyeing properties of fibrous materials as herein defined finished to the same degree of covering with another cellulosic body carrying large amounts of mineral fillers.

To the inventors knowledge, the complex of the new effects (particularly of the effect set forth above under (6)) and, thus, the technical advances of the present invention have never been hitherto observed with any other cellulosic bodies.

Owing to the novel eifects specified above, the present invention marks a great technical advance in the industries of fibrous materials as 1 herein defined.

For, it makes for the first time possible to convert a fabric or yarn which has a certain opacity.

fullness, density, thickness and weightinto a fabric or yarn which has a greater or even far greater opacity, fullness, density, thickness and weight.

In fact, it is possible, according to the present invention, to increase, in the fabric being treated,

the degree of opacity, fullness, density thickness and weight without considerably impairing conglutinated, which are soft to the touch, substantially fast to laundering and which, if in a conglutinated state, can be worked up into useful articles and, if in the non-conglutinated state, can be even spun and, if desired, thereafter woven into fabrics or knitted into knitted goods.

In summing up, it is possible, according to the present invention, to produce perfectly novel textile materials cheaper than textile materialscellulose as are prepared by treating cellulose or a near conversion product of cellulose with one or more degrading or hydrolyzing or degrading and oxidizing agents of the acid type or with oxidizing agents until a product forms with the above mentioned properties. In other words, the

cellulose is degraded to the extent of forming awater-insoluble non-coherent-film-forming a1- kali-dispersible degraded cellulosic material.

The present invention is further based on the recognition that the most perfect embodiment of the present inventionconsists in using for the treatment of the fibrous material with a degraded cellulosic material made by first mercerizing the cellulose or near conversion product of cellulose and thereafter subjecting the mercerized material to the degrading or hydrolyzing or degrading and oxidizing treatments as defined herein, then washing and optionally drying.

Particularly useful results are obtained when the mixing of the caustic alkali solution with the degraded cellulosic material is performed (during the whole or a part of the mixing) at a temperature below room temperature, for example at a temperature between 0 C. and room temperature or at 0 C. or at a temperature below 0 C. or even at a temperature at which. freezing or formation of crystals occurs.

The inventor was able to make the observation I generic term intimate fluent mixture as defined,

for brevity.

The carrying out of the invention in practice consists in bringing together a non-coherentfilm-forming alkali-dispersible cellulosic. material with caustic alkali solution into an intimate fluent mixture as defined, and that is then applied to a fibrous material as herein defined,

particularly to a textile material, such as a fabricv .or knitted material or yarn consisting of, or

containing, natural fibres of any kind, such as cotton, wool, silk, linen, flax, hemp, jute, ramie or the like or artificial fibres of any kind, such as artificial silk, artificial wool, artificial cotton, staple fibre or the like; This group will be hereinafter termed textile material.

It is to be understood that in the present invention degradation products of cellulose may be used which are made by any process or method whatever suitable for the production of degradation products of cellulose, whos solutions or partial or incomplete solutions or dispersions or partial or incomplete dispersions or pastes or magmas or colloidal suspensions in caustic alkali solution are incapable of yielding coherent films or films which do not disintegrate in the coagulating bath or in the washing water into which they are introduced therefrom or on being dried.

A preferable method or process (but to which the invention isnot limited) for the preparation 1 of degradation products of cellulose having the properties defined above is the treatment of cellulose or a near conversion product of cellulose with such agents or mixtures of agents as exert a hydrolyzing or degrading or an oxidizing or a hydrolyzing and oxidizing or a degrading and oxidizing action on cellulose, the conditions, particularly the temperature and/or duration of the treatment being such as to convert the cellulose into a product whose solutions or partial or incomplete solutions or dispersions or partial or incomplete dispersions or pastes or magmas or colloidal suspensions in caustic alkali solution are incapable of yielding coherent films-r films which do not disintegrate in the coagulating bath or in the washing water into which they are introduced therefrom or on being dried.

Among the hydrolyzing and/or degrading agents which may or may not have an oxidizing effect on cellulose substances having an acid reaction, such as acids or acid salts and also substances, for instance salts, capable of generating acids have proved very suitable for the aforesaid treatment of cellulose.

The acids (inorganic and organic) or mixtures of acids may be used in the concentrated state or in concentrated or moderately concentrated or dilute solutions.

When, instead of acids, one or more acid salts by themselves or together with one or more acids are used, they may be appliedwto the cellulose in concentrated solutions or in moderately concentrated solutions or in dilute solutions.

Since, according to the inventors "present knowledge, the preparation of degradation products having the properties defined above by means of dilute acids is preferable to, and in many cases simpler and easier to control than,

the treatment withconcentrated acids or mod-.

erately concentrated acids, it is often preferable to efiect the conversion of cellulose into degradation products having the properties defined above by means of media which contain small or very small proportions of acids or acid substances.

The conversion of cellulose into such degradation products as have the properties defined above may be efiected in various ways. Some of these methods are described in the following lines by way of examples to which, however, the present invention is not limited.

Weak acids First meth0d.-'I'his method consists in treating cellulose with an excess ofa dilute mineral acid in the cold, i. e. at room temperature or at a temperature not substantially exceeding room temperature or at a temperature below room temperature.

Thus, for instance, cellulose in sheets or lumps or, preferably, in a finely divided state is im mersed in, or otherwise mixed with, an excess of a dilute hydrochloric acid or sulphuric acid or phosphoric acid or nitric acid or hydrobromic or sulphurous acid or the like and the mixture allowed to stand at room temperature until the cellulose is degraded to the extent above indicated. In some cases, particularly when the acid is very dilute, the treatment must last 2 to 3 months or even longer until the desired result is attained. 1

Second method.-This method is similar to the first, but the acid treatment is conducted at a raised temperature with or without pressure. Thus, for instance, cellulose in sheets or lumps or, preferably, in a finely divided state is immersed in, or otherwise mixed with, an excess of hydrochloric acid or sulphuric acid of 0.05 to 2 per cent. strength and heated in a closed or open vessel or with reflux cooling to 50 to C. or to the boiling point and kept at this temperature until the cellulose is converted into a product having the properties defined above.

Or, for instance, cellulose in sheets or lumps or, preferably, in a finely divided state is immersed in, or otherwise mixed with, an excess of hydrochloric or sulphuric acid of 3 to 8 per cent. strength and heated in a closed or open vessel to 40 to 50 C. and kept at this temperature until the cellulose is converted into a product having the properties defined above.

Or, for instance, cellulose in sheets or lumps or, preferably, in a finely divided state is immersed in, or otherwise mixed with, an excess of a the cellulose is converted into a product having the properties defined above.

Third meth0d.This method consists in impregnating or otherwise mixing cellulose with an excess of a dilute mineral acid, for example with dilute hydrochloric acid or sulphuric acid or phosphoric acid or nitric acid or the .like, removing the excess of the acid by pressing, centrifuging or the like, drying the pressed and preferably comminuted material and then leaving it in the air until the cellulose is converted into a product having the properties defined above. I

Thus, for instance, cellulose in sheets or lumps or, preferably, in a finely divided state is im mersed in, or otherwise mixed with, an excess of sulphuric acid of 1 per cent. strength and left in the sulphuric acid for a few minutes, whereupon the excess of the sulphuric acid is removed by pressing or centrifuging until the press cake or residue of. the centrifuging retains 0.3 per cent. to 0.5 per cent. of E804. Thereupon, it is comminuted or otherwise finely divided and either allowed to remain in the air at room temperature or, with or without intermediate drying at room temperature or at a temperature not substantially exceeding room temperature, heated in a closed vessel at 40 to 100 C. until the eellulose is converted into a product having the properties defined above. In the former instance the pressed and. comminuted material or even 1 to 2 days until the desired result is attained. Or, for instance, cellulose in sheets or lumps or, preferably, in a finely divided state is immersed in, or otherwise mixed with, an excess of sulphuric acid of 3 to 4 per cent. strength and left in the sulphuric acid for a few minutes, whereupon the excess of the sulphuric acid is removed by pressing or centrifuging until the press cake or residue of the centrifuging retains l per cent. of sulphuric acid (i'. e. approximately 25m 40 per cent. of the dilute acid calculated on the original weight of the cellulose). Thereupon, it is comminuted orotherwise finely divided and either allowed to remain in the air at room temperature or, with or without intermediate drying at room temperature or at a temperature not substantially exceeding room temperature, heated in a closed vessel at 30 to 100 C. until the cellulose is converted into a product having the properties defined above. In the former instance, the pressed and comminuted material must remain in the air for about 1 to 2 months, whereas in the latter case the heating must be conductedfor several hours until the desired result is attained.

Or, for instance, the treatment is conducted as in the foregoing two modifications, but with the difference that the concentration of the sulphuric acid is only 1.2 to 1.5 per cent.

In the foregoing methods, instead of the acids, also aqueous solutionsof acid salts, for example of bisulphates or bisulphites can be used, and also such salts of inorganic acids as exert acid action by way of hydrolysis in their aqueoussolutions, for example aluminium sulphate or magnesium chloride or zinc chloride or alkali chlorides or the like.

Particularly, when they are conducted at a raised temperature, in the foregoing three methods, instead of the mineral acids, organic acids by themselves or in mixture with mineral acids may be used, for example formic acid, acetic acid, oxalic acid or a hydroxy acid for example glycollic acid, lactic acid, tartaric acid, citric acid or the like. When the organic acids are used by themselves, the concentrations must be higher than the concentrations of the mineral acids. In some cases it is possibleto attain the desired recult according to the present invention by treating cellulose with a concentrated organic acid, for example with glacial acetic acid, preferably in the heat.

Strong acids Fourth method-This method consists in treating cellulose, preferably with stirring or otherwise agitating, with strong sulphuric acid of a concentration which is incapable of dissolving the cellulose or a substantial part thereof.

Thus, for instance, cellulose preferably in a finely divided state is immersed in; or otherwise degradation, the duration of the treatment is, for

instance, between about 6 and 12 hours.

Fifth method.-This method consists in treating, preferably with stirring or otherwise agitating, cellulose in a finely divided state at room temperature or at-a temperature aboveor below room temperature with strong sulphuric acid of a concentration which is capable of dissolving cellulose, treating the cellulose with the sulphurir acid at room temperature or at 20 to 30 C. until it dissolves in the acid and then at the same temperature until a degradation product forms which has the properties set forth above. Thereafter the solution or paste or magma is precipitated with hot or cold water or another precipitant therefor, for example alcohol or a solution of a salt or a dilute acid or the like.

Sixth meth0d.This method consists in treat-.

ing, preferably with stirring or otherwise agitating, cellulose preferably in a finely divided state at room temperature or at a temperature not substantially exceeding room temperature with strong hydrochloric acid, e. g. of 33 to 34 per cent. strength until the cellulose is converted into a product having the properties defined above. In general, the desired result according to the present invention is attained after a comparatively long treatment, for example after 12 to 24 hours or longer.

Seventh method-This method consists in treating cellulose at a temperature not substantially exceeding room temperature or at a temperature below room temperature with gaseous hydrochloric acid in presence of a small or moderate amount of water until the cellulose is converted into a product having the properties defined above. The water may be introduced either by using the gaseous hydrochloric acid in the moist state,(which is the case when the gaseous hydrochloric acid is not dried before coming in contact with the cellulose) or by using a parent cellulose containing moisture or by moistening the parent cellulose.

This method can also be carried out at a raised temperature, for example at 40 to 100 C., for example in such a manner that the cellulose is first saturated'with the gaseous hydrochloric acid and then transferred to a closed vessel, for example a pressure vessel and heated to 40 to 100 C. until the cellulose is converted into a product having the properties defined above.

Eighth method.-This method consists in treating cellulose in presence of alkali, for example in presence of a caustic soda solutionof 18 to 20 per cent. strength with a small proportion (for example 0.2 to 2 per cent.) of chlorine until the cellulose is converted into a product having the properties defined above.

Ninth method.This method consists in treating cellulose with chlorine or bromine in presence of water, which may be introduced, as described in the seventh method until the cellulose is converted into a product having the properties defined above. (In presence of water the chlorine exerts a hydrolyzing or degrading and oxidizing .action. on cellulose.)

Tenth meth0d.This method consists in treating cellulose preferably in a finely divided state with a strong organic acid, for example glacial acetic acid, containing chlorine or bromine, at a raised temperature, preferably at a temperature of 30 to C. until the cellulose is converted into a product having the properties defined above.

Eleventh meth0d.-This method consists in treating cellulose preferably in a finely divided ment with the hydrochloric acid in small portions) at a raised temperature, for example at a temperature between 40 and 70 C. The treatment is conducted until the cellulose is converted into a product having the properties defined above. In general, the desired result according to the present invention is attained after 1 to 2 hours.

In all eleven methods described above, after the treatment is completed, the product must be washed with water or alcohol or the like until free from acid.

Regardless of whether the hydrolyzing or degrading or hydrolyzing or degrading and oxidizing agents, particularly acids, are used in the concentrated or more or less diluted state, care must be taken that the treatment is carried out under such conditions as to ensure the production of a degradation product of cellulose which is soluble or partially soluble or incompletely soluble in caustic alkali solution or at least dispersible or partially or incompletely dispersible are introduced therefrom or on being dried. To

avoid great losses in substance, it is further recommendable not to drive the treatment so far tion whether or not the' desired endpoint is reached. For example, if after a certain time of treatment the degradation product ofcellulose has become more or lessfriable, for instance if it canbe easily pulverized or easily crushed or ground, the treatment can be regarded as completed.

When the endpoint or endpoints of the treatment of a certain type of cellulose with a certain degrading or hydrolyzing agent, for example acid of a certain concentration and at a certain temperature are determined by one or more preliminary experiments as described above, no further preliminary experiments are necessary if it is desired to produce a degradation product of cellulose having the desired properties by means of the very same treatment with the very same materials and at the sametemperature.

Since also other substances or mixtures of substances or other materials and also some physical means (for example heating with or without pressure in absence or presence of drganic or inorganic substances, such as Water or glycerineor oils or liquid or solid hydrocarbons, salts, etc.

as to cause formation of considerable amounts I (for example amounts substantially exceeding 50 per cent. of the weight of the initial cellulose) of products which are so deeply degraded as to become soluble in water, for example glucose or a water-soluble dextrin.

Since the paramount factors giving the desired result are either the time of the treatment or the temperature of the treatment or both, to obtain the desired result, it is necessary to adapt the time of the treatment to the temperature and vice versa.

In order to ascertain the point for stopping the degradation treatment, according to which a product having just the desired properties will be obtained, for use in the present invention, it is recommended to establish the time by means of one or several preliminary experiments in which a test sample of the cellulosic material under treatmentis withdrawn, washed with water, and then dissolved in '7 to 10 per cent. caustic soda solution at room temperature orat a lower temperature, for example at 0 C. to minus 10 C., after which the resulting solution or dispersion or paste or swollen mass or magma or colloidal suspensionis spread on a glass plate and immersedin a coagulating'bath, (for example, in a dilute acid, such as 10 per cent. sulphuric acid, which if desired, may contain sodium sulphate or magnesium sulphate, or a salt solution, for example ammonium sulphate or. ammonium chloride solution). yield a coherent film in the coagulating bath or in the wash liquor or on drying, or if it falls to If this treatment does not p eces at any stage of the operation, the desired end point has been attained, and the duration of the treatment of the cellu os c material is terminated. 4} characteristic feature of the starting material of the present invention may be said to be its incapability of forming coherent films.

In some cases, particularly when a far-going degradation is aimed at, the physical condition of the washed and preferably dried product may serve as a guiding line with regard to the quesuntil a solution or dispersion or magma or the like of the degraded cellulose in caustic alkali solution having the degree of degradation defined above) which in chemistry are known as hydrolyzing or as degrading or as hydrolyzing and degrading agents can also be used in the present invention for the treatment of cellulose, it must be expressly stated that it is not intended to limit that modification of the carrying out of the present invention in practice in which cellulose is treated with hydrolyzing or degrading or hydrolyzing and degrading media to "the treatment of cellulose with hydrolyzing or degrading or hydrolyzing and degrading agents containing one or more acid substances, and as acids or acid salts.

If it is desired'to carry the present invention into efiect, i. e. to produce degradation products having the above defined degree of degradation, practically all known oxidizing agents can be used to obtain degradation products of cellulose having the aforesaid properties; a few oxidizing agents being, by way of examples to which the present invention is not limited, set forth in th following lines.

(1) Chloride of lime (bleaching powder), preferably in a solution of 2 to 15 B. at room temperature or at a raised temperature, for example at 30 to C., with or without subsequent treatment with carbonic acid for which treatment air or carbonic acid produced chemically may be used.

(2) A hypochlorite of an alkali metal, such as sodium hypochlorite, preferably in solution, at room temperature or at a raised temperature or at a temperature below room temperature, or an electric current may be conducted through a suspension of the cellulose in a neutral solution of potassium chloride.

3) A solution of chlorine or bromine in water at room temperature or at a raised temperature or at a temperature below room temperature.

4 (4) Chlorine in presence of sunlight and water at room'temperature or at a raised temperature or at a temperature below room temperature.

(5) Potassium permanganate at room temperature or at a raised temperature or at a temperature below room temperature, preferably in solution, for example of 1.5 to 4 per cent. strength in absence or presence of an alkali, such as caustic soda.

(6) Nitric acid at room temperature or at a raised temperature or at a temperature below room temperature.

('7) Chromic acid, for example in the form of potassium bichromate and sulphuric acid.

(8) Strong caustic soda solution (for example of 20 to 50 per cent. strength) in the heat and in presence of oxygen. For this purpose the oxygen of the air or chemically produced oxygen can be used.

(9)-Hydro gen peroxide or an alkali peroxide in a concentrated or dilute solution at room temperature or at a raised temperature or at a temperature below room temperature. In some cases, also ozone can be used in the present invention.

As stated above, the present invention gives particularly good results, when mercerized cellulose is used as parent material for the preparation of the degradation products of cellulose having the properties set forth above which properties are characteristic of the present invention. The mercerized cellulose may be prepared by means of any mercerizing agent known in cellulose chemistry, such as caustic alkali solution or strong mineral acids or zinc chloride solution, the preferable mercerizing agent for the pre-treatment of the cellulose for the present invention being caustic alkali solution. Thus, for instance, cellulose is steeped in caustic alkali solution of mercerizing strength, for example in a caustic alkali solution of 18 to 21 or 25 or of 30 or of 40 per cent. strength, whereupon the excess of the caustic soda solution is removed by pressing or centrifuging and the pressed residue, optionally after comminution (preferably shredding) and/or optionally after having matured for a shorter (say 12 to 24 hours) or a longer (say 48 to 200 hours) time, washed with water, optionally acidified and re-washed, and, if desired, dried. If the mercerized and washed cellulose is used in the moist state, the water contained therein must be taken into account when the concentration and quantity of the hydrolyzing or degrading or oxidizing agent used for the degradation is calculated.

Instead of being steeped in the caustic alkali solution and then pressed and centrifuged, the cellulose may be also mixed withsuch an amount of. caustic alkalisolution as is desired in the alkali cellulose.

If it is desired to use for the mercerization a dilute caustic soda solution, for. example of 8 to 12 per cent. strength, the treatment of the cellulose with the caustic soda solution must be conducted at a low' temperature, for example at C. or preferably at a temperature below 0" C.

filler-and/or another suitable colloid, such as an alkali-soluble or water-soluble cellulose ether capable of forming films, or cellulose xanthate or another cellulose derivative, or starch or dextrin, in short, any colloidal substance which is suitable for the production of finishes as herein defined.

The degradation products of cellulose may be dissolved or partially or incompletely dissolved or dispersed or colloidally suspended or converted into a paste or magma in caustic alkali solution at room temperature or at a temperature below room temperature or even at a temperature below 0 C., for example at minus 5 to minus 10 I C., or even at a temperature at which formation of crystals or freezing occurs, for example at minus 10 to minus 15 C. (with regard to low temperatures see British Specification No. 212,864).

In some cases, instead of in caustic alkali solution, the degradation products of cellulose may be dissolved or partially dissolved or incompletely dissolved'or dispersed or colloidally suspended in any other substance ormixtures of substances known as solvent or dispersion medium for cellulose or forits conversion products, for instance a solution of a strong organic base, such as guanidine or a quaternary base (or of a derivative of a strong organic base) alone or containing caustic alkali, or a caustic alkali solution containing an ammonia derivative of carbon dioxide or of an ammonia'derivative of a sulphurated carbon dioxide, e. g. urea or cyanamid or thiourea or dicyanamid or a solution of a thiocyanate, for example calcium thiocyanate or the like.

As a matter of course, this application involves in some cases the treatment of the complete or partial or incomplete solution or dispersion or paste or magma or colloidal suspension applied to the fibrous materials as herein defined with an appropriate precipitating or coagulating agent of chemical orphysical nature, for) example with any coagulating or precipitating agent or bath capable of coagulating or precipitating a solution of cellulose or of a conversion or degradation or oxidation product of cellulose or of an alkali-soluble cellulose derivative, such as viscose or an alkali-soluble cellulose ether in caustic alkali solution.

Thus, for instance, coagulating or precipitating baths containing an acid or an acid salt or an acid salt and a neutral salt of a monovalent or divalent or trivalent metal or a solution of one or more neutral salts, for example of ammonium chloride or of ammonium sulphate or of an alkali chloride or the like, which baths may or may not contain an organic substance, for instance glucose or glycerine, may be successfully used in the present invention as coagulating or precipitating baths. 7

Also water or solutions of secondary or primary alkali carbonates can be used in the present invention as coagulating or precipitating baths. These baths ofier the possibility of recovering at least part of the caustic -alkali contained in the solution of the degradation 'product of cellulose and in the case of the alkali carbonates also at least part of the coagulating agent.

The application of the solution or dispersions or pastes or magmas or-suspensions of the degradation products of cellulose having the properties defined above to fibrous materials as herein defined, such as the production of coatings, layers and impregnationsof any kind, dressings of fabrics, textile printing, book-cloth, tracing cloth, sizing of yarn, paper-sizing, paper-like surfacing, etc., and the subsequent coagulation or precipitation may be accomplished by wholly or partially impregnating, printing or otherwise covering or imbuing a fibrous material as herein defined with the solution or partial or incomplete solution or dispersion or partial or incomplete dispersion or paste or magma-or colloidal suspension of the deg adation. product of cellulose and, with or without intermediate drying, treating the materi -l witha coagulating bath, by either introducing the material into the coagulating bath or by spraying the coagulating bath on'the material or conducting the material through a mist of the coagulating bath or by any other method of applying a liquid to a fibrous material as herein defined, particularly to a textile material as herein defined.

In this inventors U. S. Patents 1,682,293, 1,722,- 928, 2,224,874, 2,231,729, 2,265,916, and 2 265,917 and in British Patents Nos. 374,964, 462,456, 474,-

1 223 and 503,830, processes and methods of applyplication ofthe intimate fiuent mixture, as defined in caustic alkali solution of the degradation products of cellulose having the properties hereinbefore defined to fibrous materials as herein defined in general and to textile materials as herein defined in particular.

- Any suitable softening agent, such as glycerine or a glycol or a sugar, such as glucose or a soap or Turkey-red oil, or a drying of non-drying oil, or a halogen derivative of a dior polyvalent alcohol, particularly a halohydrin, such as a dichlorohydrin or a monochlorohydrin or ethylene chlorohydrin, in short, insofar as it is compatible with the degradation products having the properties specified above, any substance known in the art of alkali-soluble cellulose ethers or in the viscose art as additions to viscose or to solutions of alkalisoluble cellulose ethers, may be added to the solutions or partial or incomplete solutions or dispersions or partial or incomplete dispersions or pastes or magmas or colloidal suspensions of the degradation products of cellulose prior to their application to fibrous materials as herein defined.

The intimate fiuent mixtures, as defined, of the degradation products of cellulose having the properties defined above, may also contain dissolved therein another alkali-soluble cellulosic tion product of cellulose having the properties as herein defined.

After having been treated according to the present invention, the fibrous materials (e. g.

textile materials) may be subjected to any finishing process or method or operation known in the textile art, for example as coating, impregnating, dressing-filling, sizing, printing or the like by means of any other finishing or binding material, for instance starch or dextrin or British gum or tragasol or cuprammonium cellulose or viscose or any other cellulose derivative, cellulose ethers included, or to any other finishing process or method, such as mercerization in the unstretched or stretched state or dyeing or printing etc.

With regard to the practical carrying out of the present invention in practice, the following examples are given, without restrictingthe invention thereto, the parts are by weight:

Example I, A to C A. 1000 parts of air-dry wood-pulp or cotton linters (preferably in a finely divided. state) of a quality customary in the viscose art are immersed in, or otherwise mixed with, 30,000 parts of hydrochloric acid of 0.5 per cent. strength at rooni temperature, for instance in an open or closed acid resistant vessel which may be provided with reflux cooler until homogeneous. Then the mixture is heated to 100 C. for 6 to 12 hours. Then the heating is discontinued and the product is washed, for instance on a straining cloth or in a centrifuge or the like until free from acid. Then the water is removed as far as possible by pressing or centrifuging and the prodnot, if desired, is dried.

body or cellulose derivative, such as a cellulose xanthate or an alkali-soluble cellulose ther or a cellulose ether xanthate or another colloid, for example starch or dextrin or tragasol or the like.

These combinations can be produced, for example, by mixing an intimate fluent mixture, as defined in caustic alkali solution of a noncoherent film forming alkali dispersible degraded cellulosic material with a solution of an alkali-soluble cellulosic body or an alkalisoluble cellulose derivative, such as a cellulose xanthate or an alkali-soluble cellulose ether or a cellulose ether xanthate or another colloid, for example starch or dextrin or tragasol or the like, or bymixing a degradation product of cellulose having the properties-defined above, before contacting it with caustic alkali solution, with an alkali-solubl cellulosic body or an alkali-soluble cellulose derivative, such as cellulose xanthate,

must be effected in such a manner that the other cellulosic body or cellulose derivative or other colloid is at least partially dissolved in the "intimate fluent mixture, as defined, of the degrada- In either case shredder ora kneading machine or the like with so much caustic alkali solution of 9 per cent.

strength at 15 to 20 C. as to yield a suspension containing (any water in the'material being taken into consideration) 7 per cent. of the prodnot (dry basis). As soon as the mass is homogeneous, the suspension is cooled down with continuous'stirring or kneading to 0 C. or minus 5 C. or minus 10 C. respectively and kept at this temperature for 1 hour to 10 minutes, then brought back to room temperature.

A woven fabric, such as a cotton fabric is provided by means of a suitable machine, for example a back-filling machine or a padding machine .or a spreading machine, with one or (optionally with intermediate drying) more coatings of the solution thus produced and the coated or impregnated or filled material, in the wet state or after intermediate drying, is introduced into any precipitating bath known in the Y viscose art, such as the. so-called Muller-bath,

for instance a bath containing-per litre 160 grams of sulphuric acid monohydrate and 320 grams .of sodium sulphate, or parts of sulphuric acid monohydrate and parts of sodium sulphate, or into a bath composed of 64 parts of water, 10 parts of sulphuric acid, 9 parts of glucose, 12 parts of sodium sulphate, 12 parts of ammonium sulphate and 1 to 3 parts of zinc sulphate, or into sulphuric acid of 10 to 20 per cent. strength, or into a bath composed of 11 parts of sodium sulphate, 14 parts of magnesium sulphate, 9 parts of glucose, 1 to 3 parts of zinc sulphate and 65 to 63 parts of water, or'into a bath consisting of sodlumcarbonate of 20 to 28 per cent. strength, the temperature of the bath being 45 to 50 C.

But, not only the so-called Muller-bath or any'modification thereof come into consideration as coagulating baths in the present process, but all baths known in the viscose art regardless of whether or not, in addition to the purely coagulating constituents, such as acids and/or acid or neutralsalts, they contain any other inorganic or organic (liquid, oily, crystalline or colloidal) substance or substances.

The material is washed, dried and finished in the usual manner.

It is to be understood that the material may be desulphurized or bleached in any know manner before or after it has been dried.

B. Mode of procedure as in A, but with the difference that, instead of 7 per cent., the suspension is caustic soda solution of 9 per cent. strength contains 9 per cent. of the degraded cellulose products (calculated on the dry residue).

0. Mode of procedure as in A, but with the difference that, instead of '7 per cent., the suspension in caustic soda solution of 9 per cent. strength contains 12 per cent. of the degraded cellulose product (calculated on the dry residue).

Example II, A to C The process is conducted as in Example I, A to C, but with the exception that, instead of hydrochloric acid of 0.5 per cent. strength, hydrochloric acid of 1 per cent. strength is used and that the duration of heating is only 2 to 6 hours.

Example III, A to C The process is conducted as in Example II, A to C, but with the difference that, instead of hydrochloric acid of 1 per cent. strength, hydrochloric acid of 2' per cent. strength is used.

Example IV, A to C' The process is conducted as in Example I, A to C, but with the difierence that, instead of hydrochloric acid of 0.5 per cent. strength, sul-. phuric acid of 0.5 per cent. strength is used.

Example V, A to C The'process is conducted as in Example-IV, A to C, but with the difference that, instead of acid of per cent. strength is used.

Example VI, A to C The process is conducted as in Example IV, A to C, but with the difierence' that, instead of sulphuric acid of 0.5 per cent. strength, sulphuric acid of 2 per cent. strength is used:

Example VII, A a c The process is conducted as in any one of the Examples I, A to c to VI, A to 0, but with the difierence that 100 to 200 per cent. of talcum or China clay.,(based on the amount of the degraded cellulose material) are incorporated with the solution prior to its being used as finishing agent.

\ Example VIII, A to C The resulting mass is then pressed to 3000 to 3400 parts and comminuted at 15 C. for 3 to 18 hours in a Werner-Pfleiderer shredder or another -suitable comminuting machine or in a Werner-Pfleiderer xanthating machine whose blades may be dentated. This alkaline treatment is commonly called fmercerization of the cellulose raw material. Thereafter the mass is washed in a suitable washing appliance, for example on a straining cloth or in a centrifuge or the like until free from alkali and, if desired, acidified with a weak mineral acid, such as sulphuric acid of 5 to 10 per cent. strength or hydrochloric acid, or with an organic acid, such as acetic acid of 10' to 20 per cent. strength, and l e-washed. After having been washed, the thus obtained mercerised cellulose may be dried and treated with hydrochloric acid or sulphuric acid as described in any. one of the Examples I, A to C to VII, A to C.

If the mercerized and washed cellulose is subjected to any one of the treatments described in Examples I, A to C to VII, A to C in the moist state, the water contained therein must be taken into account when the concentration and quantity of the hydrochloric acid or sulphuric acid. is calculated.

Example IX, A to C The process is conducted as in Example VIII, A to C. but with the exception that, instead of hydrochloric acid of 0.5 to 2 per cent. strength or sulphuric acid of same strength, hydrochloric acid or sulphuric acid respectively of 0.05 to 0.2

sulphuric acid of 0.5 per cent. strength, sulphuric per cent. is used.

Example X, A to C The process is conducted as in Example VIII,

A to C, or m, A to 'C, but with the difference that the duration of heating is only 1 to 2 hours.

Example XI, A to C The process is conducted as in any one of the Examples VIII, A to C, to X, A to C, but with the difierence that the heating is conducted at 50 C.

Example XII, A to C a The process is conducted as in any one of the Examples VIII, A to C to XII, A to C, but with the difference that, instead of being pressed to 3000 to 3400 parts, the alkali cellulose is pressed to 2000 to 2500 parts.

' Example XIV, A to C The process is conducted as in any one of the Examples VIH, A to C to XIII, A to C, but with the difference that, instead of the caustic soda solution of 18 to 20 per cent. strength, a caustic soda solution of 25 to 40 .per cent. strength is used for the preparation of the alkali cellulose.

Example XV, A to C The process is conducted as in any one of the Examples VIII, A to C to XIII A, to C, but with Example XVI, A to C 1 Mode of procedure as in any one of the Examples VIII, A to C to XV, A to C, but with the diiference that, instead of being prepared by steeping the cellulose in an excess of caustic alkali solution and removing the excess by pressing, the alkali cellulose is prepared by mixing the cellulose in a suitable mixing apparatus, for example a shredder or a kneading machine or a mill or a disintegrator or an edge runner or the like with an amount of caustic alkali solution corresponding with the quantity of caustic alkali which is desired to be present in the alkali cellulose, i. 9. corresponding with the quantity of caustic alkali remaining in the alkali cellulose used in the relative examples after pressing to 2000 to 3400 parts. The mixing of the cellulose with the caustic alkali solution may be conducted at room temperature or at a temperature above room temperature, for example at 24 to 30 C., or with cooling, for example to 15 C. or C. or lower. The time of'mixing may be varied between wide limits, for example from 1 hour to 24 hours or longer.

Example XVII, A- to C 1000 parts of air-dry wood-pulp or cotton linters (preferably in a finely divided state) of a quality customary in the viscose art mixed with, 30,000 parts of hydrochloric acid or sulphuric acid of 0.5 per cent. strength at room temperature in an acidresistant vessel, which may be provided with reflux-cooling and then heated to.

responding with 1000 parts of the dry residue (if I used in the moist state it is necessary, prior to, its use, to determine the water content) are mixed at 18 to 20 C. for 3 to 12 hours in a suitable mixing apparatus, for example aWerner- Pfleiderer shredder or a kneading machine or the like with 1000 to 2400 parts of caustic soda solustrength is allowed to standat 18 to 25 Clfor 40 to 96 'hours.

Example XIX, A to C 1000 parts of air-dry wood-pulp (preferably in a. finely divided'state) of a quality customary in the viscose art or cotton linters of similar quality are mixed in a suitable vessel with 20,000

tion of 20 per cent. strength at 15 to 18 C. (if

the mass is used in the moist state the water adhering to the product is to be taken into account and an appropriately strong caustic soda solution is to be used). i

Immediately after shredding; the NaQH content of the product thus obtained is determined and the product mixed with so much caustic soda solution of appropriate strength as, on taking into account the proportion of NaOH contained in the mass after shredding, to yield a suspen sion containing '1 per cent. or 9 per cent. or 12 per cent. respectively of celluloseand 9 per cent. of NaOH. After having stood at room temperature for a shorter (for example 1 hour) or longer (for example 3 to 6 hours) time. the suspension Example XVIII, A to C The process is conducted as in Example XVII, A to C, but with the exception, that the mixture with the caustic soda solution of 20 per cent.

to 30,000 parts of a solution of chloride of lime- (bleaching powder) of 4 B. to 10 B. until the mixture is homogeneous and allowed to stand at room temperature for 12 to 24 hours. After that time, the mass is washed in a suitable washing appliance, for instance on a straining cloth or in a centrifuge until free from chlorine, acidified with a weak organic acid, for example acetic acid of 3 to 5 per cent. strength, and then freed from the acetic acid by washing it again.

After the washing step the product may be dried and in the dried or moist state dissolved in caustic soda solution and applied to a textile material as described in Example -I, A to C. If

the product is not dried, i. 'e. used in the moist state, the water content is to be determined and ,m-ust be taken into account when calculating the strength of the caustic soda solution to be used for the dissolution of the mass.

Example XX, A to C Mode of procedure as in Example XIX, A to C, but with the difference that, instead of being washed immediately after the treatment with the solution of chloride of lime of 4 to 10 B., the product is, after removal of the excess of the solution of chloride of lime by straining or centrifguing, exposedto the action of air at room temperature for 12 to 24 hours, then washed 1000 parts of air-dry wood-pulp (preferably in V a finely divided state) of a quality customary in the viscoseart or cotton linters of similar quality are steeped in a solution containing 140 parts of potassium permanganate in 20,000 parts of water which have been mixed with 760 parts of a caustic soda solution of 4.5 per cent. strength, the mixture is well stirred and then with frequent stirring allowed to stand at 18 to 20 C. for

4 hours. Afterwards the mixture is placed on a straining cloth or another suitable Washing appliance, for example a filter press, and washed with water until free from alkali. After having removed the excess of Water by pressing. or centrifuging, the residue is mixed with 2300 to 2400 parts of caustic soda solution of 18 per cent;

strength, and the mixture with constant stirring slowly heated to 50 C. and allowed to stand at 18 to 20 C. for 12 to 36 hours. After that time the mixture is, if desired, after previous dilution with an appropriate amount of water, acidified with dilute sulphuric acid or with any other suitable acid and then decolorized in known manner. This, for instance, may be performed in such a manner that gaseous sulphurousacid is passed into-the mixture or that sodium'bisulphite in the solid or dissolved state is added to the mixture until the mixtur 'becomes colourless. The prodin Example I, A to C.

. uct of the reaction is then washed andpif desired,

Example .XXIgI, A to C Mode of procedure as in Example XXII, A to C,

but with the exception that no caustic soda solution is added to the potassium permanganate and that, instead of at room temperature, the oxidation is'carried out at 90 to 100 C., the duration being 1 hour.

Example XXIV, A t C The process is conducted as in Example m, A to C or mm, A to C, but with the difierence that the treatment of the reaction product with the caustic soda solution at 50 C. is omitted and that the washed product, if desired after suitable dilution, for instance with water, is discoloured with sulphurous acid as described in Example XXII.

' Example XXV, A to C' 1000 parts of air-dry wood-pulp (preferably in a finely divided state) of a quality customary in the viscose artor cotton linters of similar quality are mixed or kneaded at 18 to 20 C. for 6 to 12 hours in a suitable apparatus, for example a Werner-Pfieiderer shredder or a kneading machine with 5000 to 10,000 parts of sulphuric acid of 55 to 60 per-cent. strength (i. e. about 45 to 49 B.) at 15 C. After that time, the reaction mass is washed on a suitable washing apparatus, for example ona'straining cloth or in a centrifuge or the like until free from sulphuric acid.

The product thus obtained is dissolved and the solution applied to textile materials as described Example XXVI, A to C To 1000 parts of air-dry wood-pulp (preferably in a finely divided state) Of aquality customary in the viscose art or cotton linters of similar quality 3400 to 10,000 parts of sulphuric acid of 60 B. are added in small portions in a suitable apparatus, for instance a Werner-Pflelderer shredder or a kneading machine or the like at 0 C. to

minus C. and shredded or kneaded at minus 4 to 0 C. or 0 C. to plus 5 C. for 30 minutes to 2 hours, the resulting product being a tough, clear, pasty solution containin'ga small amount of unchanged cellulose or being free from undissolved cellulose. After that time, the product is precipitated with water (preferably with ice or ice water) which is added in small portions and the precipitated product washed in a suitable washcribed in Example I, A to C.

.Examples for sizing yarn follow automatically from the foregoing examples.

In certain prior patents, this inventor has disclosed the dressing of textiles with alkaline solutions of alkali-soluble cellulose derivatives, which cellulose derivatives are.,themselves capable of yielding coherent films,.-foilowed by treatment with a coagulating bath. .Such a process is not covered-in-the present case. In such a treatassures ment, the cellulose derivative is regenerated in the textile material treated, in the form 01! minute films on the fibers, whichact to stiffen the latter, but in the present case the cellulosic body is so far degraded as to be incapable of giving films, and accordingly will be regenerated in the form of innumerable discrete particles throughout the textile material and attached to the fibers thereof. Such discrete particles, as will be seen, cannot constitute stifiening means for the fibers.

The term fibrous material used in the specification and claims is, wherever the context permits, intended to include any material consisting of, or containing fibres, such as loose fibres, whether vegetable or' animal or artificial or mixed, or any kind and in any form, or textile materials as herein defined or paper in any stage of its preparation; paper pulp included.

The expression textile material in the specification and claims includes, wherever the context permits, any spun or woven textile fibres, whether animal or vegetable (for example, silk, linen, flax,-

hemp, ramie, jute, wool and particulary cotton), as well as artificial fibres of any kind (for example, artificial silk or artificial cotton or artificial wool or staple fibre any one of them in the form of yarn or fabrics or knitted goods consisting of, or containing, artificial fibres) in the form of pure fabrics or pure knitted goods or in the form of mixed fabrics or mixed knitted goods or in the form of pure or mixed yarn in skeins, cops or warps. I

In the specification and claims, the term finish is. wherever the context permits, intended to include impregnating, coating, dressing, filling,

weighting, sizing, printing, stencilling, in short every finish produced by coating the whole or part of the surface of, or incorporating with, or introducing into, the totality or part of the fibrous materials as herein defined in general or textile materials as herein defined, in particular one or more organic materials that may or may not terial by itself or in conjunction with one or alkali solution" are intended to include such more inorganic materials suitable for the production of any finish as herein defined. I

The expressions applying" and application as used in this specification includes, wherever the context permits, any manner of application, whether manual or mechanical, such as is customary in dressing, sizing, filling, weighting, impregnating, finishing, coating, or printing or stencilling fibrous materials as herein defined, whether yarn or fabrics.

The term cellulose used in the specification and claims is, wherever the context permits, intended to include cellulose and such conversion and oxidation products of cellulose whose solutions in caustic alkali olution are capable of giving coherent films.

In the specification and claims, wherever the context permits. the expressions "alkali-soluble cellulose derivative, "cellulose derivative which is soluble or partially soluble or incompletely soluble in caustic alkali solution and cellulose derivative which is at least partially soluble in caustic simple and mixed cellulose derivatives as are soluble or partially or incompletely soluble in caustic alkali solution at room temperature and at a lower temperature, for example at a temperature between room temperature and C. or lower and such simple or mixed cellulose derivatives as are insoluble or incompletely soluble or partially soluble in caustic alkali solution at room temperature, but as can be dissolved or dispersed or incompletely or partially dissolved or dispersed in caustic alkali solution by cooling their mixtures with, or suspensions or incomplete solutions in, caustic alkali solution to a temperature between room temperature and 0 C. or to 0 C. or to a temperature below 0 0., for example to minus C. or to minus C.or lower and such simple or mixed cellulose derivatives as are insoluble or incompletely soluble or partially soluble in caustic alkali solution at room temperature or at a temperature between room temperature and 0 C. or even at 0 C., but as can be dissolved or dispersed or incompletely or partially dissolvedor dispersed in caustic alkali solution by cooling their mixtures with, or suspensions or incomplete solutions in, caustic alkali solution to a temperature below 0 C., temperatures at which freezing or formation of crystals occurs, for example minus 5 C. or minus 10 C. or minus to C. or more, included.

Wherever the context permits, the term "alkali cellulose means alkali cellulose prepared in any usual manner, namely by steeping cellulose in caustic alkali solution and removing the excess of .the latter by pressing, or by mixing cellulose with such an amount of caustic alkali solu-' tion as is desired to be present in the final alkali cellulose.

Wherever the context permits, the expression degradation products of cellulose is intended to include degradation products and hydrolyzation products and oxidation products of cellulose as well as degradation and hydrolyzation products of cellulose and degradation and oxidation products of cellulose and hydrolyzation and oxidation products of cellulose.

What is claimed is:

1. A process which comprise applying to a textile material, an intimate fluent mixture con- 3. A process which comprises subjecting a,

cellulosic material to a degrading process to an extent substantially equivalent to maintaining 1000 parts of cellulose mixed with 30,000 parts of hydrochloric acid solution of 0.5% strength at C. for 6 to 12 hours, forming an intimate fluent mixture as defined by mixing about 7 to 12% of said degraded cellulosic material with an alkaline liquid and subjecting said fluent mixture to refrigeration sufiiciently to put a substantial part at least of said degraded cellulose into solution, dressing a textile with such fluent mixture, subjecting saiddressed textile to treatment with a coagulating agent which is capable of coagulating viscose, then washing and drying said dressed textile, whereby a dressed textile with a soft finish is produced.

. Y PAUL ABEL, Executor of the Last Will and Testament of Leon Lilienfeld, Deceased.