US2028769A - Treatment of textile or other materials - Google Patents

Description

Patented Jan. 28, 1936 r TREATMENT Spondon,

tion of Delaware OF TEXTILE OR OTHER MATERIALS George Holland Ellis and Ralph Charles Storey, near Derby, England, assignors to Celanese Corporation of America, a corpora- No Drawing. Application May 28, 1931, Serial l1$o1540,800. In Great Britain February 20,

13 Claims.

This invention relates to the treatment of textile materials of natural origin and to the treatment of textile and other materials of artificial origin, and more especially those made of or con- 5 taining cellulose esters or ethers, and is particularly concerned with the fixation of insoluble metallic compounds therein.

The fixation 'of insoluble metallic compounds in natural silk goods has been practised for many years, mainly with the object of weighting the goods. Such processes are not applicable to the treatment of materials made of or containing cellulose acetate or other cellulose esters or ethers probably by reason of the water resistant character of these goods. Nevertheless processes have in the last few years been devised for the purpose of incorporating metallic compoundsin'such materials. These processes overcome the inherently small absorption exhibited by\.the goods for metallic compounds by a previous or simultaneous swelling of-the goods either with an extraneous swelling agent or.by means of the weighting solution itself applied under suitable conditions. It was found that, apart from the improved properties directly attributable to the weighting as in the natural silk industry, the weighting of the cellulose ester or ether materials increases the safe ironing point of the materials, obviously a very desirable object.

the material the latter is in general first treated with a metallic compound, for example stannic chloride, and is then treated with a precipitant for the tin or other metal. The fixation is customarily effected with cold or with warm fixing solutions for example at 60 C. We have found that when practised in this way the weighting attained raises the safe ironing point of cellulose esters or ethers approximately proportionally to the quantity of weighting substance incorporated in the material, so that in order to obtain very high maximum ironing temperatures considerable amounts of weighting arenecessary.

We have now found that the maximum ironing temperature of the materials may be very considerably increased with comparatively small amounts of weighting compounds, provided that the latter are'incorporated in the material in a voluminous form, that is to say they'permeate substantially the whole of the substance of the material to which they have been applied. When the weighted material is incinerated a voluminous ash is obtained. Various means may be adopted to achieve this result and in general it appears necessary that notonly shall the material under In fixing the insoluble metallic compounds in treatment be thoroughly impregnated with the weighting metal itself, but in addition thorough impregnation with the precipitant should be. effected. We have found that high temperatures for applying the precipitant or for the fixation 5 with the precipitant are particularly conducive to this result. For example temperatures of over C., and particularly temperatures of to 100 C. may be used. The best results obtained so far have been produced by applying the fixing 10 solution at a temperature of about to C. Another factor which comes into consideration in producing the insoluble metal compound in the material in the form of a voluminous precipitate consists in applying the fixing solution and/or 15 I the solution of the weighting metal in the form of a comparatively dilute solution. Thus solutions of disodium phosphate or trisodium phosphate, or sodium sulphate, for example, may be used in concentrations up to 15%, and prefer- 20 ably concentrations of 0.5 to 5 or 10%. Preferably both these factors are utilized for the purpose of obtaining the voluminous precipitates characteristic of the present invention.

The invention as already indicated is of great- 5 est value in its application to textile or other materials made of or containing cellulose acetate or other esters of cellulose, for example cellulose formate, cellulose propionate, or cellulose butyrate, or made of or containing cellulose 30 ethers, for example methyl, ethyl or ,benzyl cellulose, since an increase in the ironing point of these materials considerably enhances their value. Films, sheets and like materials may also have their resistance to heat improved by means 35 of the present processes, and this. particular application of the invention is of the greatest advantage when used, as hereinafter described, in conjunction with a process adapted to fireproof the materials. The process may also be applied 40 to the treatment of natural silk goods and is of value in the treatment of artificial cellulosic materials, for example viscose, cuprammonium and nitro cellulose artificial silks. ,In addition, materials containing any of the above fibres in associ- 45 ation with each other and/or'in association with other materials, such as cotton orwool, may be treated.

The metal, a compound of which is to be incorporated in the goods in accordance with the 50 present invention, may be any metal capable of yielding insoluble compounds, for example tin, aluminium, barium, calcium, magnesium, chro mium and iron.; If desired, it may be chosen in accordance with any object it is desired to achieve 55 acteristic of the materials treated according to the invention. For example if a simple weighting of the material is to be achieved, tin or other suitable weighting metals may be used, while if it is desired to colour the goods with mordant dyes, mordant metals may be incorporated, for example tin, iron, chromium or aluminium. Again if in addition to'thehigh ironing point a delustering of 'the goods is required it is preferable to employ metals which canyield opaque metallic compounds in the materials, as for example the alkaline earth metals, barium being particularly important. In this connection reference is made broadly to the description in U. S. o application No. 303,602 filed 1st September, 1928. As already indicated the present processes may be' applied to the materials in conjunction with a treatment adapted tofireprgof the materials, that is to say to modify their properties in such a way that the materials do not propagate flame and preferably do not glow when a source of heat applied to ignite them removed. This aspect of the invention is most valuable in connection with artificial silks and other artificial fibres, especially those made of or containing cellulose acetate or other organic derivatives of cellulose, including nitro acetate of cellulose and also films and sheets and like materials. Nitro cellulose films and sheets may also be treated by the process. The fireproofing may be effected in any convenient manner simultaneously with or separately from the process for raising the ironing point or resistance to heat. The best fireproofing agents to use are compounds or mixtures of compounds containing a volatile element or group of elements, for example ammonia or I organic bases, and containing or leaving a substance or residue capable of comparatively easy fusion. The substances which are most valuable for this purpose are those described in British patent No. 391,105, which consists of the borates or phosphates of volatile basesor ,mixtures of boric or phosphoric acid with salts having volatile bases or of borates or phosphates with salts having volatile bases. Preferably such compounds or mixtures are employed with salts of (ammonia and especially ammonium halides, as for example ammonium bromide. Thus for instance the best agents which we have yet found for this purpose are mixtures of ammonium borate with ammonium bromide 'or of ammonium phosphate with ammonium bromide. If desired the fireproofing treatment may be applied simultaneously with any part of the ironproofing treatment characteristic of the invention. We have however found it convenient to apply the fireproofing treatment separately from the ironproofing treatment characteristic of the invention, and in fact to apply the fireproofing treatment subsequent to the ironproofing" treatment, it being convenientto apply any desired dyeing or 001- curing treatment between the ironproofing and the fireproofing treatment.

It is desirable in applying high percentages of fireproofing substance to the materials to be dried therein to employ in conjunction with the fire-v proofing substance, for example ammonium bromide and ammonium phosphate, a suitable to electrolytes, so that they are compatible with the solutions applied for fireproofing purposes.

soluble metallic compound adapted to yield on For this purpose we have found that the modern wetting agents which are highly sulphonated are particularly suitable, and especially highly V sulphonated aliphatic hydrocarbons, acids or alcohols. The sulphonated amides of higher fatty 5 acids, for instance the sulphonated ethylene diamide of oleic acid, are also suitable.

Any convenient method of application may be utilized to impregnate the materials with the treatment with a suitable precipitant the ironpr'oofing compound of the invention. In the case of natural silk goods or artificial cellulosic materials, simple impregnation with soluble salts of the desired metals is usually suflicient. When treating materials made of or containing cellulose acetate or other cellulose esters or ethers, special measures have in general to be taken to introduce the metals in a satisfactory manner, and reference is made to U. S. Patents Nos. 1,631,-

062, 1,731,298, 1,806,048, 1,817,741, 1,821,464 and 1,867,658 and U. S. applications S. Nos. 143,789 filed 23rd October, 1926, 228,506 filed 24th October, 1927, and 406,537 filed 11th November, 1929 The metal salt solution used to apply the metal may itself be a swelling or gelling agent for the material, as for example in the case of stannic chloride, stannic chlorothiocyanate or barium thiocyanate, or a gelling or swelling agent may be caused to act upon the material either simultaneously or prior to the treatment with the metallic salt solution. A combination of such methods of increasing the. absorptive power of the fibre or material for the metal salt may be employed. Examples of suitable gelling or swelling agents for cellulose esters or ethers are given in the patents referred to. They may for example 40 be aqueous solutions of thiocyanates, of glycollic acid, lactic acid, acetic acid, ethyl alcohol,

acetone, diacetone alcohol, diacetone phenol,

'hydroquinone or other water soluble phenols or polyhydric phenols, the mono and di-ethers or esters or ether-esters of ethylene glycol or other glycols or of polyolefine glycols, e. g. glycol mono methyl ether, glycol mono. ethyl ether, glycol mono acetate, and methyl-glyco1 mono acetate or diethyl lactate or other ester swelling agents.

The solutions of the soluble metal compounds I may be applied by simple bath treatments orby local application of the metal may be achieved,

for example, by printing or spraying methods.

In the case of artificial materials, a further methodfor impregnatingfithe materials with the metal consists in incorporating a compound of the metal in question in the'spinning. solution used for the manufacture of the materials. Such a method is described in US. application S. No. 455,969 filed 26th May, 1930. The spinning solutions may be spun by dry or wet methods, the coagulating bath in the latter case being so chosen that substantial elimination of the metal from the filaments or other products does not take place.

The conditions under which the fixing solution is applied or under which the fixing is eifected is the factor which affords the most valuable means of achieving the voluminous precipitate or precipitates yielding voluminous ash characterisuiiscontinuously ning by dry or wet methods.

tic of the invention. High or comparatively high fixing temperatures, especially when used in conjunction with the application of the precipitant or weighting metal solution in relatively dilute solution, afiord the most suitable means of carrying the present'invention into efiect. Any suitable precipitants may be used, for example disodium hydrogen phosphate or trisodium hydrogen phosphate (especially when the metal has been applied by padding; spraying or other mechanical impregnation methods without subsequent washing as described in U. S. application S. No. 406,537 filed 11th November, 1929), ammonium phosphates, sodium sulphate, particularly for use with barium as the metal, and sodium carbonate, more especially for use when mordant metals are applied. Similarly, instead of sodium or ammonium salts, other soluble salts may be employed. If it is desired to reduce the water-permeability of the goods, soaps or the corresponding, acids may beused as the precipitants as describedin U. S. applications S. Nos. 374,288 filed 27th June, 1929 and 378,821 filed 16th July, 1929.

The precipitants may be applied in the form of a bath, or again as with the metal compound itself, may be applied by spraying, printing, padding or other mechanical impregnation methods, and reference is made to of such processes in U. .8. application S. No. 406,537 filed 11th Novembe 1929 and Patent No. 1,847,816. .The best results are obtained by effecting the fixation at comparatively high temperatures, such as 80 to 90 C. These temperatures may be achieved either during the actual application of the fixing or precipitating solution, or the goods carrying the metals may be first impregnatedwit-h the fixing solution and subse quently raised to the desired temperature to effect the fixation. Thus the invention contemplates not only bathtreatments at the high temperatures. but in addition contemplates applying the precipitating solution by padding, spraying or other methods either at high temperatures or at low temperatures followed by fixation -at high temperatures. If the goods are liable to be delustered at the temperature used for the fixation, preventive measures may be adopted if such delustering is not desired, as for example by the use of salts or sugars as described in U. S. Patent No. 1,765,581 and U. S. Patent No. 1,808,061. In the case of incorporating a soluble metal compound in the spinning solution used for the manu facture of artificial materials, the precipitant may be contained in the coagulating medium when using wet spinning processes or in a subsequent treatment bath, applied either continuously or with the spinning, when spin- By the above means the weighted material yields upon incineration a very voluminousv ash, so that the whole of the substance of the material may be presumed to be impregnated with the insoluble metallic compound. This is probably responsible for the very high*ironing points obtained. We find in fact that by means of the present invention the ironing point of a cellulose acetate fabric may be raised by 3 or 4 times as much as when the materials are weighted by the previous methods with two or three times the amount of the weighting agent. Thus with a cellulose acetate fabric which has a normal safe ironing point of 220 to 230 0., whereas the known weighting treatments may raise the safe ironthe detailed description off well, first hot and then ing point to 260 to 275 C., the safe ironing point may be raised by means of the present invention to 300 0., and in fact the fabric or other material may remain unmelted at as high as 340 or 350 or even 360 C., and this with an ash of 0.5 to- 2%, and especially 1 to 115%. When it is considered that cotton is readily scorched at a temperature of 260 to 280 C., the extreme value of the present invention in the treatment of materials of cellulose acetate or other cellulose esters or ethers will readily be appreciated. Such materials having an ironing point above 260 to 280 C. are entirely novel products and form an important part of the present invention.

As already indicated, the materials treated in accordance with the present invention may have various properties depending upon the type of insoluble metallic compound which has been incorporated therein. For example they may be delustered due to the presence of an opaque metallic salt, they may have the property of fixing mordant dyestuffs to obtain the true lake shades, or they may have improved impermeability to water, particularly if insoluble metallic soaps have been fixed therein in accordance with the process claimed broadly in U. S. applications filed 16th July, 1929.

In addition to their affinity for the dispersed insoluble colours and affinity for mordant colours depending on whether or not a mordant compound has been applied, the materials may have acquired an afiinity for a large number of direct and acid dyestuffs, which is especially useful from the point of view of obtaining discharge effects thereon. Cellulose ester materials may, previous or subsequent to the application of the weighting metal, be saponified as described in U. S. application S. No. 363,706 filed 16th May, 1929, such saponification being effected, if desired, simultaneously with the fixation of the metal, for example by fixing with a solution of trisodium phosphate at a suitable concentration, or with any other suitable precipitant in conjunction with caustic alkali or other saponifying agent. The materials may then exhibit an afiinity for direct cotton colours, vat colours of all kinds, the sulphur colours and mordant colours, both natural and artificial, and reference is made to U. S. application S. No. 363,706 filed 16th May, 1929 for further details in this respect and also for details of obtaining discharge effects upon materials so coloured.

The following examples illustrate the invention but they are not to be considered as, limiting it in any way:-

Example 1 ,the batching operation. They are then batched at G. for 4 to 5 hours, after which the fabric is passed withbut intermediate washing into a bath of 30:1 volume ratio containing a 5% solution of trisodium phosphate at 85 C. The fabric is treated in this bath for 10 minutes, washed cold, and finally soaped in a solution containing 1 gram per litre of soap at C. ;for 15 minutes. The fabric S. Nos. 374,288 filed 27th June, 1929 and 378,821

treated in this manner gives an ash of 1.5 cal- 3 culated as SnO-z.

Example 2 justed so that the fabric feels quite 'dry on emerging'. The fabric is then passed directly into water at 90 to 100 C. for 10 minutes, treated at the same temperature in a bath containing 37% of trisodium phosphate on the weight of the goods and a volume ratio of :1 for 15 to minutes.

The goods are then washed ofi thoroughly, and finally soaped in a solution containing-1 gram per litre of soap for 15 minutes at 45 C. The fabric so treated has acquired a matt appearance and is analogous in properties to that described in Example 1.

The fabric may then be dyed by any suitable method, as for example by means of the dispersed insolubie colours now customarilyapplied to cel-' lulose acetate.

litre 0t ammonium bromide, 100 grams per litre" of ammonium phosphate and 50 grams per litre 3G of Igepon A and dried without washing.

Example 3 A fabric is treated exactly as described in Ex ample 2 with the exception that instead of 20:1

bath containing 37% on the weight of the goods Erample 4 A mixed lining fabric composed of cotton warp and cellulose acetate weft yarns is processed ex actly as described in Examples 1, 2 and 3, Greatly enhanced resistance to ironing and hot pressing treatments renders the fabric particularly valuable in practical usage for lining purposes.

What we claim and desire to secure by Letters Patent is: v i 1 v1. Process for increasing the heat resistance of materials comprising an organic ester of cellulose, which comprises incorporating therein a small proportion of an insoluble compound of a metal by impregnating the material with a comof the metal and fixing the metal therein, by' means of a dilute solution of an alkaline. fir.-

ing agent, at a temperature of 75 to 100 C., the

small proportion of an insoluble compound of a metal by impregnating the material with a compound of the metal and fixing the metal therein, by means of a dilute solution or an alkaline fixing agent, at a temperature of 85 to 100 C., the conditions of treatment beingsuch that the amount of metal compound incorporated in the material imparts thereto an ash content of 0.5 to 2%.

3. Process for increasing the heat resistance of materials comprising an organic ester of cellulose, which comprises incorporating therein a small proportion of an insoluble compound of After such treatment the fabric is padded in a solution containing "150 grams per tin by impregnating the material a compound of tin and fixing the tin therein, by means of a dilute alkaline solution, of a phosphate, at a temperature-oi 85 to 100 C., the conditions of treatment being such that the amount of tin compound incorporated inthe material imparts thereto an ash content of 0.5.to 2%.

4. Process for increasing the heat resistance of 4 materials comprising cellulose acetate, which comprises incorporating therein a small proportion of an insoluble compound of a metal by impregnating the material with a compound of the metal and fixing the metal therein, by means of a dilute solution of an alkaline fixing agent,.at a temperature of 75' to 100 C., the conditions of treatment being such that the amount of metal compound incorporated in the materialimparts there- :which comprises incorporating therein a small proportion of, aninsoluble compound of tin by impregnating the material with a compound .of tin and fixing the,tin therein, by means of a dilute alkaline solution of a phosphate, at a tom perature 0105 to 100 C., the conditions of treatment being such that the amount of tin compound incorporated in the material imparts there-- ment being such that the amount of tin compound incorporated in the material imparts thereto an' ash content of 0.5 to 2%.

'7. Process for increasing the heat resistance of textile materi comprising cellulose acetate, which comprises incorporating therein' a small proportion of an insoluble compound of tin byimpregnating the material with a compound of tin and fixing the tin therein, by means of a 5 to 10% solution of trisodium phosphate, at a temperature of 35 to 100 C., the conditions of treatment being such that the amount of tin compound incorporated in the material imparts thereto an ash content of 0.5 to 2%.

5 8. Process for increasing the heat resistance of textile materials comprising cellulose acetate, which comprises incorporating therein a small proportion of an insoluble compound of a metal by impregnating the materials with a dilute solution of a compound of the metal and fixing the metal therein, by means of a dilute solution of an alkaline fixing agent, at a temperature of '75 to 100 C., the conditions of treatment being such that the amount of metai compound incorporated in the material imparts thereto an ash content of 0.5 to 2%.

9. Process for increasing the heat resistance of textile materials comprising cellulose acetate, which comprises incorporating therein a small proportion ,of an insoluble compound of .'tin by impregnating the materials with a dilute solution parts thereto an ash content of 0.5 to 2%.

' Process for-increa ing the heat resistance of textile materials comprising cellulose acetate which comprises incorporating therein a small proportion of an insoluble tin compound by impregnating the material with an aqueous solution containing 125 grams per litre of stannic chloride crystals and 100 grams per litre of ammonium thiocyanate and fixing the tin therein by means of a solution of trisodium phosphate of substantially 5% concentration at a temperature of 85 to 100 C., the conditions of treatment being such that the amount of tin compound incorporated'in the material imparts thereto an ash con tent of 0.5 to 2%.

11.'Textile materials comprising organic derivatives of cellulose .and containing a small proportion of an insoluble metallic compound in a form yielding on incineration a voluminous ash of 0.5 to 2%, and having a safe ironing point oi vat least 300 C.

containing a small proportion of an insoluble tin 10 compound, said materials yielding on incineration a. voluminous ash of 0.5 to 2%, and having a safe ironing point of at least 300 C.

GEORGE HOLLAND ELLIS. RALPH CHARLES STOREY.