IL37159A - Treatment of synthetic fibres - Google Patents

Description

of synthetic fibres invention to a process for modifying synthetic materials in fibrous to materials so It is vel to treat textiles comprising synthetic fibres with softening agents such as polyethylene of ethylene oxide phenols or and eationie compounds such as amine or aminoamide softener is preferably applied the wet fabric just after ing and it is highly desirable that it exhusts on to Many conventional agents fail this and even when exhaustion does it is a high proportion of the so ener a considerable amount of the softener lost on washing the It now been found by the use of certain synthetic materials having improved in particular textiles having a and more resilient handle and improved an soil release antieoil redeposi and antistatic has also been found that these substances can exhaust onto the fibres in many cases practically and that the effects are resistant to trashing and dry These thiols may also serve as spinning lubricants and as knitting and weaving is also known Patent to impart antistatic properties to synthetic hydrophobic textile by with a composition comprising polyoxyalkylene compounds containing at least terminal groups selected from o is hydrogen or lower and certain The present invention provides a for ing synthetic fibres containing polyvinyl alcohols or cellulose triacetate or mixtures or blends whleh process treating the in the absenoe of keratinous with a polyhiol having at least two thiol groups per molecule and containing a radical of a polyhydric bound to this at least two bound through oxygen atoms to carbon atoms the said pol at least two residues selected the group prising an residue of a aliphatic carboxylie acid and the after removal of a hydroxyl of a aliphatic and curing the polythiol on the The present Invention further provides synthetic fibrous the absence of keratinous ing thereon a polythiol as aforesaid the cured or still with an in structure those used in the patent mentioned in which case treatment and curing the and the can take place in any desired For the fibres may be impregnated with a miKture of the aminoplast and the and the the aminoplast and pol thiol are Or the fibres may be impregnated first with the and with the or vice then the aminoplast and polythlol are Or an aminoplast can be cured on the which are then treated with the polythlol and the polythlol is In place of the be used other resinous or substances which can be on the synthetic for example epoxide Synthetic fibres which may be subjected to the cess of the present invention may be in the of loose and knitted fabrics and and woven and tufted and other fibrous and are preferably polyamides and polyvinyl The is taken herein to include made fibres of origin in which all three available hydrox groups per anhydrogluco unit have been chemically mod by etherif or cyanoethyl tio cellulose triacetate is for the purpose of this as a synthetic Mixtures of two or more synthetic fibrous or blends with cellulosic may also be but is should be clearly understood that blends of synthetic fibrous materials with material are not included within the scope of the present Polythiols used in the process of this invention contain and preferably not more than six thiol groups per Especially good results have obtained with those containing two or three thiol groups per Preferred polythiols are those having a molecular weight between and particularly those of X in which is an integer of at least 1 and may have different values in each of the p and n is a positive integer of at most p is a positive integer of at least q is a positive integer such that equals at least 3 and at most each group contains a chain of at least 2 and at 6 carbon between consecutive oxygen represents an aliphatic radical containing at leant 2 carbon and X represents on aliphatic radical containing at least The units in individual chains be They nay be if by phenyl or There be thus used the partially or fully esterified of the in which and have the meanings previously and r is a positive integer which be as high 18 or even Further are esters of the formula in which ass u is a positive integer of at Host and represents an aliphatic radical having at least 2 and at 6 carbon Yet furthe p and u have t e ngs prev ously gn represents 2 or is zero or such that equals 2 or denotes an integer of at least 3 and at 2 and E represents an alxphatic hydrocarbon radical having at least 3 and at most Still further preferred are esters based on ethylene or propylene and ethylene oxide propylene or and those of the formulae H SH 2 t 2t u 2u SH t 2 J t 2u H SH SH CH H SH u 2u and CH an integer of at least 2 and and CH in the polythiol having an average molecular weight between 1000 and where ra has the previously Polythiol esters preferred for the purposes of the present invention are those obtained from glycerol or propylene propylene and thioglycollic of having a weight within the range to or even 2 3 o 2 OH and CH having a molecular weight within the range 1000 to where has the meaning previously Such esters are These pol esters are readily prepared he reaction of a alcohol with an alk oxide followed by partial or complete ester fication of the terminal hydroxyl groups with a propylene pol and adducts of alkylene oxides with or such as diethanolanine and tetrakis Suitable alkylene oxides include ethylene propylene tetrahydrofuran less If the alcohol be treated with one alkylene say propylene and then with a different alkylene such as ethylene The preferred acids for the ester cation as already thioglyeoilic acid and but other mercaptomonocarboxylic acids which be used include mercaptoundecylic acid and mercaptostearic The second class of includes those in vh R de or C lkylene and u have the meanings previously and v is an of at least 1 and have different The lene units in individual pol chains may likewise be but are pr the and may be substituted if desired by phenyl or Preferred such ethers are those which are also of in which and have the meanings previously and further preferred are those of the formula in which R and have the meanings previously The particularly preferred ethers are of in which R and have the meanings prevooisly 3 The ethers of formula I in which denotes may be prepared in a known Eianner by reaction of an alkylene oxide with a polyhydric etherif on of the hydroxy1 product vith and treatment with to replace the chlorine by a sulphhydryl see United States Patent and United Kingdom Spec fications In cases the average number of thiol groups per molecule is not an integer for raay be This is attributable partly to the replacement of the chlorine atoms by the not to and partly to for the ether by reaction with epichlorohydrin also react with so an Ethers of formul 2 R t and p have the previously are likewise part cul rly Ethers of formula I in which R denotes may be prepared by treating the product vhich obtained from n alkylene oxide and the polyhydric alcohol first with an alkylene oxide and then with sodium hydrosulphide see United Kingdom Specification The most preferred ethers are of formula where has the meaning previously especially such ethers having a molecular weight within the range 700 to 500 up to The ether of formula I in which R 3 denotes C SII or O SH are obtainable cy v u 2u esterifi cation of the corresponding alcohol with a acid H00CC u 2u Many of these are insoluble in water but can be applied as aqueous dispersions or They may also applied organic solvents for example lover such as ethyl alcohol lover ketones such as ethyl methyl ketone and hydrocarbon solvents chlorinated fluorinated carbons containing not more than tr chloroethylene and perchloroethyiene The amount of the polythiol to be used depends on the effect For nost purposes froa to by weight calculated on the weight of the material to be treated is The or handle of the material will of course depend on the amount of polythiol and by simple experiment the least amount re uired to give the desired effect may readily be the composition of the fibres and the construction of the fabrics also influence the amount of polythiol a of from about to gives the required Whe are employed in conjunction with the they per at least groups of ly attached to nitrogen atom denotes a hydrogen an group of from one to fou carbon atoms or an acetyl Examples of such are the and derivatives of the following amides and like substances and the cyclic ureas having the formula in wh ch Y denotes either a group of formula HC CH which be and hydroxy and which nay be interrupted by denotes an alkyl hydroxyalkyl group containing up to carbon atoms and denotes oxygen or of such cyclic ureas are ethyleneurea dihydroxyethl eneurea uron hydroxypropyleneurea diiaethylpropyleneurea and and and Carbamates and dicarbamates of aliphatic nonohydric and dihydric alcohols containing up to four carbon and and ethylene and Melanine and other If aminoplasts containing both and or and be for a in which 1 5 of the methylol have been So etherified or The is usually applied as such if when a ure or product is to it be in situ in a conventional manner a formaldehyde concentrate o concentrate and the requisite additional urea or and he applied aqueous or they may applied aqueous solutions in the solvents already or from solutions in mixtures of vater and a suitable such as The proportions of the polythiol and the can vary usually there will be per thiol group equivalent of the 2 to or but usually to or group equivalents of the The desired effects may not be fully obtainable until substantially all the polythiol on the material has At temperatures this take from to ten days or even The curing reaction be greatly b the use of a catalyst and generally it is preferred to add the catalyst to the material to be treated at the same as the polythiol is although it be added before or afterwards if The curing can be controlled by selecting an appropriate catalyst and the choice of curing time will depend on the particular application of the process according to the The catalysts may be containing organic catalysts such as peroxides and combinations of As organic bases there may be u3ed primary or secondary amines such as the lower alkanolaaines and and lower alkylena tetraethylene and and As inorganic bases there may strongly basic salts such as sodium and sodium and also organic compounds which may be used as catalysts include those in which the sulphur are not exclusively present as especially and their thiuram xanthogen sulphides and Examples of siccatives are cerium cobalt naphthenates Examples of peroxides and hydroperoxides are cumene dilauryl methyl ethyl ketone and chlorobenzoyl Yet other catalysts are salts a heavy znetal with an acid having an acid strength below or chelates of a heavy including chelates which are also B is meant one classified as i Handbook of revised 10th Book at that a metal of group or a metal of group having an atomic number at least a metal of group IVA havin an atomic number of at least or metal of group VA having an of at least the metal is a member of group or particularly the first series of such and especially and Suitable acids are mineral especially and phosphoric and organic acids such as citric Suitable chelating agents include those in which the chelating atoms are oxygen for and diketones such as such as and more acetic The amount of catalyst used can vary In general from preferably 1 to by based on the weight of the polythiol used is although larger quantities can be Curing of the polythiol takes rapidly at a pH of more than from to Curing is also assisted by using elevated from to or even the treated fibres may be heated at a temperature of to but of above to as high as may be met with if curing is combined with In high humidities curing is also The where one is may be cured under the usual at room temperature or at elevated It may be desirable to include a catalyst for curing the Catalysts which may be used include latent acid compounds be metal or mixtures or certain basic Ammonium salts which are latent developing acidity in the on include ammonium ammonium dihydrogen ammonium sulphate and ammonium These ammonium salts may be used admixed with metal salts also have similar catalytic Amine salts may also be Among the suitable latent acid metal salts are zinc zinc sine zirconium magnesium magnesium generally used at of to by weight calculated on the weight of materials of the There may also be used stronger acids such as hydrochloric or sulphuric acids which may be used as an aqueous solution as to normal or which may be dissolved in a of water and a solvent which is immiscible or partly with and also acidic Basic substances which be used include sodium bicarbonate and sodium strong acid catalysts are in liquid or gaseous heating may not be In other it may be necessary to heat the treated at a temperature of to for 30 seconds to 10 and preferably at from to for from 2 to The and the catalyst if can be applied to the material in conventional For where fabric or yarn is to be they may be padded on froia a or or the material may be immersed in a If garments or garment are to be then it is convenient to spray then or to tumble them with the or A effective way of carrying out the process of this invention comprises the fibres in an aqueous medium containing the polythiol and which is heated at a in the range from to Exhaustion onto the fibres is favoured by working under slightly acid conditions the aqueous medium having a in the range 3 to The compositions used in the process of this invention may also contain or vetting also contain repellents such as paraffin or fluorescent whitening The following illustrate the Unless otherwise parts and percentages are by weigh The thiols used were prepared as Thiol A A of 800 g of a polyoxypropylene triol having an average molecular weight and from glycerol and propylene oxide g of thioglycbllic g of and 350 ml of toluene wa3 heated to reflux with stirring for in an atmosphere of Water during the was removed as its azeotrope with The was cooled and washed with and the organic layer was On removing vacuum the solvent from the organic layer there remained 793 g of the theoretical of the desired tris ogl collate having a content of on A An aqueous emulsion of this thiol was then Thiol A 500 g emulsifying agent 50 g sodium g water g The components were mixed at room with a mixer until a uniform emulsion The emulsifying agent was an adduct of a mixture of and aliphatic amines 1 with ethylene oxide 70 This stock emulsion then diluted with 99 parts of water to form Thiol B This denotes a ether prepared a oxide adduct having an average molecular weight of about and It had a content of corresponding to SH groups per average Thiols C to were prepared as described for Thiol Their are shown in Table Table Thiol is a Thiol is similar to Thiol but the propylene oxide adduct used as the polyol had average molecular weight of Thiol M had a mercapta content of corresponding to SH groups per average C were as described for Emulsion substituting the same weight of the corresponding Emulsion for purposes of was by substituting a polyoxypropylene triol of average molecular weight OOO for Polythiol Emulsions H and 0 Emulsions N and 0 were prepared from Thiols A and G by at room temperature with a Silverson mixer the Thiol A or G 500 g emulsifying agent g sodium carboxymethylcellulose 5 g vater g The staining test referred to in the Examples consisted of immersing the patterns in an aqueous containing 2 iodine and 20 potassium iodide at room temperature for 30 were washed in water for 10 pressed between filter papers to remove excess and then allowed to at room temperature for about 10 Staining was then assessed using the Standard a value of denotes no change in and denotes a complete loss in corresponding to no and to complete of the An liquor vas prepared by adding 10 of A to 190 of The liquor vas heated to and a 10 g hank of of short st le fibres of the polyethylene vas The temperature of the liquor vas naintained at for 30 ninutes with continual movement of the yarn in the liquor by of a glass The which vas initially milky in showing that exhaustion of the polythiol onto the fibres had The yarn vas then removed from the spun in spin and further dried at The yarn so treated had a high of softness and a pleasant EXAMPLE Three impregnation liquors were each comprising the A 20 ml ffionoethanolataine aqueous solution water 175 Three 10 of a scoured polyester fabric obtained under the designation Trade were carefully weighed and placed in the impregnation liquors which were then heated to different The liquors were stirred while the respective for The of the fabric vere spun in a spin dryer and further dried as in 1 and The following were Temperature of Treatmen We f 2 60 7 3 All the treated of the fabric shoved irrproved degrees of softness and handle compared with untreated EXAMPLE Three impregnation liquors were prepared exactly as in Example and 10 of polyester fabric were carefully weighed and placed in the solutions as The of solutions in this case vere all at and times of treatment vere respectively 10 30 and 90 After these times the of the fabric were dried and The following increases in weight were e Time of Treatment Weight 10 0 7 5 30 6 90 All the treated of the fabric showed degrees of softness and handle compared with untreated EXAMPLE An impregnation liquor was the followin on A 20 The liquor was heated to and a 20 of polyester yarn was for 30 during which time the temperature was maintained at yarn was continually in liquor a after being it was 3pun in a spin dryer and dried at The impre nation liquor was virtually clear on of the showing that exhaustion of the polythiol had The yarn so treated possessed a greatly which be described as soft and EXAMPLE A plain weave fabric of polyester yarns was treated according to the method of Exairiple Exhaustion of the impregnation liquor and the fabric so treated possessed a softer and On creasing the treated in the hand and releasing it found to have greatly improved springiness and recovery to its state with untreated of crease recovery angles have confirmed this as shown by the Crease Recovery and Untreated fabric Polyester fabric treated by of Example standard test method in which specimens of fabric are creased under a standard weight and the angle Measured alter a specified is The figures quoted are the sum of the angles on cut in the warp and weft EXAMPLE 6 A series of impregnation liquors was prepared consisting the A 20 aqueous solution water These liquors were to Scoured hanks of synthetic fibres each weighing 10 g and comprising the following polyester staple fibre cellulose triacetate staple fibre acrylic staple fibre obtained under the designation Trade polyaride hand knitting yarn were iaanersed in the respective liquors and in the liquors which were maintained at for 30 The hanks were and dried as The hanks were then assessed for in handle as compared with the untreated The effect on the polyester yarn was outstandingly while pleasing softening were obtained on all the other Thiols A and B were applied to a variety of yarns perchloroethylene The yarns were dipped into perchloroethylene solutions of the thiol at the solutions also contained diethylenetriaciine as The yarns were then centrifuged so as to leave by weight of the thiol and by weight of After being dried in an oven at the yarns were allowed to stand an of relative at before the handle was assessed according to the following 0 No improvement with untreated 1 Slightly softer compared with untreated 2 Substantially softer than untreated 3 Very soft compared with untreated Handle after with Yarn Thiol A Thiol Polyester 3 3 hand 3 3 Polyaer 2 Cellulose triacetate 3 3 and are Registered Trade EXAMPLE 8 This Example illustrates that the used to prepare Thiol had negligible effect on the fibres Emulsions A and were applied to scoured fabric at a liquor ratio of using the following impregnation liquors Emulsion A or Z 20 g Water 180 of scoured Crimplene were treated with these liquors for 30 at spun in a spin dryer without and dried in an oven at for 30 minutes Some samples were also then at for 30 seconds The treated with A were softer than those treated with Emulsion the handle of which was indistinguishable from that of the untreated EXAMPLE 9 This Example illustrates the enhanced degree of fixation obtained when catalysts for curing Emulsion A are incorporated in the Application liquors having a pH of about were prepared according to Table 2 Pieces of scoured Cririplene were in a liquor for 30 minutes at The liquors which were originally milky in appearance clearer as The patterns were spun in a spin without being rins dried at for 30 and then allowed to cure overnight the thiol was then assessed by either washing the patterns in water at for 10 containing of a nonionic detergent or boiling in hexane for 10 minutes then staining the unwashed and washed patterns in iodine and assessing the difference in staining Table 2 EXAMPLE 10 Aqueous liquors containing A C and G were applied to scoured Crimplene the liquors containing on of of each of the thiols The of the liquors was adjusted to with acetic and was carried out at a liquor ratio of for 30 minutes at After 15 hydrogen peroxide uas added to the liquor so that a 1 volume concentration The liquors gradually froa thei initial white appearance The patterns spun in a spin dryer without being and dried in an oven at for 30 They vera then conditioned overnight an atmosphere relative at before of handle were carried Thiols F and G an extremely soft and pleasant handle to the Thiols A and gave a very soft while with C the handle was considerably softer than that of untreated EXAMPLE 11 Thiol A is fast to washing when applied as shown by the Thiol A applied in Example 10 to the treated patterns were allowed to condition for 3 days at room and the fastness of the finish was then assessed by The excellent fastness properties of the finish are shown by the fact there was no difference in handle or degree of staining between and patterns after the following washing treatments nonionic detergent or soda ash or scda ash plus In all cases washings were carried out for 10 at The treated patterns were unaffected by simulated perspiration tests at pH and EXAMPLE 12 In this Example the finish is applied under acidic conditions to obtain exhaustion onto the fibres and then the pH of the liquor is de alkaline to o tain fixation and curing of the was treated at a liquor ratio of with a diluted suspension of Λ set at pH with acetic the fabric being iranersed at during the course of 15 minutes the liquor substantially cleared losing its initial The liquor was then adjusted to pH 5 or by addition of either disodium phosphate dodecahydrate phosphate dodecahydrate or 5 1 disodiura phosphate dodecahydrate trisodium phosphate dodecahydrate and then hydrogen peroxide vol was added by to the solution treated with Treatment was continued for 15 at after which the cloth way spun in a spin dryer and dried at Some of the treated patterns were washed in a solution of nonicnic detergent for 10 at The handle of the treated both washed and unwashed was considerably softer than that of the untreated Iodine staining tests washed and unwashed samples indicated that there was no loss of the polythiol on EXAMPLE 13 Aqueous liquors containing emulsions and were applied to a scoured coarse polyester the liquors containing on the weight of the fibre of each of the The pH of the liquors was adjusted to with acetic acid and treatment was carried out at a liquor ratio of 20 for 30 minutes at After 15 minutes hydrogen peroxide was added to the liquor so that a 1 volume concentration The which initially were white gradually The patterns were spun in a spin dryer and dried in an oven at for 30 They were then conditioned overnigh in an of relative and at patterns were washed in a solution of a nonionic detergent for 10 minutes at 70 and conditioned as Handle assessments vers carried out on the conditioned washed and unwashed patterns and the fastness properties were also assessed by iodine The results are given in Table Handle was assessed according to the 1 Extremely soft and pleasant 2 Very soft 3 Soft Slightly softer than untreated 5 Harsh Table 3 EXAMPLE of other curing catalysts for the fixation of Emulsion A is illustrated in this A was diluted with and acetic acid was added in of fabric were treated with these for 15 minutes at C using a liquor ratio of 20 The curing were solids apidly dissolved added to the bath was continued for a further 15 under the above conditions and the fabric samples were then spun in a spin dryer without rinsing and dried in an oven at for 30 minutes Fixation of the thiol was then assessed by washing the in water containing 1 1 of a nonionic detergent for either 10 minutes at or 5 minutes at Unwashed and washed patterns were stained with iodine and the difference in staining assessed by grey scale The results are given in Table All of had a softer and pleasant handle than had A cotton blend plain weave fabric was padded with one of liquors b or c to p dried at its original dimensions on tenter at and heated for 5 at The dry crease angles of the fabric were by the Monsanto twelve six folded wise six folded being used in each test and allowed to suspended a for 3 the crease angles were values given below are the average of the six obtained by adding the warpwise value to the corresponding value and dividing by Tear strengths were determined the raethod according to Standard Three each X were and the tear strengths were Measured in the In the following denotes a aqueous solution of Table 5 EXAMPLE 16 This illustrates that antistatic properties can be imported by the thiol A 10 g piece of scoured fabric was treated with a liquor comprising Emulsion A 20 g Aqueous acetic acid Water 176 ml 30 at The which originally milky in clear as treatment After 15 minutes hydrogen peroxide was so that a 2 concentration The was spun in a spin dryer and dried in an oven at for 20 The sarple and a piece of untreated were for 30 seconds at On placing both about 6 rain a tray of cigarette the untreated became covered in the whereas there no trace on the treated 17 This le illustrates that properties and resistance to can be by the thiol was treated by the of Example but was not of treated and untreated fabric vere then in a striped pattern with three different soiling each applied as a bond 3 en vide and separated the adjoining band by an unsoiled strip of the is a of used dirty oil and petroleum is a solution of lanolin and trichloroethylene is a of sieved vacuum cleaner dust lanolin and trichloroethylene The treated patterns vere dried in an oven for 2 hours at Portions of the treated and untreated soiled fabric were then vashed for 30 at in a washing with a solution of 5 of an The fabric were then in an oven at and the resistance to soil redeposition were The treated sample lo3t nearly all of each of the soil3 on washing and there was virtually no soil redeposition on the portions of the The untreated pattern retained a portion of the soil during washing there vas deposition of soil on the regions of insufficientOCRQuality

Claims (1)

1. A process for modifying synthetic fibres containing polyvinyl alcohols or cellulose triacetate or mixtures or blends thereof which process treating the fibrest in the o a pol thiol having at least tvo thiol groups per molecule and containing a radical of a pol hydric bound to at least two bound through oxygen atoms to carbon atoms the at least two residues selected frost the group an acyl residue of a containing aliphatic carboxylic and the after removal of a of a aliphatic curing the pol hiol on the according to claim wherein the polythiol containo up to six thiol groups per Process according to claim 1 or wherein the polythiol has a weight of between and Process aocording to any of claims 1 to wherein polythiol is of in JO is of at least 1 and have different values in each of p n a positive integer of at p is a integer of at least a positive such that equals at 3 at each group contains a chain of at least 2 and at most 6 carbon between consecutive R represents an aliphatic radical containing at least 2 carbon and X represents an aliphatic radical containing at least one thiol Process according to claim vherein the polythiol is of the SH vhich and q have the assigned in and r is a positive Process according to claim wherein the polythiol is of the formula SH u in which and q have the meanings assigned in claim u is a positive integer of at roost and represents εη aliphatic radical having at least 2 and at 6 carbon Process according to claim wherein the polythiol is of the formula H in which and have the meanings assigned in claim t u has the ireaning assigned in 6 is 2 or 3 is zero or 1 such that equals 2 or 2 and R represents an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms Process according to 7 wherein the polythiol is the formula or in which alkylene and ra have the assign u has the meaning assigned in 6 2 R has the assigned and denotes an integer of at least 3 and at 9 Process according to claim 7 where in the po lythiol is of the 36 CH SH t u H SH t 2t or CH H SH 3 j t 2t E U 2U SH 2 t 2t 2u in which has the assigned in u has the assigned in and t is an integer of at least 2 and at most Process according to or wherein the polythiol is of the formula H CH 3 o or the polythiol having an average Eolecular weight between 1000 and 3β the meaning assigned in claim Process according to claim wherein the polythiol is of in vhich R denotes or y u 2u and q have the meanings assigned in claim has the assigned in claim and v is an integer of at least 1 and have different values in each of the p chains Process according to 11 wherein the polythiol is of the in which and q have the assigned in claim has the meaning assigned in claim and has the meaning assigned in claim 1 Process according to claim 12 the is of the formula in vhich and have the meanings assigned in claim R has the assigned in claim has the assigned in claim has the assigned in Process according to claim the polythiol or in which has the meaning assigned in claim 2 R has the meaning assigned in claim has the meaning assigned in claim t has the meaning assigned in claim v has the meaning assigned in claim Process according to claim l vhich the polythiol of the formula CH 3 6 2 in which 1 has the assi in claim having an average molecular weight within the range 750 to Process according to any of claims 1 to 5 which there is used from to by weight of the calculated on the weight of the synthetic Process according to any of claims 1 which the treated synthetic fibres are heated to a in the range to to cure the Process according to any of 1 wherein the polythiol is applied a solution in an organic solvent or as an aqueous dispersion or Process according to claim wherein the polythiol is applied as a solution in a chlorinated fluorinated hydrocarbon containing not more than three carbon Process according to claim wherein the polythiol is applied to the fibres by immersing them in an aqueous medium which contains the polythiol and which is heated to a temperature in the range to Process according to any of claims 1 to wherein the polythiol is applied to the fibres from an aqueous dium having a pH in the range to Process according to any one ofclaims wherein a catalyst for curing the polythiol is also Process according to claim wherein to by weight of the catalyst is calculated on the weight of the Process according to claim 22 or wherein the catalyst is a a a taining organic compound in which the sulphur atoms are not exclusively present as mercaptan a a salt of a heavy metal with an acid having an acid strength lop below or a chelate of a heavy including chelates which are also Process according to claim wherein the catalyst is hydrogen Process according to any of claims 1 to wherein the polythiol is cured at a pH in the range 5 to Process improving the handle or imparting antisoil or applying to the in the absence a pol thiol as in any of claims 1 Proceas according to any of 1 in which the synthetic fibres are of a a a a polyvinyl cellulose triacetate or of mixtures or blende Synthetic ibrous material being of a a polyvinyl cellulose triacetate or of mixtures or blends thereof from keratinous aaterial and thereon a polythiol as specified in any of 1 the cured or still curable insufficientOCRQuality