Patent Publication Number: US-3968146-A

Title: Esters of sulfothio alkanoic acids

Description:
The present invention relates to novel polymeric compounds containing thiosulphuric acid or thiosulphate groups, or their cured products, which have useful applications to textile fibres and to living human hair. 
     The invention provides novel polymeric compounds containing at least one poly (oxyalkylene) chain and at least one thiosulphuric acid or thiosulphate group (hereinafter referred to as a Bunte salt group). Compounds containing a single Bunte salt group are water soluble and may have surface active properties. Compounds having more than one, and especially more than two, Bunte salt groups in addition to being water soluble may also be surface active and can be cured to novel water-insoluble condensation products. Such curable resins can be used in textile finishing. For example they may be employed for pigment-dyeing and printing of fibrous materials such as wool fabrics, polyester fabrics, cellulosic fabrics and paper. When applied as textile finishing agents to cotton, rayon, polyamide or polyester fibres or fabrics they can impart shape stabilisation thereto. In addition they may also act as antistatic agents. When applied to keratinous fabrics they can impart shrink resist properties and additionally certain compounds can be used for flat setting and permanent creasing of the fabric. They may also be used for the treatment of living human hair. Because of their surface active properties they can be incorporated into shampoos and can impart to the hair an attractive handle. In addition they may be employed for the permanent waving or setting of hair. 
     The preferred compounds are curable and contain one or more polyoxyalkylene chains and substantially two or more Bunte salt groups each bound through a linking group to a chain terminating oxygen atom. A preferred group of such compounds comprises: 
     A. a radical of a polyhydric alcohol; 
     B. bound to this radical at least two poly (oxyalkylene) chains; and 
     C. at least two Bunte Salt groups each bound through a linking group to a chain terminating oxygen atom. Linking groups in the form of alkylenecarbonyl groups occur in polymers which are novel per se, as well as in the cured condition. 
     Compounds of especial interest contain three polyoxyalkylene chains and up to three Bunte Salt groups per molecule and have molecular weights in the range 500-10,000, especially 1,500-5,000. The linking groups may be the same or different in different poly (oxyalkylene) chains, and may be, for example, alkylene chains which may contain from 1 to 6 carbon atoms and may be unsubstituted or substituted with, for example, one or more hydroxyl groups. The linking groups may also be divalent acyl radicals or carboxylic acids. The compounds of the invention may also contain free hydroxyl or thiol groups or polyoxyalkylene chains linked together by thioether or disulphide bridges. 
     Compounds according to the invention may be represented by the general formula: ##EQU1## or of the general formula 
     
         Y.sub.1 O.sub.3 SSX -- (O-alkylene).sub.m -- XSSO.sub.3 Y  II 
    
     wherein 
     p is an integer from 2 to 6; 
     g is O or an integer from 1 to 4 subject to the proviso that (p+q) is in the range 3 to 6; 
     m is an integer of value at least 1 (most usually from 5 to 25) and may have different values in each of the p and q chains; 
     R represents a radical formed by removal of the hydroxyl groups from an aliphatic polyhydric alcohol containing at least two carbon atoms; each `alkylene` group contains a chain of at least 2 and at most 6 carbon atoms between consecutive oxygen atoms; 
     X represents a divalent group containing 1 to 10 carbon atoms; 
     Y represents a hydrogen atom or a salt forming ion or group. 
     The preferred compounds are of the general formula 
     
         R.sub.1 [(O-alkylene).sub.m O X SSO.sub.3 Y]p.sub.1        III 
    
     wherein m, X and Y and `alkylene` are as defined in formula I, R 1  represents a radical derived from an aliphatic polyhydric alcohol containing from 3 to 6 carbon atoms and from 3 to 6 hydroxyl groups and p 1  is an integer from 3 to 6. 
     The compounds may also contain disulphide linkages between polyoxyalkylene chains. Where the linkage is between chains attached to different groups R 1  the compounds may be of the formula IV. ##EQU2## wherein R 1  has the meaning given in formula III, `alkylene`, m, X and Y have the meaning given in formula I and p 2  represents an integer from 2 to 5. The compounds may also contain disulphide linkages between polyoxyalkylene chains bound to the same group R 1  and in this case may be of the general formula V. ##EQU3## wherein R 1  has the meaning given in formula III, m and `alkylene` have the same meanings as in formula I and p 3  represents an integer from 1 to 4. 
     The group R represents a radical formed by notional removal of the hydroxyl groups from an aliphatic polyhydric alcohol. Suitable radicals are, for example, those derived from ethylene glycol, propylene glycol, cyclohexane 1,4- diol, 1,1,1-trimethylolethane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol and sucrose. The group R may also comprise a hydroxy terminated adduct of one or more alkylene oxides with ammonia or an amine, examples of such compounds being the propylene oxide adducts of ammonia, ethylenediaimine, or triethanolamine. Preferably R is derived from an alcohol containing three hydroxyl groups, and the preferred radical is derived from glycerol. 
     The alkylene groups may be C 2  H 4 , or C 3  H 6  or C 4  H 8  radicals. Compounds containing C 3  H 6  and/or C 4  H 8  radicals are hydrophobic and the Bunte Salt compounds derived therefrom act as surface active agents. The compounds may, for example, contain mixture of C 2  H 4  and C 3  H 6  derived groups and may be random or block copolymers. The surface tension properties may be adjusted by selection of the ratio of C 2  H 4  to C 3  H 6  radicals. For example a suitable triol may be formed as a block copolymer by condensing glycerol with propylene oxide and &#34;tipping&#34; the resulting triol with ethylene oxide. 
     Condensation products of glycerol and ethylene oxide and/or propylene oxide are available commercially, for example those sold under the trade names Polyurax (B.P. Chemicals), Caradol (Shell Chemical Co) and Propylan (Lancro Chemicals Ltd.) 
     The group X is preferably a substituted or unsubstituted divalent aliphatic radical and may for example be of the formula 
     
         -- (CH.sub.2).sub.n -- or -- CO(CH.sub.2).sub.n-1 
    
     where n is an integer of 1 to 6, or may be of the formula ##EQU4## 
     Compounds of especial interest have molecular weights in the range 1,500-5,000 and are of the formula ##EQU5## wherein m has the same meaning as in formula I. Water soluble salts, for example the alkali metal (especially sodium), ammonium or amine salts may also be used. Other useful compounds of molecular weight 1,500-5,000 are of the formula ##EQU6## or their alkali metal (especially sodium), ammonium or amine salts. 
     PREPARATIVE METHODS 
     Polymeric compounds according to the invention may be prepared by esterifying an alcohol containing at least one poly (oxyalkylene) chain and at least two terminal hydroxyl groups with a halogen substituted carboxylic acid or functional derivative thereof and reacting the resulting halogeno-ester with a water soluble thiosulphate. If the alcohol is of the general formula 
     
         [ R ] [ (O-alkylene).sub.m OH] p+q                         VIII 
    
     where R, `alkylene`, m, p and q have the meanings given above and is reacted with an acid Cl(CH 2 ) n  COOH where n is an integer of value 1 to 5 or a chloride or anhydride thereof there is produced an intermediate chloro compound of the general formula ##EQU7## which reacts with a water soluble thiosulphate to produce a compound of formula I where X presents a --CO(CH 2 )-- n  residue. 
     The esterification reaction can conveniently be carried out by refluxing the polyol and the halogenocarboxylic acid in an organic solvent, for example toluene. A catalyst e.g. toluene -- p -- sulphonic acid is normally present and the water produced is distilled off and collected in a Dean and Stark trap. The chloro-ester so obtained can be converted to the Bunte Salt by reaction with dosium thiosulphate in an aqueous/alcoholic medium under felux. The compounds thus prepared are novel per se. 
     In an alternative method an alcohol containing at least one poly (oxyalkylene) chain and at least two terminal hydroxyl groups, for example a polyol of the general formula VIII can be reacted with the epihalohydrin, for example epichlorohydrin, followed by reacting the resulting epihalohydrin adduct with a base to produce an epoxyy terminated adduct with a water soluble thiosulphate. The polyol of general formula VII reacts with epichlorohydrin in the presence of Sn Cl 2  under reflux in an organic solvent such as toluene and subsequently with a base to produce a compound of the formula ##EQU8## where R, `alkylene`, m, p and q have the meanings previously assigned. This epoxy compound can readily be converted by treatment with sodium thiosulphate in an aqueous/alcoholic solvent into a compound of formula I wherein X represents a ##EQU9## group. These compounds are also novel, at least when cured. 
     Compounds according to the invention can also be produced by treatment of the corresponding thiol compounds with a water-soluble bisulphite and a water-soluble tetrathionate. Suitable thiol compounds have 
     a. a radical containing at least one poly (oxyalkylene) chain and at least two chain terminating oxygen atoms notionally derived from terminal hydroxyl groups; 
     b. at least two thiol groups each bound through an alkylene, hydroxy-substituted alkylene or alkylcarbonyl group to a chain terminating oxygen atom. 
     Suitable thiols are of the general formula 
     
         [ R ] [ (O-alkylene).sub.m O CO CH.sub.2 SH ]p.sub.1       XI 
    
     or of the formula ##EQU10## wherein R, `alkylene` and m are as defined in formula I and P 1  is an integer from 3 to 6. 
     The compounds of formula XI or XII can produce Bunte salt terminated compounds of the general formula I on warming with sodium bisulphite and sodium tetrathionate in an aqueous/alcoholic medium. Suitable thiol terminated starting materials are disclosed, for example, in British Patent Specification No. 1,278,934. The reaction may also give rise to compounds containing disulphide linkages, such compounds being of the general formula IV or V. Normally these disulphide compounds which are within the scope of the invention, are minor components of the reaction products. 
     CURING REACTIONS 
     Polymeric compounds containing substantially two or more Bunte Salt groups per molecule are curable and may be converted into insoluble cross-linked condensation products. It has been found that when preparing the compounds by substitution of terminal halo-atoms, substitutions of about 60% give satisfactory curable products. The resins cure on prolonged exposure to light or heating. Curing is effected by treatment with acids, bases or reducing agents. Suitable reducing agents inculde quaternary phosphonium compounds, for example THPC (tetrakis -- (hydroxymethyl) phosphonium chloride), sodium borohydride, thioglycollic acid and thiol containing compounds such as thioethanol, cysteine, thioglycerol and resins containing free thiol groups such, for example, as those mentioned in British Specification No. 1,278,934. Curing may also be assisted by nucleophilic substances such as thiourea, nitrous acid, acid hypo-chlorite, iodide ions or thiocyanate ions. Diamines, such as ethylene diamine, diethylene triamine 1,6 diaminohexane and piperazine, are valuable curing agents by the reaction 2 [--OCOCH 2  SSO 3  -- Na.sup. +  ]+ H 2  NRNH 2  → -OCOCSNHRNHCSCOO- In addition tertiary amines may promote curing. 
     The compounds of this invention may be insolubilised by treatment with polyvalent metal ions, for example magnesium ions, and it may be advantageous to treat the compounds in this way and simultaneously or subsequently treat them with a curing agent. 
     TEXTILE APPLICATIONS 
     Textile material can be treated by applying thereto a curable compound according to this invention and curing the resin on the material. The compound may be of any of the general formulae I to VII and from 0.1 to 15% of the resin, preferably 0.5 - 5% by weight of material can conveniently be applied. 
     The compounds may be applied to synthetic fibers, for example polyamide, polyester or acrylic fibres and impart an attractive handle thereto. In addition they may also act as antistatic agents. They are useful pigment binding agents on all fibres both natural and synthetic. The compounds may be applied to natural or regenerated cellulosic fibres and can impart wrinkle resist and permanent press properties thereto. 
     The compounds are of especial value for the treatment of keratinous textile materials, usually derived from the wool of sheep, or from alpaca, cashmere, mohair, Vicuna, guanaco, camel hair or llama or blends of these materials with sheep&#39;s wool. The treatment of such materials according to the invention can be used to impart shrink-resist and/or permanent press properties thereto. The wool may be mixed with other textile fibres, for example polyamide, polyester or cellulosic fibres but in the shrink-resist treatment of wool-containing fabrics generally at least 30% of the material is wool, and wool rich blends, for example 60:40 wool/cotton blends, 80:20 wool/nylon blends and 80:20 wool/polyester blends may be used. 
     The polymeric compounds of this invention may be applied to the textile material by any conventional technique, for example by padding or by exhaustion from a dyebath. In the treatment of wool the resins have the advantage that they are anionic and are compatible with wool dyes which normally contain anionic solubilising groups. Thus acid levelling, acid milling, premetallised and solubilised vat dyes can be used but for best dye fastness to washing it is preferred to use fibre-reactive dyes, i.e. dyes that can react with the keratin fibre and become covalentyl bonded thereto. The acid levelling dyestuffs can be, for example, of the azo type and should be water soluble and contain at least one anionic solubilising group, generally a sulphonic acid group. Acid milling dyes generally have a greater molecular weight and fewer solubilising groups than the acid levelling dyes, but there is no rigid distinction between the two classes. The premetallised dyes comprise a class of dyes having o,o&#39; - dihydroxy azo, o-amino-o&#39;-hydroxy azo or o-carboxyl-o&#39;-hydroxy azo groups which are co-ordinated to a metal atom, for example chromium or cobalt. The dyes may be used as 1:1 or 2:1 complexes. Vat dyes, which are most commonly of the indigoid or anthraquinone structure, are solubilised by conversion to their water-soluble leuco esters and can subsequently be developed after application by oxidation to the insoluble form. It has also been found that pigments can be applied to wool fibres by pad-dyeing or printing, with good wash and rub fastness, in the presence of a curable compound according to this invention. 
     The process is especially advantageous when combined with dyeing with an aqueous solution of a wool dye. Previous shrinkproofing resins have been found to be incompatible with reactive dyes owing either to the formation of ion complexes or to their water insolubility. A preferred process for dyeing with such a dye comprises impregnating the fibres at a pH of 5-12, e.g., by padding, with an aqueous composition comprising a reactive dye and a water soluble polymer according to this invention, a reducing agent for the keratin and an additive for facilitating penetration of the dye into the keratin fibres, storing the dyed and polymer-treated fibres in the presence of moisture to allow penetration of the dye into the fibres and deposition of the resin thereon, and thereafter subjecting the fibres to a washing treatment. If necessary the washing solution may contain 0.1-2.0% by weight of a curing agent for the resin. When producing shades on wool or similar materials by a method of impregnation followed by storage, it is accepted practice to add to the dye liquor a surfactant which produces rapid wetting of the wool at room temperature. These additions are exemplified by non-ionic condensation products of e.g. lauryldiethenolamide. The anionic Bunte Salts can themselves serve as wetting agents. 
     The reactive dyes which may be employed also include whitening agents which react with fibres in the same way. Dye-stuffs falling within this class can incorporate the following groups: 
     epoxy-, ethylene-imino-, isocyanate, isothiocyanate, carbamic acid aryl-ester-, propiolic acid amide, monochloro- and dichloro-crotonylamino, chloroacrylamino-, thiosulphato, labile halo atoms, trichloro-pyridazino-, dichloroquinoxalino-,allysulphonyl-, monochlorotrizinyl-, vinylsulphonyl-, and certain reactive ammonium or hydrazinium residues. 
     Especially good results in pad-dyeing are obtained with highly reactive dyes, for example those incorporating a 2,4 dichlorotriazinyl, 2,3 dichloroquinoxalino, 2-chloro -- 4 methoxytriazinyl, 2,4 dichloro -- 5 -- carbonyl-pyrimidine or 2,4 -- difluoro -- 5 -- chloropyrimidine group. 
     Reducing agents are preferably incorporated into the pad liquor, and examples include alkali metal, ammonium and amine sulphites and bisulphites, for example, sodium bisulphite, sodium metabisulphite and monoethanolamine bisulphite, certain quaternary phosphonium compounds, for example, tetrakis-(hydroxymethyl) -- phosphonium chloride, sodium borohydride, and thioglycollic acid and other materials capable of breaking disulphide bonds in the keratin molecule. The amount of reducing agent per 100 parts by weight of paste may for example be from 1 to 50, preferably from 1 to 20 parts by weight. Sodium bisulphite is preferred and has the advantage that it exerts a bleaching action on the wool and therefore allows very bright shades to be obtained, and also appears to promote reaction between the wool and the resin. 
     It is preferred to include an additive in the pad liquor to assist penetration of the dye into the keratin fibres. While the invention does not depend on any theory as to its mode of action, it is believed that the additive can cause swelling of the keratin fibre and/or disaggregation of the dyestuff. Suitable additives include acid amides or thioamides, for example urea, thiourea, sulphamide, or derivatives thereof, furfuraldehyde and cinnamaldehyde, and the additive is preferably present in the aqueous composition in a concentration of 100 - 400 grams per liter, especially in the case of urea about 300 g/l. 
     The simultaneous dyeing and resin treatment can be carried out by dissolving the reactive dye and the resin in water, preferably in the presence of an acid amide or thioamide, for example, urea, and in the presence of a reducing agent for the keratin, for example sodium bisulphite, and subsequently impregnating the fibres with the dye composition, for example, by impregnation with a pad mangle. The process can be carried out at ambient temperatures or from 10° to 60°C. although slightly elevated temperatures, preferably below 50°C are best. Generally speaking, temperatures in the range 10° to 60°C are suitable. The dyeing can be carried out at a pH in the range 2-12 but is preferably conducted at a pH of about 10. The fibres are allowed to remain in contact with the dye for the minimum time for proper penetration, e.g. between 10 min. and 72 hrs., typically between 1 and 24 hrs. For example, the fibres may be removed, squeezed to express liquid and then stored in the presence of moisture for 10 mins. to 72 hrs. to ensure that the bulk of resin and of the dye becomes attached to the keratinous fibres leading to a full shade development of the dye. After the storage period the fibres are normally washed off with a solution of a curing agent, for example a mixture of magnesium chloride and ammonium thioglycollate and optionally are subsequently treated with an aqeous solution of a base. Conventional equipment can be used for applying these solutions, for example, a beam washer, a winch or a conventional washing range. 
     PIGMENT DYEING 
     The resins of the invention can be used to advantage in the production of fast dyed shades on all fibres using pigments. Pigments are generally classified as water insoluble colours and their current use on textile materials is limited by the following restrictions: 
     i. Pale depths only can be achieved due to the poor rub fastness of deeper shades. 
     ii. A pigment dyeing or print always appears `glassy` to the trained observer. 
     iii. Usually up to 10% o.w.f. polymer binder is employed which has a very great effect on harshening the `handle` of the material. 
     The use of the Bunte Salt polymers either alone or in a mixture completely eliminates the above problems and allows the production of a wide range of satisfactory shades on all fibres by printing or dyeing. Printing or dyeing is carried out with a mixture of the Bunte Salt polymer, pigment and thickener followed by a curing step which may be a simple cold rinse in a solution of reducing agent or diamine, or which may be a heat curing step carried out for example for 5 minutes at 140°C. Washing in cold water completes these processes. 
     One great advantage of the pigment dyeing procedure is that solid shades can be achieved on wool/synthetic fibre blends. Other advantages include the shrink proofing effect imparted to wool and the antistatic effects and wrinkle resistance imparted to such fibres as polyester cotton. 
     TREATMENT OF HAIR 
     It has been found that the polymeric compounds of the invention can be employed for the treatment of hair including living human hair. 
     They can be formulated into a composition for the treatment of hair comprising the polymeric compound and at least one inert solvent or diluent. Such composition contains from 0.5 to 15% by weight, preferably from 2 to 6% by weight, of the polymeric compound. The composition preferably also contains a reducing agent for the keratin (other than a curing agent for the polymer), for example sodium bisulphite, and optionally also a nucleophilic substance such as thiourea. The reducing agent is conveniently present in an amount of from 0.2 to 10% by weight based on the weight of the composition. In order that the composition should have satisfactory storage stability it preferably contains at least 20% by weight of water and is adjusted to pH in the range 3 - 10, preferably about 7.  The composition may be in the form of an aqueous or aqueous/alcoholic solution and may be, for example, in the form of a shampoo or wave-setting lotion. It may alternatively be in the form of a cream or gel, the resin being dissolved in the aqueous phase thereof. The composition may contain any other conventional ingredient for use in cosmetics provided that the ingredient does not react with Bunte Salts. For example the composition may additionally contain one or more surfactants, hair dyes, pigments, perfumes, swelling agents or thickening agents. The composition may also be formulated as an aerosol. 
     In a further aspect of the present invention provides a process for the treatment of hair including living human hair, which comprises applying thereto a curable water soluble polymer containing at least one poly (oxyalkylene) chain and two or more thiosulphuric acid or thiosulphate groups and curing the polymer on the hair. The polymeric compounds when applied to hair can enhance its appearance by making it brighter and may also facilitate combing out of the hair. When the hair has become degraded by the action of, for example, sea water, sunlight, bleaching agents or permanent waving agents, the compounds may have the effect of increasing the strength thereof. The compounds may also be used for the shape stabilisation of hair and are therefore of value for incorporation into permanent waving compositions. The hair may be formed into the desired shape or configuration, a solution of the resin is applied thereto and the polymer is subsequently cured. 
     The compounds can be applied to the hair by any conventional method, for example by brushing, spraying or dipping, and preferably remain in contact with the hair for a period of 5-30 minutes. The hair is then rinsed with an aqueous solution of a curing agent, for example a mixture of ammonium thioglyvollate and magnesium chloride. 
    
    
     The invention is illustrated by the following Examples. 
     EXAMPLE I 
     A polythiol was prepared from a mixture of 800 g (0.2 g-mol.) of a triol of average molecular weight 4,000 made from glycerol and propylene oxide, 55.2 g (0.6 g-mol.) of thioglycollic acid, 5 g of toluene-p- sulphonic acid and 350 ml of toluene by heating to reflux with stirring in an atmosphere of nitrogen. Water (10.8 ml, 0.6 g-mol.) formed during the reaction was removed as its azetrope with toluene. The mixture was cooled and washed with water, and the organic layer was separated. On removal under vacuum of the solvent the organic layer there remained 793 g (94% of the theoretical yield) of the desired tris(thioglycollate) having a thiol content of 0.59 equiv./kg. 
     The above polythiol resin (1 mole) was treated with sodium bisolphite (4 moles) in water and isopropanol was added to the liquor until a clear solution was obtained. The solution was heated to 60°C for 4 hours and sodium tetrathionate (Na 2  S 4  O 6 , 2 moles) was added, the solution then being maintained at 60°C for a further hour. A further 4 moles of sodium bisulphite and 2 moles sodium tetrathionate were then added as before. A yellow oil separated from the solution and was discarded. The solution was cooled and allowed to stand overnight, and the solvent was evaporated off in vacuo to give a clear, viscous, curable, organic resin which was soluble in water and exhibited surface active properties, and the infrared spectrum of the product showed bands characteristic of Bunte Salt groups at 1030 cm -   1  and 1050-1190 cm -   1 . The product was anionic and readily precipitated when treated with the blue basic dye Basacryl Blue XRL. White precipitates of cured resin formed readily on treatment with hydrochloric or sulphuric acid, magnesium chloride, THPC or ammonium thioglycollate, and at pH 2.0 with thioglycollic acid in the presence of tertiary amines or thiourea. Boiling in dilute mineral acids produced the corresponding insoluble thiols, but disulphides can be formed under these conditions if thiourea is present. 
     EXAMPLE II 
     A triol (100g) of average molecular weight 3,000 prepared by condensation of glycerol with propylene oxide (Polyurax G3000, B.P. Chemicals Ltd) was dissolved in toluene (300 ml). Chloroacetic acid (15 g) was added together with toluene p-sulphonic acid (5 g). The mixture was refluxed for 4 hours at 110°C in an atmosphere of nitrogen and the water liberated was collected as its azeotrope with toluene in a Dean and Stark apparatus. The theoretical yield of water (1.8 ml) was recovered. The reaction mixture was washed with water and sodium bicarbonate (1% w/v) several times to remove excess chloracetic acid and catalyst, and the toluene was removed by rotary vacuum evaporation. The residual tris-chloroacetyl ester (95 g) was dissolved in isopropanol (300 ml) and sodium thiosulphate pentahydrate (30 g) in water (50 ml) was added. Isopropanol and water were subsequently added as required to maintain a clear solution, together with acetic acid to bring the pH to 5.0. Refluxing was carried out for 4 hours at 80°C with stirring and at the end of this time a sample of the reaction liquor dissolved in water without turbidity. The solution was cooled and allowed to stand for 10 hours after which it was observed that separation into two phases had occurred. The upper resin phase was separated from the lower aqueous phase which contained a high proportion of dissolved salt. The resin phase was evaporated down in vacuo to give a clear viscous resinous material (92 g) which was readily soluble in water and exhibited surface active properties. The infra-red spectrum exhibited bands of 1030 and 1050-1190 cm -   1  characteristic of Bunte Salt groups. Estimation of the Bunte Salt groups by conversion to thiol groups and subsequent titration indicated the presence of three Bunte Salt groups per molecule. 
     The reaction is believed to take place as follows: ##EQU11## 
     In like manner Bunte Salt resins were prepared from the following polyol starting materials:- Propylan G 1000, G 1500, G 3000, G 4000 and G 5000 (Lancro Chemicals Ltd) and Voranol CP 700 (Dow Chemical Co), the figures indicating the molecular weight of the polyol. 
     EXAMPLE III 
     The resin prepared in Example II decomposed over the course of a few days when allowed to stand. A composition which could be stored for prolonged periods was prepared by diluting the evaporated product with water until the solids content was 80%, and adding a buffer (disodium hydrogen phosphate) to maintain the pH at about 7. The resulting concentrated solution was stored for a period of several months without noticeable deterioration. 
     EXAMPLE IV 
     Polyurax G 3000 (100 g) was dissolved in toluene (100 ml) and stannic chloride (0.4 g) was added. Epichlorohydrin (12 g) was then added and the mixture was refluxed for 2 hours at 110°C. The solution was cooled and washed with a solution of sodium hydroxide at pH 12. The organic phase was evaporated to dryness on a rotary vacuum evaporator and the resulting epoxy-terminated resin was dissolved in isopropanol (200 ml). A solution of sodium thiosulphate pentahydrate (30 g) in water (50 ml) was added. Further isopropanol and water were then added as necessary to give a clear solution. The pH was adjusted to 7.0 and the mixture was refluxed for 4 hours. During this period a little dilute acid was added as necessary to maintain the pH at 7.0. The mixture was cooled and allowed to stand overnight. The mixture was observed to have separated into two layers, the upper of which contained a resin similar to that prepared in Examples I and II. The upper layer was separated and solvent was removed by rotary vacuum evaporation. The resulting pale yellow resin was water soluble and surface active. Its infra-red spectrum showed bands attributable to Bunte Salt groups. 
     A stable aqueous concentrate of the resin was prepared as described in Example III. The reaction is believed to be as follows: ##EQU12## 
     EXAMPLE V 
     Propylan 3 (300 g), glycerol/propylene oxide condensation product of molecular weight 3000, was dissolved on toluene (300 ml) and β-chloropropionic acid (80 g) and toluene p-sulphonic acid (15 g) were added. The mixture was refluxed for 5 hours at 110°C and the expected 5.4 ml of water was distilled off and collected at its azeotrope with toluene in a Dean and Stark trap. The mixture was cooled, washed with aqueous sodium bicarbonate and the resulting tris(β-chloropropionyl) ester was recovered by evaporation. A portion of the ester (200 g) was dissolved in ethanol (200 ml) and potassium iodide (12 g) was added. The mixture was refluxed for 1 hour after which a precipitate of sodium chloride was noted, the product now being in the form of the tris(β-iodopropionyl ester). Sodium thiosulphate pentahydrate (70 g) in water (100 ml) was added and the mixture was refluxed for 6 hours. At the end of this time a sample of the mixture when added to water was completely miscible and no turbidity appeared. The mixture was cooled and allowed to stand overnight. It separated into two phases of which the upper phase contained a pale yellow curable resin which was readily soluble in water, exhibited surface active properties, and gave an immediate precipitate with THPC. The product is believed to be ##EQU13## The remaining ester portion was similarly treated, but without iodide catalysis; no Bunte Salt was formed. 
     EXAMPLE VI 
     A diol of molceular weight approximately 2,000 containing propylene oxide derived units (Propylan D 2112  Lankro Chemicals Ltd.) (212 g.) was dissolved in toluene (150 ml) and chloracetic acid (50 g) and toluene p-sulphonic acid (12 g) were added. The mixture was refluxed for 1 hour at 125°C and cooled. The excess acid was removed by stirring with sodium carbonate (30 g) in water (500 ml) for 1 hour. The organic layer was separated and the dissolved ester was recovered by evaporation. 
     The ester was dissolved in isopropyl alcohol (200 ml) and sodium thiosulphate pentahydrate (170 g) in water (150 ml) was added. The mixture was refluxed for 2 hours, cooled and allowed to stand. Separation into 2 phases occurred, and the upper resin-containing phase was separated and concentrated as described in Example I. A water-soluble resin was obtained which exhibited surface active properties and gave an immediate precipitate with THPC. The infra-red spectrum of the product showed bands characteristic of Bunte Salt groups. 
     EXAMPLE VII 
     The following composition was applied by padding to a carbonised woollen flannel cloth and to worsted serge:- 
     
         Resin of Example I                                                        
                  30 g/l, corresponding to 3%                             
                 on the weight of fabric(o.w.f.)                          
Urea             300 g/l                                                  
Polysaccharide-base                                                       
thickener (Guaranate AP5)                                                 
                  6 g/l                                                   
Sodium metabisulphite                                                     
                  20 liter                                                
Procion Red MG (a                                                         
reactive dye)     20 g/l                                                  
 
    
     The material was wound up on a batch, covered with a polyethylene sheet and stored for 24 hours. It was then washed with water, then with a solution of aqueous ammonia (1cc 880 ammonia per liter) at 60°C for 15 minutes and then with dilute acetic acid. The area felting shrinkages determined after test washing in a 15 liter &#34;Cubex&#34; washing machine at 40°C and pH 7 at a 15:1 liquor:goods ratio are shown in Table I. 
     
                                           TABLE I                                 
__________________________________________________________________________
                       % AREA SHRINKAGE                                   
Fabric    Resin treatment                                                 
                    pH 1 hr. Wash                                         
                              2 hr. Wash                                  
                                     3 hr. Wash                           
__________________________________________________________________________
Worsted serge                                                             
          Untreated -- 32%    --     --                                   
          As Example VII                                                  
                    4   1%    3%     8%                                   
Woollen flannel,                                                          
          Untreated -- 18%    29%    32%                                  
scoured and milled                                                        
          As Example VII                                                  
                    4   0%    0%     1%                                   
(not carbonised)                                                          
__________________________________________________________________________
 
    
     EXAMPLE VIII 
     A wool serge fabric was treated by padding to the wet pick up indicated in the following Table with the following liquor. 
     
         ______________________________________                                    
Resin of Example II   38 g/l                                              
Urea                  300 g/l                                             
Procion Red Mg        100 g/l                                             
Sodium bisulphite     20 g/l                                              
Guaranate AP 5        6 g/l                                               
______________________________________                                    
 
    
     The treated fabric was wound up, covered with a polyethylene sheet and stored for 24 hours at room temperature. It was then washed as indicated in Table II and the felting shrinkage was determined by washing as in Example VII. The results are shown in Table II in which &#34;MgCl 2  wash&#34; means a wash with a 2% aqueous solution of magnesium chloride at the indicated temperature and pH values followed by a wash with 0.5% aqueous ammonia for 15 minutes. It may be seen that the red dyed material exhibited a low felting shrinkage after washing, especially when treated with T.H.P.C. or magnesium chloride. 
     Some of the fabric treated in the above manner was sprayed with a solution of monoethanolamine bisulphite to give 2% solids on weight of wool and then creased in a hot steam press. This fabric was then tested for 3 hours by the above Cubex method and it was observed that no felting shrinkage occurred and that the crease remained completely intact. Thus the Bunte Salt resins are capable of imparting very high antifelting properties coupled with permanent press. 
     
                                           TABLE II                                
__________________________________________________________________________
                                        % Area Shrinkage                  
Fabric   Wet Pick Up                                                      
                 % resin o.w.f.                                           
                         Aftertreatment 1 hr wash                         
                                              2 hr wash                   
                                                    3 hr                  
__________________________________________________________________________
                                                    wash                  
Wool Serge                                                                
         130%    4.9     0.5% aqueous ammonia                             
                                        11    24    40                    
                         1% THPC (15 mins. 20°C)                   
                                        3     5     11                    
                         MgCl.sub.2 wash (20°C, pH                 
                                        2)    4     12                    
                         MgCl.sub.2 wash (20°C, pH                 
                                        1)    1     1                     
                         MgCl.sub.2 wash (60°C, pH                 
                                        1)    1     2                     
Uncarbonised                                                              
         166%    6.3     0.5% aqueous ammonia                             
                                        2     4     12                    
Flannel, scoured         1% THPC (15 mins. 20°C)                   
                                        -1    -2    -2                    
and milled               MgCl.sub.2 wash(20°C, pH                  
                                        1)    0     1                     
Double Jersey                                                             
         129%    4.9     0.5% aqueous ammonia                             
                                        2     4     12                    
                         1% THPC (15 mins. 20°C)                   
                                        1     1     1                     
                         MgCl.sub.2 wash (20°C, pH5)               
                                        1     1     2                     
__________________________________________________________________________
 
    
     One of the dyed and magnesium chloride after-treated serge samples was exposed to the Xenotest accelerated fadeometer until Standard 6 on the Blue Scale had just started to fade. The fabric was then test washed as before and the results compared with an untreated sample. 
     
         ______________________________________                                    
Sample   % Area Felting Shrinkage                                         
       1 Hr Wash 2 Hr Wash   3 Hr Wash                                    
______________________________________                                    
Unexposed                                                                 
         -1          0           0                                        
Exposed  -1          0           0                                        
______________________________________                                    
 
    
     There was therefore no substantial deterioration in the shrinkproofing effect observed with this sample on exposure to light. 
     EXAMPLE IX 
     A wool serge fabric was impregnated by padding with the following composition to a wet pick-up of 130% by weight on the weight of the fabric 
     
         Urea                300 g/l                                               
Thioglycerol         0 g/l or 5 g/l                                       
Resin of Example IV  50 g/l                                               
Sodium bisulphite    20 g/l                                               
Guaranate AP 5       6 g/l                                                
Procion Red MG       20 g/l                                               
 
    
     The impregnated fabric was stored for 24 hours as in Example VIII and then washed in an aqueous magnesium chloride solution for 15 minutes at 60°C. The resulting red dyed fabric showed the following shrink resist results on test washing as before 
     
                        % Area Felting Shrinkage                                   
               1 hour wash                                                
                      2 hour wash                                         
                             3 hour wash                                  
__________________________________________________________________________
UNTREATED      45%    --     --                                           
WITHOUT THIOGLYCEROL                                                      
               9%     19%    26%                                          
WITH THIOGLYCEROL                                                         
               0%      5%     8%                                          
__________________________________________________________________________
 
    
     EXAMPLE X 
     A worsted serge fabric was padded to 100% wet pick up with a solution containing 
     
         Resin of Example II   4% o.w.f.                                           
Sodium bisulphite     10 g/l                                              
Thiourea              20 g/l                                              
Sodium Carbonate      to give pH 8                                        
 
    
     After padding the fabric was rinsed with an aqueous solution of 2% v/v magnesium chloride and 2% v/v ammonium thioglycollate adjusted to pH 9, then with water, and then dried. A sample of the treated fabric exhibited about zero area felting shrinkage after 3 hours test washing. 
     EXAMPLE XI 
     Light Stability of the Polymers 
     Worsted serge was padded through the following pad liquors: 
     
          (i)  Polyol-based Bunte salt (80%)                                       
                              40 g/l                                      
      Sodium Sulphite         20 g/l                                      
(ii)  As (i) but including Polyamide-                                     
      based Bunte Salt (50%) (for                                         
      preparation see Exammple XXVI)                                      
                              20 g/l                                      
 
    
     Immediately after padding the fabrics were cured in the following solutions for 10 minutes at 20°C. 
     a. Ammonium thioglycollate (2% w/v) Mg Cl 2  6H 2  0 (2% w/v), 
     b. Hexamethylene diamine (2% w/v) NaCl (5% w/v). 
     passed well with water and dried. Samples from these experiments were then exposed for 72 hours in the Xenotest machine, an exposure time, in fact, sufficient to fade the blue standard number 6 on the Blue Wool Scale. The exposed and non-exposed samples were then wash-tested for shrink resistance as before. The results are shown in Table III. 
     
                                           TABLE III                               
__________________________________________________________________________
                          % AREA SHRINKAGE                                
Pad Liquor                                                                
       After Treatment                                                    
                 Light Exposure                                           
                          1 hr.                                           
                              2 hr.                                       
                                  3 hr.                                   
__________________________________________________________________________
 (i)   a         No       0   0   O                                       
 (i)   a         Yes      9   22  25                                      
 (i)   b         No       0   1   1                                       
 (i)   b         Yes      7   10  17                                      
(ii)   a         No       -1  -1  -1                                      
(ii)   a         Yes      0   0   0                                       
(ii)   b         No       -1  0   0                                       
(ii)   b         Yes      0   1   2                                       
__________________________________________________________________________
 
    
     It is evident from this table that the use of the polyamide-based Bunte Salt improves the stability of the cured fabric to light. 
     EXAMPLE XII 
     Wool serge samples (a) without pretreatment, (b) pretreated with 5% o.w.f. THPC or (c) pretreated with 10 g/l ammonium thioglycollate were treated by exhaustion in a bath at a liquor:goods ratio of 30:1 with Glaubers Salt (10% o.w.f.), formic acid (1% o.w.f.) and the resin of Example II (4% o.w.f.). The bath was raised to the boil over a period of 1 hour and maintained at the boil for a further 30 minutes. Each sample was then divided into two portions, one of which was not treated further, while the other half was washed for 15 minutes at ambient temperature with aqueous magnesium chloride (2%) solution, adjusted by addition of ammonia to pH 9. The samples were tested for felting shrinkage by washing as previously described. The results obtained are shown in Table IV. 
     The method was repeated except that Lanasol Blue 3R (2% o.w.f.) and an amphoteric levelling agent containing ethylene oxide derived groups, Albegal B, (1% o.w.f.) were included in the resin treatment liquor. An excellent dyeing was obtained and the fabric had good shrink resist properties. 
     
                                           TABLE IV                                
__________________________________________________________________________
                        % AREA FELTING SHRINKING                          
FABRIC        AFTERTREATMENT                                              
                         1 hr. Wash                                       
                                2 hr. Wash                                
                                       3 hr. Wash                         
__________________________________________________________________________
Untreated     --         45     --     --                                 
Pretreated with 3% owf                                                    
              Nil        9      15     24                                 
THPC                                                                      
Pretreated with 10 g/l                                                    
              Nil        21     35     49                                 
ammonium thioglycollate                                                   
              MgCl.sub.2 wash                                             
                         3      4      5                                  
No pretreatment but resin                                                 
              Nil        22     49     --                                 
treated       MgCl.sub.2 wash                                             
                         15     46     --                                 
__________________________________________________________________________
 
    
     EXAMPLE XIII 
     Wool yarn was treated in a package dyeing machine for a period of 20 minutes with an aqueous solution containing 5% by weight on the weight of yarn of THPC and 15 g/l ammonium thioglycollate. An aqueous solution containing the following composition was then applied. 
     
         ______________________________________                                    
Resin of Example I   4% o.w.f.                                            
Formic Acid          1.5% o.w.f.                                          
Glauber&#39;s Salt       10% o.w.f.                                           
Lanasol Blue 3R      2% o.w.f.                                            
______________________________________                                    
 
    
     After 2 hours the resin and dye were observed to have exhausted onto the yarn and an excellent blue dyed yarn having a high degree of resistance to felting shrinkage was obtained. 
     EXAMPLE XIV 
     A wool fabric was impregnated by padding with an aqueous composition containing the pigment dye Hostaperm Red E3B (1.5 g/l), the resin of Example II (50 g/l) and sodium bisulphite (10 g/l). The impregnated fabric was stored for 15 minutes and then washed in a dilute solution containing magnesium chloride and ammonium thioglycollate. A blue dyed fabric was obtained having good shrink resist properties. The pigment was well retained by the fabric and exhibited satisfactory fastness to washing, light and mechanical abrasion. 
     EXAMPLE XV 
     A sample of bleached human hair was treated with an aqueous composition comprising 
     
         Resin of Example II  20 g/l                                               
Sodium bisulphite    10 g/l                                               
 
    
     The solution was allowed to remain in contact with the hair for 10 minutes, after which it was washed with a dilute aqueous solution containing ammonium thioglycollate and magnesium chloride. The hair was then allowed to dry. It was found to have an improved handle and gloss and was easier to disentangle on combing than the untreated hair. 
     EXAMPLE XVI 
     A sample of human hair was wound around a small diameter hair curler and treated with the aqueous composition of Example XV. The composition was allowed to remain in contact with the hair for 15 minutes at 40°C after which the hair was washed with a 2% by weight aqueous solution of magnesium chloride. The hair was then set in the usual way on a large diameter curler, washed with water and dried in a current of warm air. An excellent permanent curl was obtained which was very resistant to washing. The test was repeated in the absence of the resin, and the curl obtained was much less pronounced and less resistant to washing. 
     EXAMPLE XVII 
     A sample of human hair was impregnated with the following composition. 
     
         ______________________________________                                    
Hostaperm Red E3B    1.5 g/l                                              
Resin of Example II   50 g/l                                              
Sodium bisulphite     10 g/l                                              
______________________________________                                    
 
    
     Hostaperm Red is a pigment dye. The hair was immediately wound onto a small diameter hair curler and allowed to remain thereon for 16 minutes. It was then rinsed in a dilute aqueous solution of magnesium chloride and ammonium thioglycollate. The hair was dyed red and permanently curled. Both the curl and the dyeing were fast to washing. In the absence of the resin no dyeing is observed and the permanent waving is less pronounced and less fast to washing. 
     EXAMPLE XVIII 
     A print paste was prepared comprising 
     
         Bunte Salt of Example II                                                  
                     30 g/l                                               
Hostaperm Red E3B     6 g/l                                               
Sodium sulphite      10 g/l                                               
Alginate/starch ether                                                     
                     50 g/l                                               
thickener                                                                 
 
    
     The above paste was applied by screen printing to a wool serge fabric and to cotton cloth, knitted polyester fabric, polyamide fabric and knitted acrylic fabric. Each fabric was then washed in saturated aqueous salt solution containing 2% ammonium thioglycollate for about 5 minutes at ambient temperatures. The fabric was washed in water and dried. In each case a bright red dyeing fast to washing, rubbing and dry-cleaning was obtained. 
     EXAMPLE XIX 
     A knitted double jersey Crimplene polyester fabric was printed with the following print pastes (1-3) to a 3-colour flowered design. 
     1. 50 g/l Bunte Salt concentrate of Example III 6 g/l Hostaperm Pink E 50 g/l of a 50:50 mixture starch ether: alginate thickener 10 g/l thiourea (adjusted paste to pH 9.0) 
     2. as 1 but using 12 g/l Helizarin Blue BT as pigment. 
     3. As 1 but using 3 g/l Helizarin Green GG as pigment. 
     After being printed the fabric was aftertreated for 5 minutes at 20°C in a saturated salt solution containing 2% (w/v) ammonium thioglycollate and then washed off in cold water and dried at 110°C. A very bright, clear print was produced, fast to washing, wet rubbing and light. The fastness to wet rubbing is particularly satisfactory in the deeper shades and is unexpectedly high for a print based on the use of pigment dyes. 
     EXAMPLE XX 
     The procedure of Example XIX was repeated except that the fabrics used were 
     a. 100% wool worsted 
     b. 100% nylon continuous filament knitwear 
     c. Triacetate continuous filament knitwear 
     d. Cotton woven poplin 
     e. 50:50 wool/polyester worsted In all cases fast prints of high wet rub fastness and lightfastness were produced. 
     EXAMPLE XXI 
     The procedure of Example XIX was followed except that curing was by a Thermosol treatment at 140°C for 5 mins. Again fast prints of high fastness were produced. 
     EXAMPLE XXII 
     The prints on 100% wool from EXample XX were test washed for 3 hours at pH 7.0, and felting occurred only in the unprinted areas, producing an attractive seersucker effect. 
     This effect could be produced in the absence of colour by printing an unmilled woollen cloth in a floral design with the following paste: 
     50 g/l Bunte Salt concentrate of Example III 
     50 g/l of a 50:50 mixture starch ether/alignate thickener 
     20 g/l Sodium sulphite 
     The fabric was cured by immersion for 10 minutes cold in a solution at pH 9.0 containing: 
     2% MgCl 2  w/v 
     2% ammonium thioglycollate followed by rinsing in cold water and drying. 
     The fabric was then milled in a `Cherry Tree` milling machine in the presence of dilute acetic acid. An attractive floral effect was produced whereby the white printed floral areas had completely resisted milling and the weave structure was clear, but the unprinted areas had milled normally. 
     EXAMPLE XXIII 
     The following liquor was applied by padding to wool serge, polyester knitwear, wool/polyester knitted fabric and blended worsted and nylon knitwear to give 100% wet pick up in each case 
     6 g/l Hostaperm Red E3B 
     50 g/l Bunte salt concentrate from Example III 
     12 g/l Guaranate AP5 
     10 g/l Thiourea 
     Adjusted to pH 9.0 
     The fabrics were then cured as in Example XIX. An attractive dyeing,, fast to light, wet rubbing and washing was achieved on all the above fabrics. It was noted that the coloration was solid on the wool/polyester blend fabrics. 
     EXAMPLE XXIV 
     Woollen fabric was padded with the following composition 
     50 g/l Bunte salt concentrate of Example III 
     5 g/l Sodium bicarbonate and dried for 5 mins at 130°C. 
     The fabric was then test washed for 3 hours and found to be resistant to felting. 
     EXAMPLE XXV 
     The following surface coating mixture was preparedHostaperm Red E3B         10 g/lBunte salt concentrate of Example III                          50 g/lHydroxyethylcellulose thickener                          20 g/lThiourea                  20 g/l 
     The mixture was applied to wood and lead-primed metal surfaces. These materials were then heated for 10 minutes at 140°C. A bright red, water resistant coating was obtained on both materials.