US3706527A

US3706527A - Treatment of keratinous fibres and fabrics with polythiols

Info

Publication number: US3706527A
Application number: US66903A
Authority: US
Inventors: Bryan Dobinson; Kenneth Winterbottom
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1969-09-02
Filing date: 1970-08-25
Publication date: 1972-12-19
Anticipated expiration: 1989-12-19
Also published as: ZA705831B; FR2060352B1; CH1264570A4; JPS4924837B1; ES383286A1; GB1316416A; FR2060352A1; DE2042989A1; CH527318A; NL7012936A; BE755576A; CA942007A

Abstract

A PROCESS FOR MODIFYING KERATINOUS MATERIALS BY USING A POLYTHIOL ESTER OF THE FORMULA

(HO-(R''-O)A)QY-R(-((CO)X-(O-R1)AY-O-(CO)Y-R2-SH)P)-

(CO2H)QX

WHEREIN R REPRESENTS A HYDROCARBON RADICAL, CONTAINING A CHAIN OR AT LEAST 3 AND AT MOST 60 CARBON ATOMS, R1 REPRESENTS AN ALKYLENE GROUP CONTAINING AT LEAST 2 AND AT MOST 6 CARBON ATOMS, R2 REPRESENTS A HYDROCARBON RADICAL, A, X, AND Y IN EACH OF THE P CHAINS ARE INDIVIDUALLY CHOSEN FROM THE GROUP COMPRISING ZERO AND 1, WITH THE PROVISO THAT X AND Y ARE UNEQUAL, P IS AN INTEGER OF AT LEAST 3 AND AT MOST 6, Q IS CHOSEN FROM THE GROUP COMPRISING ZERO AND POSITIVE INTEGERS OF AT LEAST 1 AND AT MOST 3, (P+Q) IS AT MOST 6, OPTIONALLY IN COMBINATION WITH OTHER POLYMERIC POLYMEROPTIONALLY IN COMBINATION WITH OTHER POLYMERIC POLYMERCAPTANES, AMINOPLASTS, EPOXY RESINS, ACRYLIC RESINS, ACRYLAMIDE OR POLYISOCYANATES. THE POLYMERS CURE ON THE FIBRE. THE KERATINOUS MATERIALS ARE RENDERED RESISTANT TO SHRINKAGE AND DURABLE PRESS CHARACTERISTICS ARE IMPARTED TO THEM. THE TREATED MATERIAL RETAIN THEIR DIMENSION AND SHAPE WHEN WASHED IN MACHINES AND HAVE GOOD RECOVERY FROM WRINKLING.

Description

United States Patent Office 3,706,527 Patented Dec. 19, 1972 3,706,527 TREATMENT OF KERATINOUS FIBRES AND FABRICS WITH POLYTHIOLS Bryan Dobinson, Duxford, and Kenneth Winterbottom, Whittlesford, England, assignors to Ciba-Geigy AG No Drawing. Filed Aug. 25, 1970, Ser. No. 66,903 Claims priority, application Great Britain, Sept. 2, 1969,

43,478/69 Int. Cl. D06m 3/06, 13/20, 13/26 US. Cl. 8127.5 19 Claims ABSTRACT OF THE DISCLOSURE A process for modifying keratinous materials by using a polythiol ester of the formula -oo OH] L q:

R represents a hydrocarbon radical, containing a chain of at least 3 and at most 60 carbon atoms,

R represents an alkylene group containing at least 2 and at most 6 carbon atoms.

R represents a hydrocarbon radical,

a, x, and y in each of the p chains are individually chosen from the group comprising zero and l, with the proviso that x and y are unequal,

p is an integer of at least 3 and at most 6,

q is chosen from the group comprising zero and positive integers of at least 1 and at most 3,

(p-l-q) is at most 6,

optionally in combination with other polymeric polymercaptanes, aminoplasts, epoxy resins, acrylic resins, acrylamide or polyisocyanates. The polymers cure on the fibre. The keratinous materials are rendered resistant to shrinkage and durable press characteristics are imparted to them. The treated material retain their dimension and shape when washed in machines and have good recovery from wrinkling.

wherein The present invention relates to a process for modifying keratinous material, and, in particular, to a process for rendering the material resistant to shrinkage and to a process for imparting durable press characteristics to the material.

A number of shrink-resist processes for keratinous material are known, some of which comprise the application of a resin to the material which may be in fabric or fibre form. Shrink-resist processes stabilize the dimensions of keratinous materials against shrinkage due to felting.

Durable press processes for keratinous material are also known and many of them employ resins the same or similar to those used in shrink-resist processes. In some durable press processes the desired shape is imparted to the keratinous material before the resin is cured and then curing is allowed to take place whilst the material is maintained in the desired shape, e.g. in form of creases or pleats. In others the resin is applied after the desired shape is imparted to the material. Durable press processes stabilize the shape and surface smoothness of the material against deformation in the presence of aqueous solutions. The desired shape may be imparted to the material before or after resin treatment by well known methods involving the use of setting agents such as water, reducing agents, and bases.

A desirable, though not essential, feature of shrinkresist and durable press processes is that the keratinous material so treated should be washable in domestic washing machines. To be machine-washable the finish on the treated material should withstand vigorous agitation in warm or hot water containing detergents, and this requirement sets a sever test for the durable press and shrink-resist treatments.

We have now found that certain thiol-terminated esters can be used in durable press and shrink-resist processes successfully. These esters cure, i.e. undergo reaction, on the keratinous fibre and we have further found that the rate of curing may be largely controlled by selection of the appropriate catalyst.

Accordingly, the present invention provides a process for modifying keratinous material which comprises (1) Treating the material with a polythiol ester of the formula wherein R represents a radical, containing at least 3 carbon atoms, preferably an aliphatic or araliphatic hydrocarbon radical of at most 60 carbon atoms, other than a radical of a polyhydric alcohol having at least two oxyalkylene chains attached thereto with the indicated radicals attached to the said oxyalkylene chains,

R represents an alkylene group containing at least 2 and at most 6 carbon atoms,

R represents a hydrocarbon radical,

a, x, and y in each of the p chains individually represent zero or 1, with the proviso that x and y are unequal,

p is an integer of at least 3 and at most 6-,

q is zero or a positive integer of at most 3,

(p+q) is at most 6, and

(2) Curing the polythiol ester on the material.

This invention also provides keratinous fibrous materials, in the form of fabrics if desired, bearing thereon a polythiol as aforesaid in the cured or still curable state.

The treatment according to the invention, whether to achieve shrink-resist or durable press effects, provides fibres or garments which will withstand washing in ma chines and still retain their original dimension and shape. The treated material also has good recovery from wrinkling, which is an important attribute in fabrics employed in trousers where there is a strong tendency to wrinkles in the areas of the knee and back of the knee. Of course, wrinkle-resistance is an important advantage in many garments.

The polythiols used in the process according to the invention, as well as inhibiting or preventing felting shrinkage, also inhibit or prevent relaxation shrinkage, which is an important problem associated with both knitted and Woven goods.

The term keratinous material as used throughout this specification includes all forms of keratinous fibres or fabrics and garments made therefrom, e.g. fleeces, tops, card sliver, noils, yarns, threads, pile fabrics, non-woven fabrics, woven fabrics, and knitted goods. The treatment may be applied to fabrics or made-up garments but it may be desirable in some circumstances to shrink-resist fibres, e.g. in the form of tops. Indeed, treatment of keratinous material as loose wool, sliver, slubbing, tops, and yarns in the form of hanks or packages is a particularly suitable embodiment of the invention: in some cases treatment leaves a slightly harsh film on the fibre, but this film is largely removed on subsequent mechanical handling of the fibre, e.g. in weaving. The material to be treated can consist either wholly of keratinous fibres or of blends of these fibres with synthetic fibrous and filamentary material such as polyamides, polyesters, and poly(acrylonitrile) and with cellulosic, including regenerated celluosic, material. In general, however, the material should contain at least 30% by weight of keratinous fibres and better results are obtained with 100% keratinous fibre-containing material.

The keratinous material may be virgin or reclaimed: preferably, though not necessarily, it is sheeps wool. It may also be derived from alpaca, cashmere, mohair, vicuna, guanaco, camel hair, and llama, or blends of these materials with sheeps wool.

Preferred polythiols are those of formula FOR] [1.

in which group.

One perferred class of such polythiol esters are those of formula OE] ]/E q OCOR*-SH] L p m and further preferred are those which also conform to Formula IV o-o OR=SH] D where R, R p, and q have the meanings previously assigned and R denotes an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms.

These polythiols are, in general known substances, and are readily prepared by partial or complete esterification of a polyol [R] [OH] (1,) with a mercaptocarboxylic acid HOOC--R SH. The mercaptocarboxylic acid is preferably thioglycollic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, or mixtures thereof, although other mercapto-acids such as mercaptoundecylic acid, mercaptostearic acid, and o-mercaptobenzoic acid may also be used.

Polyols suitable for use as starting materials include glycerol, 1,1,l-trimethylolethane, 1,1,1-trimethylolpropane, hexane-1,2,5-triol, hexane-1,2,6-triol, pentaerythritol, dipentaerythritol, mannitol, sorbitol, polyvinyl alcohol, styrene-allyl alcohol copolymers, partially hydrolysed polyvinyl esters or acetals, and hydroxyalkyl acrylate, methacrylate, and itaconate polymers and copolymers.

Most preferred are the polythiol esters of Formula IV where q is zero.

Another preferred class of polythiol esters are those of formula oo-o-n -sn t 1 Eooon] in which R and b have the meanings previously assigned, and R represents an alkylene group, such as one of formula C H where n is an integer which is at least 2 and may be as high as 9 or even 12, and is especially --CH CH or -CH CH(CH and u is zero or 1.

Further preferred are polythiols which are of the formula Polycarboxylic acids which can be used as starting materials include citric acid, tricarballylic acid, mellitic acid, trimellitic acid, pyromellitic acid, trimerised linoleic acid and polymers or copolymers of monoethylenically unsaturated acids and anhydrides such as acrylic acid, methacrylic acid and maleic anhydride.

The polythiols may be used alone or in conjunction with I aminoplasts, polymeric and non-polymeric polymercaptans, epoxy resins, (i.e. substances containing on average more than one 1,2-epoxide group per molecule), acrylic resins, including polymers and copolymers of acrylate esters, e.g. ethyl, n-butyl and Z-hydroxyethyl acrylates, and acrylamide, or polyisocyanates, including prepolymers of, for example, a poly(oxyalkylene) glycol and an aromatic diisocyanate or of a poly(oxalkylene) triol and an aliphatic diisocyanate.

Particuar useful polymeric polymercaptans for use with the polythiol esters are those esters or ethers 'which have at least two mercaptan groups per molecule and which contain (a) A radical of a polyhydric alcohol (b) Bound to this radical, at least two poly(oxyalkylene) chains,

(0) Bound through oxygen atoms to carbon atoms in the said poly(oxyalkylene) chains, at least two residues selected from the group comprising an acyl residue of a thiol-containing aliphatic carboxylic acid or a residue, after removal of a hydroxyl group, of a thiol-containing aliphatic alcohol,

The said ester or ether having a molecular weight of at least 400 and at most 10,000.

Examples of such said esters and ethers are those of the formula o-aik lene -on] 1 l. t

[ O-a1kylene OCHzCHCHzSH] H IX wherein R represents an aliphatic radical containing at least 2 carbon atoms,

each alkylene group contains a chain of at least 2 and at most 6 carbon atoms between the indicated consecutive oxygen atoms,

.9 denotes an integer, which may have different values in each chain,

v denotes an integer of at least 2 and at most 6,

t denotes zero or a positive integer such that (t-i-v) is at most 6, and

R has the meanings previously assigned, especially such esters and ethers having a molecular weight of from 1,000 to 5,000.

The aforesaid esters and ethers are commercially available.

Other polymeric polymercaptans which may be used with the polythiol esters of this invention include homopolymers or copolymers of butadiene or methylbutadiene having SH groups directly attached to carbon atoms of the polymer, such as those containing structures of formula in which b and d are each a positive integer such that the polymer has an average molecular weight of at least 1,000 and at most 10,000,

is zero or a positive integer,

X represents hydrogen or methyl, and

Y represents CN, COOH, --CONH COOZ, C H or OCOZ, where Z is an alkyl group of from 1 to 8 carbon atoms.

Thiol-terminated polybutadienes of this type are also commercially available.

There may also be used nonpolymeric polymercaptans such as the bis(thioglycollates) and bis(3-mercaptopropionates) of ethylene glycol and propylene glycol.

Many of the polythiol esters used in the process of this invention are insoluble in water but can be applied as aqueous dispersions or emulsions. Preferably the poly thiols are applied to fabrics and garments from organic solvents, for example alcohols, lower ketones such as ethyl methyl ketone, benzene, and halogenated hydrocarbon solvents, especially chlorinated and/ or fluorinated hydrocarbons containing not more than three carbon atoms such as the dry cleaning solvents, carbon tetrachloride, trichloroethylene, and perchloroethylene.

The amount of polythiol used depends on the effect desired. For most purposes 0.5 to 15% by weight based on the material treated is preferred. Stabilization of knitted fabrics usually requires from 1 to by weight of the resin. A high level of shrink-resistance, crease-setting and substantial resistance to wrinkling can be achieved on woven fabrics with rather smaller quantities, especially from 1 to 5% by weight. The hand or handle of the treated material will, of course, depend on the amount of polythiol employed and by simple experiment the least amount of polythiol required to give the desired effect may readily be determined. Further, the construction of the fabric also influences the amount of polythiol required.

The desired effects are not fully obtainable unt1l the polythiol on the material has substantially cured. At ordinary temperatures this may take from five to ten days or even longer. The curing reaction can, however, be accelerated greatly by the use of a catalyst, and generally 1t 18 preferred to add the catalyst to the material to be treated at the same time as the polythiol is applied although it may be added before or afterwards if desired. The curing time can be controlled by selecting an appropriate catalyst and the choice of ccuring time will depend on the particular application of the process according to the invention. The catalysts may be organic or inorganic bases, siccatives, oxidative curing agents, and free-radical catalysts such as azodi-isobutyronitrile, peroxides and hydroperoxides, or combinations of these. As organic bases there may be used pnmary or secondary amines, especially the lower alkanolamrnes, e.g. monoand di-ethanolamine, and lower polyammes, e.g. ethylenediamine, diethylenetriamine, triet hylenetetramine, tetraethylenepentamine, propane-1,2- dramme, propane-1,3-diamine, and hexamethylenediamine. As inorganic bases there may be used the water-soluble oxides and hydroxides, e.g. sodium hydroxide, and also ammonia. Examples of suitable siccatives are calcium, copper, iron, lead, cerium, and cobalt naphthenates. Examples of peroxides and hydroperoxides which may be used are cumene hydroperoxide, tert.-butyl hydroperoxide, dicumyl peroxide, dioctanoyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide, di-isopropyl peroxydicarbonate, and chlorobenzoyl peroxide. Other types of catalysts include sulphur, and sulphur-containing organic compounds in which the sulphur is not exclusively present in mercaptan groups, namely, mercaptobenzothiazoles or derlvatives thereof, dithiocarbamates, thiuram sulphides, thioureas, disulphides, alkyl xanthogen disulphides, or alkyl xanthates.

The fibres and fabrics are preferably treated at a pH greater than 7, typically 7.5 to 12: under acid conditions the polythiols tend to cure more slowly.

The amount of catalyst used can vary widely. However, in general from 0.1 to 20%, preferably 1 to 10%, by weight based on the weight of polythiol used is required, although much larger quantities can be used.

Curing of the polythiol is also assisted by using elevated temperatures and it especially fast results are required then temperatures in the range of 30 to C. may be used. High humidities also tend to accelerate curing in the presence of catalysts. The polythiol, and the catalyst if desired, can be applied to the keratinous material in conventional ways. For example, where wool tops or where fabric is to be treated, impregnation by padding or by immersing the material in a bath may be used. If garments or garment pieces are to be treated than it is convenient to spray them with the polythiol, and more convenient still to tumble the garments in a solution of the polythiol. For the latter method a dry-cleaning machine is a particularly useful apparatus for carrying out the process.

If a shrink-resist treatment is required, then it is usually more convenient to apply the polythiol to the fabric although, as previously stated, it may be applied to the fibres in the form of, e.g. tops or sliver. The fabric may be flatset before or after treatment with the polythiol and by this means the fabric will, in addition to retaining substantially its original dimensions, also retain its flat smooth appearance during wear and after washing. It should be stated, however, that fiat-setting may not be necessary or even desirable with certain types of cloth. Flat-setting is normally carried out either by treating the cloth with steam at superatmospheric pressure, or by treating the cloth with steam at atmospheric pressure in the presence of a setting agent and moisture and maintaining the cloth in a flat state. Flat-setting may also be achieved by applying high concentrations of a reducing agent and a swelling agent, and maintaining the cloth in a fiat state during washing off the excess reagents. In another method flatsetting may be achieved by impreg a the material with a swelling agent and an alkanolamine carbonate, e.g. urea and diethanolamine carbonate, drying the mate and then semi-decatising it. Of course, if desired, the fabric may be set in the presence of the polythio thus effecting setting and shrinkproofing treatments simultaneously.

If a durable press treatment is required, there are a number of ways this may be achieved. One method is to treat the material with the polythiol, make the material up into garments or garment pieces and insert therein pleats or creases, using reducing agents, bases, or superheated steam as setting agents. Again, the polythiol may be applied to the fibres at any stage during the manufacture of the fabric, e.g. in top form, in yarn, or in fabric form. If desired, agents which block the thiol groups of the wool, e.g. formaldehyde or higher aldehydes, may be applied to the creased or pleated garments after curing the polythiol.

A preferred method of applying the polythiol to obtain a durable press effect comprises treating the made-up garment or garment piece, which already has the desired creases or pleats imparted thereto, with the polythiol dissolved in an organic solvent. In this method it is essential that the polythiol is applied in an organic solvent because treatment with aqueous systems would only serve to remove the creases or pleats already set in the fabric.

Another method, which is primarily concerned with the production of durable press pleats or creases only, comprises impregnating the fabric in the area where a crease or pleat is to be inserted with the polythiol, imparting the crease or pleat, and maintaining it in this position whilst heat and pressure are applied.

A further method, for flat-setting and shrinkproofing keratinous fabrics, comprises treating the fabric with a setting agent and setting it in a flat configuration by heating the fabric while wet, impregnating it with an aqueous emulsion or dispersion of the polythiol and catalyst, drying and heating the fabric, and curing the polythiol. Finally the fabric is made into garments, and creases or pleats set therein if desired by steaming in the presence of a setting agent such as monoethanolamine sesquisulphite.

The setting of the fabric, whether carried out before or after treatment with the polythiol, may be effective using any of the known methods, for example by means of setting agents, e.g. reducing agents, bases, water, and superheated steam. Monoethanolamine sesquisulphite is the most frequently used setting agent and may be used in association with a swelling agent, e.g. urea.

The compositions used in the process of this invention may contain antisoiling, antistatic, bacteriostatic, rotproofing, flameproofing and wetting agents. They may also contain water-repellents such as paraifin wax, and fluorescent brightening agents.

The invention will now be illustrated by reference to the following examples. Unless otherwise specified, parts and percentages are by weight.

The treated samples of cloth were washed at 40 C. for one hour in an English Electric Reversomatic washing machine in an aqueous solution containing, per litre, 2 g. of soap flakes and 0.8 g. of anhydrous sodium carbonate, using a liquor/sample ratio of about 30:1. The samples were removed, rinsed in cold water, spun in the machine, and then dried for 30 minutes in a Parnall Tumble Drier on full heat. Shrinkage was measured as the difference in dimensions of the fabric before and after washing. .Area shrinkage was calculated from linear shrinkage measurements. I

The polythiols employed were prepared as follows:

A mixture of glycerol (184 g.), thioglycollic acid (552 g.), toluene-p-sulphonic acid (4 g.), and perchloroethylene (500 ml.) was heated under reflux in an atmosphere of nitrogen in such a manner as to entrain water formed during reaction. After 5 hours, 104 ml. water was collected (calculated quantity 108 ml.); the product partially separated from the perchloroethylene on cooling. The solvent was removed and the product was washed with water and dried to yield 600 g. of substantially pure glycerol tris (thioglycollate), a clear liquid having a thiol content of 8.88 equiv./kg. (theory, 8.93 equiv./kg.).

In a similar manner the following materials were prepared: 1,1,1 trimethylolpropane tris(thioglycollate) (thiol content 7.45 equiv./kg., theory 8.43), 1,1,1-trimethy olethane tris( h og ycol ate) V hiol. content 8.30

equiv./kg., theory 8.78), hexane-1,2,6-triol tris(thioglycollate) thiol content 7.72 equiv./kg., theory 8.40), dipentaerythritol tetrakis(thioglycollate) (thiol content 7.30 equiv./kg., theory 7.27), glycerol tris(Z-mercaptopropionate) (thiol content 7.5 8 equiv./kg., theory 8.43), and the thioglycollate of a styrene-allyl alcohol copolymer. The styrene-allyl alcohol copolymer had an average molecular weight of 1600 and contained 5.35 hydroxyl groups per average molecule. The ester had a thiol content of 2.15 equiv./kg., i.e. about of the calculated value for a pentakis(thioglycollate). Pentaerythritol tetrakis(thioglycollate) and tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(thioglycollate) and hexalcis(3-mercaptopropionate) are available commercially.

A mixture of Empol 1043 g.), Z-mercaptoethanol (26 ml., 29.5 g.), toluene-p-sulphonic acid (1 g.) and perchloroethylene ml.) was heated to reflux for 16 hours under nitrogen in such a manner as to remove water formed during the reaction (7.6 ml.). The solution was washed with water, and stripped to yield 111 g. of a pale yellow oily liquid having a thiol content of 2.20 equiv./kg., (theory approximately 2.8 equiv./kg.).

In place of perchloroethylene, other solvents may be used, e.g. toluene.

Empol 1043" denotes a trimerised unsaturated C fatty acid, having a molecular weight of about 800 and a carboxyl content of 3.42 equiv./kg. it was obtained from Unilever-Emery N.V., Gouda, Holland.

In one example, a polythiol of this invention is applied as an aqueous emulsion. Emulsions containing the polythiol dispersed in an aqueous phase, an emulsifying agent (such as an adduct of a long-chain primary aliphatic amine and ethylene oxide), and, optionally, a protective colloid (such as sodium carboxymethylcellulose or the sodium salt of a methyl vinyl ether-maleic anhydride copolymer) are particularly convenient for carrying out the treatment of keratinous material.

EXAMPLE I The cloth used was a wool flannel of approximately g. per square metre; the pH of its aqueous extract was 3J1. The flannel was padded with a 3% solution of the polythiol in trichloroethylene, containing 10% of monoethanolamine based on the weight of the polythiol, such that the uptake of the polythiol was 8% and that of monoethanolamine was correspondingly 0.8%. The solution also contained 5% of ethanol to complete solution of the monoethanolamine. Then the flannel was dried at 50 C. in a fanned oven, and stored at room temperature with free access to air. The samples were Washed and their shrinkage was measured. A sample of flannel was also subjected to this severe washing but without prior treatment with a polythiol. Table I shows the results obtained.

EXAMPLE II The test described in Example I was repeated, using other polythiols. The wool flannel used was similar to that in Example I, but the pH o its aqueous extract was 7.0.

TABLE II Area shrinkage (percent) after- 1 2 8 day days day Untreated 22. 5 22. 2 22. 2 Treated with:

Pentaerythrltol tetrakis(thioglycollate) 7. 7 9. 3 Dipentaerythritol tetrakis(thioglycollate) 14. 5 8. 7 Dipentaerythritol hexakis (thioglycollat l0. 5 7 3 Dipentaerythrltol hexakis (3-mercapto propionate 13. 1 Castor oil tris (thiolglycollate). 11. 3 7. 4 Styreneallyl alcohol poly-(thioglycollate) 15. 12. 7 Glycerol tris (thioglycollate) 10. 0 10. 7 Glycerol tris (thioglycollate) 1 a 15. 0 Glycerol tris (2-mercaptoproplonate) 1 10. 7 Glycerol tris(thioglycollate) l 4 17.3 16. 8 14. 6 Pentaerythritol tetrakis (thioglycollat 14. 5 12. 6 Pentaerythritol tetrakis (thioglycollate) 15.9 14. 5 9.4 Pentaerythrltol tetrakis (thioglycollate) 16. 8 7. 9 1,1,1-t1imethylolpropane tris(thioglycollat 19. 2 6. 4 1,1,1-trlmethylolpropane tris(thiog1ycollate) 18. 6 18. 6 5. 0 Mannitol hexakis (thioglycollate) 1 2 16. 5

1 Uptake of the polythiol was 3%. B Uptake of monoethanolaniine was 0.3%. 8 Catalyst was 1.2% of calcium nephthenate (containing 5% Ca). 4 Catalyst was 0. 3% of tetramethylthiuram disulphide. 5 Catalyst was 0.16% of diethylenetriarnine.

Catalyst was 0.8% of di-isopro yl xanthogen disulphide. Catalyst was 0.8% of tetrabuty thiuram disulphide.

EXAMPLE III This example illustrates the use of a polymercaptan of this invention with another kind of polymercaptan or with an epoxide resin. The procedure described in Example 11 was followed, and the results are given in Table III.

Thiol A denotes the bis(thioglyco1late) of a polyoxypropylene glycol having an average molecular weight of by the standard procedure. Untreated slubbing, on washing after 2 days and 8 days, shrunk linearly by 28.0 and 28.3%, whereas the results for treated slubbing were 15.0 and 11.5%.

EXAMPLE V An aqueous emulsion containing pentaerythritol tetrakis (thioglycollate) was prepared as follows.

Sodium carboxymethylcellulose (1 g.) was dissolved in water at 70-80 C., and to the solution, which had been allowed to cool, were added 100 g. of the polythiol and 10 g. of an anionic emulsifying agent (an adduct of 1 mol. of a mixture of n-alkyl primary amines containing 16 to 18 carbon atoms in the molecule with 70 mol. of ethylene oxide), and the whole was stirred with a highspeed stirrer for 5 minutes.

A 12 g. portion of this emulsion was diluted with 276 g. of water, and with 12 g. of a 1% aqueous solution of diethylenetriarnine as catalyst, and padded onto wool fiannel as described in Example II; the thiol was then allowed to cure. The uptake of the thiol was 2%, while that of diethylenetriarnine was 0.04% The wool flannel, on being washed after one days curing at room temperature, shrunk by only 9.8%

In a second experiment, an emulsion was prepared as described above but substituting for the tetrathiol an equal weight of Thiol B.

Four grams of the emulsion of Thiol B were mixed with 12 g. of the emulsion of pentaerylthritol tetrakis(thioglycollate), '12 g. of 1% aqueous diethylenetriarnine solution, and 272 g. water, and the mixture was padded on to wool as described earlier in this example. Then the cloth was cured for 1 day at room temperature and washed, when the shrinkage in area was only 8.3%.

We claim:

1. A process for modifying keratinous fibrous material, which comprises (1) treating the material with a polythiol ester of the formula Thiol B denotes Hycar MTBN of B. F. Goodrich Chemical Co. According to the manufactures, it has a number average molecular weight of about 1700, and is a R (C0) (0R1) O CQLRLSH] thiol-terminated polymer containing about 21 butadiene L /v 11 units and 7 acrylonitrile units per average molecule. It F COOH comprises structures which may be represented by the L or f mula wherein HS F/CHgCEbCHCH) l SH R represents a hydrocarbon radical, contaimng a /a k l chain of at least 3 and at most carbon atoms,

N 50 and selected from the group consisting of ali- Epoxy resin A denotes a polyglycidyl ether of 2,2- phatic radicals, bis(4-hydroxypheny1)propane having a 1,2-epoxide con- R represents an alkylene group containing at least tent of 5-5.2 equiv./kg. 2 and at most 6 carbon atoms,

TABLE III Area shrinkage (percent) after- Per- Per- Per- Ester cent (Jo-reactant cent Catalyst cent lday 2days 8days Glyceroltris(thioglycollate) 6 Ethylene glycolbis(thioglycollate). 2 Monoethanolamine 0.8 14.0 11.2 8.8 Do s Thio .-do 0.8 12.6 10.8 Pentaerythrltoltetrakis(thio- 6 Ethylene glycol bis(3-mercaptopro- 2 Diethylenetriamine... 0.16 13.1 12.2

gtlycollate pionate).

Do 2 ThiolB 1 N 14.0 10.3 2 .....dr 1 do 9.3 9.3 6.9 1.5 Epoxy resinA 1.5 Diethyleuetriamine-.. 0.06 9.8 9.8

l The treated samples were cured by heating for 5 minutes at 150 C. before storing.

EXAMPLE IV Wool slubbing was padded to 300% uptake with a solution in perchloroethylene of 1,1,1-trimethylolpropane tris (thioglycollate) and monoethanolamine such that the pick-up of the polythiol was 8% and that of monoethanolamine was 0.8%. The slubbing was dried at C. for 30 minutes, and allowed to stand in contact with air. The elfectiveness of the treatment was assessed by measuring the shrinkage of samples of the slubbing that took place when the samples were washed (enclosed in cotton bags) 2. Process according to claim 1, wherein the polythio ester is of the formula in which R represents an alkylene hydrocarbon group of formula C H where m is an integer of at least 1 and at most 12, and R, p, and q have the meaning assigned in claim 1.

3. Process according to claim 2, wherein R represents a radical selected from the group comprising those of the formulae 4. Process according to claim 1, wherein the polythiol ester is of the formula R EOCO-R -SH],, in which R denotes an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms, R represents an alkylene hydrocarbon group containing 1 to 12 carbon atoms, p has the meaning assigned in claim 1.

5. Process according to claim 1, wherein the polythio ester is of the formula co-o-av-sn Escort] in which R and p each have the meaning assigned in claim 1,

R represents an alkylene group of formula C H where n is an integer of at least 2 and at most 12, and

u is selected from the class consisting of zero and 1.

6. Process according to claim 5, wherein R denotes a group selected from those of the formulae CH CH and CH CH(CH 7. Process according to claim 12, wherein the polythiol ester is of the formula R ECO0-R SH] in which R* represents an alkylene group of formula C H where n is an integer of at least 2 and at most 12, and R and p each have the meaning assigned in claim 1.

8. Process according to claim 7, where R denotes a group selected from those of the formulae CH CH and --CH CH(CH 9. Process according to claim 1, wherein 0.5 to 15% by weight of the polythiol ester is used, based on the weight of keratinous material treated.

10. Process according to claim 1, in which a catalyst for curing the polythiol is also applied, said catalyst being chosen from the group comprising bases, siccatives, oxidative curing agents, free-radical catalysts, sulphur, mercaptobenzothiazoles, dithiocarbamates, thiuram sulphides, thioureas, organic disulphides, alkyl xanthogen disulphides, and alkyl xanthates.

'11. Process according to calim 1, in which keratinous fibres are treated with the polythiol at a pH of from 7.5 to 12. a

12. Process according to claim 1, wherein the treated keratinous material is heated to a temperature in the range 30 to 80 C- to cure the polythiol.

13. Process for subjecting keratinous fibrous material to a shrink-resist treatment which comprises applying to the material a polythiol ester of formula in which R, R R a, x, y and p have the significance indicated in claim 1, (2) making up the material into at least a portion of a garment, and (3) setting the fabric in the desired configuration.

16. Process for subjecting a keratinous fabric to a durable press treatment which comprises applying a polythiol ester of the formula in which R, R R a, x, y and p have the significance indicated in claim 1, to the fabric already set in the desired configuration.

17. Process for flat-setting and shrinkpoofing a keratinous fabric, comprising treating it with a setting agent and setting it in a flat configuration by heating the fabric while wet, impregnating it with a polythiol ester of the in which R, R R a, x, y and p have the significance indicated in claim 1, drying and heating the fabric, and curing polythiol.

118. Fibrous keratinous material bearing thereon a. polythiol ester of the formula V 03 ).011 L w in which R, R R a, x, y and p have the significance indicated in claim 1, in the cured or still curable state.

19. Process for modifying keratinous fibrous material which comprises 13 (1) treating the material with a polythiol ester of most 2, with the proviso that x and y are unthe formula equal,

q is an integer of at least 1 and at most 4, with the proviso that (p+q) is at most 7, and 5 (2) curing the polythiol ester on the material.

(ql)(:v'-l) [R [00011] References Cited F UNITED STATES PATENTS 3,437,519 4/1969 -Friedl 117-141 10 3,223,413 12/1965 Bergen s 12s 3,477,804 11/1969 Fricdl 8-128 wherein R denotes a hydrocarbon radical having a chain DONALD LEVY Primary Examiner of at least 3 and at most 60 carbon atoms and selected from the group comprising aliphatic 15 CANNON Assistant Exammer and araliphatic radicals,

R denotes a divalent radical of formula C H where m' is an integer of at least 1 and at most 8--115.5, 115.6, 115.7, 11-6, 116.2, 116.3, 127.6, 128 A, 12, DIG 4, DIG 11, DIG 21; 2-243; 38-144; 117-138.8

p denotes an integer of at least 3 and at most 6, 20 F, 138.8 N, 138.8 UA, 139.4, 141, 143 A, 145, 161 LN, x and y each denote an integer of at least 11 and at 161 UZ, 161 UN, 161 ZB UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,706,5 7 Dated December 9 197 Inventor(s) BRYAN DOBINSON ET AL 7 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 10, line 51, after "phatic" insert and araliphatic C I Column 11, line &4, after "formula" delete "C H and insert C H v I Signed and sealed this mm day or June 1971;.

(SEAL) Attest:

EDWARD mmmmcusmm. c. MARSHALL 1mm Comigsi oner of Patents Atte sting Officer