US3753649A

US3753649A - Treatment of keratinous fibres and fabrics

Info

Publication number: US3753649A
Application number: US00114398A
Authority: US
Inventors: B Dobinson; B Robinson; D Massey; K Winterbottom
Original assignee: Ciba Geigy AG; IWS Nominee Co Ltd
Current assignee: Novartis AG; IWS Nominee Co Ltd
Priority date: 1970-02-26
Filing date: 1971-02-10
Publication date: 1973-08-21
Anticipated expiration: 1990-08-21
Also published as: ZA71790B; FR2081046A1; FR2081046B1

Abstract

This 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. This process comprises treating the material with a resin having at least two thiol groups per molecule and containing a radical of a polyhydric alcohol, bound to this radical, at least two poly(oxyalkylene) chains, at least two radicals of a thiolcontaining aliphatic carboxylic acid or of a thiol-containing aliphatic alcohol. As curing catalyst a sulfur-containing organic compound is used.

Description

United States Patent [191 Dobinson et a1.

TREATMENT OF KERATINOUS FIBRES AND FABRICS inventors: Bryan Dobinson, Duxford; Derek James Rowland Massey, Linton; Kenneth Winter-bottom, Whittlesford; Brian Robinson, Meston, all of England Assignees: Ciba-Geigy AG, Basel, Switzerland; 1. W. S. Nominee Company Limited, London, England Filed: Feb. 10, 1971 Appl. No.: 114,398

Foreign Application Priority Date Feb. 26, 1970 Great Britain 9,477/70 [1.8. CI 8/127.6, 2/243, 8/1 15.6, 8/115.5, 8/115.7, 8/116.3, 8/116.4, 8/127.5, 8/128, 8/D1G. 21, 8/D1G. 4, 8/D1G. 8, 8/D1G.

Int. Cl. D06m 3/06, D06m 15/00 Field of Search 2/243; 38/144;

[451 Aug. 21, 1973 [56] References Cited UNITED STATES PATENTS 3,484,417 12/1969 Kalopissis et a1. 8/127.6 X 3,576,592 4/1971 Zviak et al 3,619,106 11/1971 Kalopissis 8/127.6 X

Primary Examiner-George F. Lesmes Assistant Examiner-J. Cannon Attorney-l-larry Goldsmith, Joseph G. Kolodny and Mario A. Monaco 5 7] ABSTRACT This 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. This process comprises treating the material with a resin having at least two thiol groups per molecule and containing a radical of a polyhydric alcohol, bound to this radical, at least two poly(oxyalkylene) chains, at least two radicals of a thiol-containing aliphatic carboxylic acid or of a thiol-contai ning aliphatic alcohol. As curing'catalyst a sulfur-containing organic compound is used.

15 Claims, No Drawings TREATMENT OF KERATINOUS FIBRES AND FABRICS This 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 curable resin or precursor thereof to the material which may be in fabric or fibre form. Shrinkresist 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 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 the effect of agitation in the presence of aqueous solutions. The desired shape maybe imparted to the material, before or after 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 severe test for the durable press and shrink-resist treatments.

One of the attractions of keratinous fibres and particularly wool is their excellent handle, and an important disadvantage associated with many of the resins used in shrink-resist and durable press processes is the harsh handle imparted to the fibre and fabric containing the fibres. Attempts to overcome this harsh handle have been made by the use of softeners, but these have not always been successful since they sometimes reduce the effectiveness of the resin.

It has recently been found that certain thiolterminated poly(oxyalkylene) resins can be successfully used in durable press and shrink-resist processes and do not impart an unattractive handle to the treated material. The resins cure, i.e. undergo reaction, on the keratinous fibre, the rate of curing being largely controlled by selection of an appropriate catalyst. Substances proposed as catalysts are organic and inorganic bases, siccatives, free-radical catalysts, and oxidative curing agents. The more effective of these catalysts are primary and secondary amines, but when these amines are used an undesirable odour is often imparted to the treated material.

We have now found that is is possible to accelerate the cure of the thiol-terminated poly(oxyalkylene) resins on a keratinous material by means of sulphur or certain sulphur-containing organic compounds in which the sulphur atoms are not exclusively present in mercaptan groups: when such a substance is used as the catalyst the treated material is generally free from undesirable odours and the rate of cure is often faster than when the catalysts previously proposed are used.

Accordingly, the present invention provides aprocess for modifying keratinousmaterial, which comprises i. treating the material with a resin'having at least two thiol groups per molecule and containing a. a radical of a polyhydric alcohol,

b. bound to this radical,-at least two poly(oxyalkylene) chains,

c. bound through oxygenatoms to carbonatoms in the said poly-(oxyalkylene) chains, at least two residues chosen from acyl residues of thiolcontaining aliphatic carborrylic acids and residues, after removal of a hydroxylgroup, of thiolcontaining aliphatic alcohols, and

ii. as curing catalyst, a sulphur-containing organic compound in which thesulphur atoms are notexclusively present in mercaptangroupsand which is a dithiocarbamate, a thiuram sulphide, a thiourea,

or an alkyl xanthogen disulphide,

and curing the resin on the material.

This invention also provides keratinous material having thereon a polythiol resin as aforesaid and a catalyst as aforesaid, and keratinous material havingthereon a polythiol resin as aforesaid cured in the presence of a said catalyst.

The polythiol preferably containsthree to six thiol groups per molecule. Especially good results have been obtained with resins containing three or fourthiol groups per molecule.

Preferred polythiols are those having arnolecular weight between 400 and 10,000, particularly those of formula,

"ito aikifineflofilqsh i i [(0-alkylene)mO(C0)s-iX] I in which n, p, and q each represent positive integers, m is an integer of atleast 1 and may have different valuesin each of the p and (q-l) chains, n is at most 2, a p is atleast 2 and at most 6,

(p q) equals at least 3 and at. most 7, each alkylene group contains a chain of at least2 and at most 6 carbon atoms betweenconsecutive oxygen atoms, 'R represents an aliphatic radical containing at least 2 carbon atoms, and X represents an aliphatic radical containing at least one thiol group. The oxyalkylene units in individual .poly(oxyalkylene) chains may be different, and they maybe substituted if desired, e.g. by phenyl or chloromethyl groups.

There may thus be used the partially orfully esterified compounds of the formula canvass) 63515-1 o-aik iene .,o-oo-c.m.sm, n

in which R, alkylene, m, p, and q have the meanings previously assigned, and r is a positive integer which may be as high as 18 or even 24.

Further preferred are esters of the formula [in] umsnrymrgae 6.63318; H1

in which alkylene, m, and u have the meanings previously assigned,

PI is an integer of at least 3 and at most 6, and R, represents an aliphatic hydrocarbon radical having at least three and at most six carbon atoms. Still further preferred are esters based on gylcerol, hexane-b 1,2,5-triol or hexane-1,2,6-triol, and ethylene oxide and/or propylene oxide, i.e. those of the formulae in which m and u have the meanings previously assigned, and t is an integer of at least 2 and at most 3.

These thiol-terminated poly(alkylene oxide) esters are readily prepared by the reaction of a polyhydric alcohol with an alkylene oxide followed by esterification of the terminal hydroxyl groups with a mercaptocarboxylic acid.

Suitable polyhydric alcohols include ethylene glycol, poly(oxyethylene) gylcols, propylene glycol, poly(oxypropylene) gylcols, propane-1,3-diol, poly(epichlorohydrin)s, butane-l,2-diol, butane-1,3-diol, butanel ,4-diol, butane-2,3-diol, poly(oxy-l ,1- dimethylethylene) glycols, poly(tetrahydrofuran)s, glycerol, l ,l l trimethylolethane, l,l l trimethylolpropane, hexane-1,2,5-triol, hexane-l,2,6 triol, pentaerythritol, dipentaerythritol, mannitol, sorbitol, and adducts of alkylene oxides with ammonia or amines, such as diethanolamine and tetrakis(2- hydroxyethyl)ethylenediamine. Suitable alkylene oxides include ethylene oxide, propylene oxide, and, less preferably, the butylene oxides, epipchlorohydrin or tetrahydrofuran. If desired, the polyhydric alcohol may 4. be treated with one alkylene oxide, said propylene oxide, and then tipped" with a different alkylene oxide. such as ethylene oxide.

The preferred mercaptocarboxylic acids for the esterification are thioglycollic acid (2-mercaptoacetic acid), 2-mercaptopropionic acid, and 3-mercaptopropionic acid, but other mercaptomonocarboxylic acids which may be used include 2-mercaptoundecylic acid and Z-mercaptostearic acid.

Polythiol esters most preferred for the purposes of the present invention are those obtained from glycerol, propylene oxide, and thioglycollic acid, i.e. of formula 0H,- 0 031mm oidfi'fijii' H-(OCaHoMOCOClLSH H,(oo,H.)moo0oH2sH VII where m has the meaning previously assigned, having a molecular weight within the range 1,000 to 5,000. Such resins are commercially available.

The second class of thio'l-terminated poly(alkylene oxides) includes those ethers of formula VIII in which R, denotes OH, --(O-alkylene ),OH, --O.CO.C,,H-

SH, or (O-alkylene),O.CO.C,,H,,,SH,

R, alkylene, m, p, q, and u have the meanings previously assigned,

and v is an integer of at least l and may have different values in each of the p chains.

Th oxyalkylene units in the individual poly(oxyalkylene) chains may likewise be different, but are preferably the same, and may be substituted if desired by e.g., phenyl or chloromethyl groups.

Preferred among such ethers are those which are also of formula in which alkylene, R,, m, R,, p,, and q have the meanings previously assigned, and further preferred are those of the formula (O-alkylone) OCH CHCH SH s] 1 1 a p, X

in which R, and p, also have the meanings previously assigned.

The particularly preferred ethers, of formula 1 [(OCtHmmOCH CHCILSH] in which R,, t, m, and p have the meanings previously assigned, are also commercially available. The ethers of formula Vlll in which R, denotes OH may be prepared in a known manner by reaction of an alkylene oxide with a polyhydric alcohol, etherification of the hydroxyl groups of the product with epichlorohydrin, and treatment with sodium hydrosulphide to replace the chlorine by a sulphhydryl group (see US. Pat. No. 3,258,495, and United Kingdom Specifications Nos. 1076725 and 1144761).

Ethers of formula CtHmvOH XII in which R t, m, v, and p, have the meanings previously assigned, are likewise particularly preferred. Ethers of formula VII] in which R denotes -(O- alkylene ),,OH may be prepared by treating the product which is obtained from epichlorohydrin, the alkylene oxide and the polyhydric alcohol, first with an alkylene oxide, and then with sodium hydrosulphide (see United Kingdom Specification No. 1144761).

The most preferred ethers are those of formula H XIII XIV wherein M represents a metal atom, or an ammonium group which may be substituted, b represents l or 2 and is the available valency of M, X and X either each represent an alkyl group containing one to six carbon atoms (which may be sub- 6 stituted by a mononuclear aryl group), a cycloalkyl group containing three to eight carbon atoms, or a mononuclear aryl group,

X and X together denote an alkylene chain of two to six carbon atoms which may be substituted by one or more alkyl groups each containing one to six carbon atoms,

when b represents 2, the two groups X may together represent an alkylene chain of two to six carbon atoms linking the N atoms of the two dithiocarbamate groups, in which case both groups X represent hydrogen atoms,

b. thiuram sulphides .of the general formula wherein X and X are as hereinbefore defined and w represents an integer of l to 4,

c. thioureas of the general formula XVI wherein X and X each represent a hydrogen atom, an alkyl group of one to six carbon atoms, or a phenyl group, and X and X" each represent a hydrogen atom or an alkyl group of one to six carbon atoms,

X and X together represent an alkylene group of two to six carbon atoms in which case X and X each represent hydrogen atoms, or

d. alkyl xanthogen disulphides of the general formula XVII wherein X represents an alkyl group of one to six carbon atoms.

Preferred catalysts used according to the present invention are compounds of formula XlV in which X and X are the same and each represents an alkyl group of one to four carbon atoms and M represents sodium, nickel, copper, or zinc, and complexes of these compounds with secondary alkylamines; compounds of formula XIV in which b represents 2 and the two groups X together denote an ethylene group, the two groups X each represent a hydrogen atom, and M represents zinc or manganese; compounds of formula XIV in which M represents a piperidinium group, and X and X together denote a chain -(CH,),, to form with the indicated nitrogen atom a piperidino group; compounds of formula XV in which X and X are the same and each represents an alkyl group containing from one to four carbon atoms; the compounds of formula XV in which X and X together represent a pentamethylene chain and w represents 1, 2,or 4; the compounds of formula XVI in which X and X together represent an ethylene group, and X and X each represent a hydrogen atom; compounds of formula XVl in which X and X each represent an alkyl group of one to four carbon atoms, and X and X each represent an alkyl group hydrogen atom; and compounds of formula XVII in which X represents an alkyl group containing from one to four carbon atoms.

The amount of catalyst applied may vary depending upon the nature of the polythiol, the keratinous material, the desired rate of cure, and other factors, but is generally within the range 0.1 to 20 percent by weight, and preferably 2 to percent by weight, on the weight of the polythiol.

The treatment according to the invention, whether to achieve shrink-resist or durable press results, provides fibres or garments which have an excellent handle and which will withstand washing in machines and still retain their original dimensions 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 process according to the invention, as well as inhibiting or preventing felting shrinkage, also inhibits or prevents relaxation shrinkage, which is an important problem associated with knitted goods, and thus the present process finds particular application in the shrink-resist treatment of knitted 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, nonwoven fabrics, woven fabrics and knitted goods. In most cases the treatment will be applied to fabrics or made-up garments through it is quite feasible, and may be desirable in some circumstances, to shrink-resist fibres, e.g. in the form of tops. 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 and regenerated cellulosic material. In general, however, the material should contain at least 30 percent by weight of keratinous fibres and better results are obtained with 100 percent keratinous fibre-containing material.

The keratinous material may be virgin or reclaimed: preferably, though not exclusively, 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 sheep's wool.

The polythiols may be used, if desired, with other resins or resin-forming materials, such as aminoplasts, epoxy resins (i.e. substances containing, on average more than one l,2-epoxide group per molecule) and polyisocyanates.

Many of the polythiols are insoluble in water but can be applied as aqueous disperions or emulsions. Suitable emulsions can be prepared by dispersing the polythiol in an aqueous plase, using an emulsifying agent such as an adduct of a longchain 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. They may also be applied from organic solvents, for example lower alkanols such as ethyl alcohol, 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 the polythiol used depends on the effect desired. For most purposes from 0.5 to 15 percent by weight based on the material treated is preferred. Stabilization of knitted fabrics usually requires from 1 to 10 percent by weight of the polythiol. 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 percent 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 agent required to give the desired effect may readily be determined. Further the construction of the fabric also influences the amount of polythiol required.

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.

Curing of the polythiols is assisted by using elevated temperatures, and if especially rapid results are required then temperatures in the range 40 to lC may be used. The resin and catalyst may be applied to the keratinous material in conventional ways. For example, wool tops or fabric may be impregnated by padding the polythiol onto the material or by immersing the material in a solution of the polythiol. Garments or garment pieces may be sprayed with the polythiol, or tumbled in a solution of it in an organic solvent, such as in the dry-cleaning machine with a solution in a drycleaning solvent.

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 fibres as tops or card sliver. The fabric may be flat-set 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 flat-setting may not be necessary or even desirable with certain types of cloth. Flatsetting 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 the maintaining th cloth in a flat state while washing off the excess reagents. In another method flat-setting may be achieved by impregnating the material with a swelling agent and an alkanolamine carbonate, e.g. urea and diethanolamine carbonate, and drying and semi'decatising the material. Of course, if desired, the fabric may be set in the presence of the polythiol, 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 madeup 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.

An alternative 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 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 if required, drying 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 resin treatment, may be effected by any known method, for example by setting agents, e.g. reducing agents, bases, water, and superheated steam. Monoethanolamine sesquisulphite is the most frequently used, and may beused in association with a swelling agent, such as 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 paraffin wax, and fluorescent brightening agents.

The invention will now be illustrate by the following Examples. Unless otherwise specified, parts and percentages are by weight. The standard wash was effected as follows.

Fabric samples were washed for about 15 minutes in an English Electric Reversomatic washing machine set on programme with the timing control set on 1. The wash liquor contained 2 g/litre of soap flakes and 0.8 g/litre of soda ash. The liquor ratio was 30:1. After being washed the samples were rinsed in the machine, spin-dried and finally tumble dried in a Parnall Tumble Dryer on full heat for 30 minutes.

The polythiols used were prepared as follows.

POLYTHIOL A A mixture of 800 g (0.2 g-mol.) of a tirol of averag 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 was heated 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 azeotrope with toluene. The mixture was cooled and washed with water, and the organic layer was separated. On removal under vac uum of the solvent from the organic layer there remained 793 g( 94 percent of the theoretical yield) of the desired tris(thioglycollate) (Polythiol A), having a thiol content of 0.59 equiv./kg.

POLYTHIOL 1B This denotes an aqueous emission containing 50 percent of Polythiol A and 5% of an emulsifying agent which was an adduct of mixed C -C primary nalkylamines (1 mol.) with ethylene oxide mol.).

POLYTHIOL C This denotes a poly(2-hydr0xy-3-mercaptopropyl) ether prepared from a glycerol-propylene oxide adduct having an average molecular weight of 4,800, epichlorohydrin, an sodium sulphide. It had a thiol content of 0.32 equiv./kg.

POLYTHIOL D This is similar to Polythiol B but also contains 0.5 percent of a protective colloid, sodium carboxymethylcellulose.

The catalysts used were as follows Catalyst 1 was N,N'-diethylthiourea,

Catalyst 2 was tetramethylthiuramdisulphide,

, Catalyst 3 was tetrabutylthiuramdisulphide,

Catalyst 4 was nickel dibutyl dithiocarbamate, Catalyst 5 was sodium dimethyl dithiocarbamate, Catalyst 6 was the 1:1 complex of zinc dibutyl dithiocarbamate and dibutylamine,

Catalyst 7 was zinc ethylenebis(dithiocarbamate),

Catalyst 8 was ethylenethiourea,

Catalyst 9 was tetramethylthiuram monosulphide,

Catalyst 10 was di-isopropyl xanthogen disulphide,

Catalyst ll was sodium dibutyl dithiocarbamate,

Catalyst 12 was piperidinium pentamethylene dithiocarbamate,

Catalyst 13 was dipentamethylenethiuram tetrasulphide,

Catalyst 14 was zinc diethyl dithiocarbamate,

Catalyst 15 was copper dimethyl dithiocarbamate.

In some of the experiments, monoethanolamine was used as catalyst or as a co-catalyst. This is denoted by the abbreviation MEA.

EXAMPLE I The cloth used as a wool flannel weighing approximately 170 g per squre metre, the pH of its aqueous extract was 7.6. Samples of the flannel were padded with a 1 percent solution of Polythiol A or Polythiol C in perchloroethylene containing the catalyst at the stated concentration such that the uptake of polythiol was 3 percent. Other samples were padded from aqueous emulsions of Polythiol B which had first been diluted with parts of water per 6 parts of the emulsion and catalyst, such that uptake of Polythiol B was 6 percent.

The samples were dried at 50C in a fanned oven and stored at room temperature and humidity.

l, or 2, or 8 days after the samples had been impregnated they were washed and dried and the shrinkage of the fabrics was determined by measurement of the di mensions before and after washing.

Untreated cloth shrank in an area by an average of 19.5 percent. Results obtained with samples treated in accordance with the method of this invention are shown in Table l. The proportions of the catalyst and co-catalyst if any, quoted in the Table, are expressed as a percentage of the weight of wool treated.

,- TABLE I sample treated with Catalyst 2 untreated sample Percent Area shrinkage (percent) after- Percent Co-catco-cat- Catalyst catalyst alyst alyst 1 day 2 days 8 days These results show that treatment with catalysts according to the present invention imparts shrinkresistant properties to wool which are as good as, or better than, those imparted using a conventional catalyst (MEA). Moreover, the odour of wool treated in accordance with the present invention was markedly less than that of wool treated with a polythiol and MBA alone.

EXAMPLE [1 Example 1 was repeated, using other combinations of Polythiol and catalyst.

Poly- Cata- I: Cata- Area Shrinkage (21) after thiol lyst lyst l day 2 days 8 days A l3 0.3 8.4 6.5

D' l l 0.3 7.4 6.9

"In this experiment the wool was first reduced by padding to 70% uptake with an aqueous solution containing, per litre, g of monoethanolamine and 29 g of a 70% aqueous solution of monoethanolamine sesquisulphite; it was then steamed wet for 2% minutes.

EXAMPLE Ill 1. Wool flannel was treated with an aqueous solution containing 29 g per litre of percent monoethanolamine sesquisulphite and 20 per litre of monoethanolamine such that the uptake was 70 percent. Samples were then steamed wet for 2% minutes to impart a crease, then they were impregnated to 270 percent uptake with trichloroethylene (266.7 g) containing 0.3 g of a catalyst and 3 g of Polythiol A, and dried in an oven for 10 minutes at 70C.

2. Wool flannel samples were impregnated with the trichloroethylene solution of Polythiol A containing the catalyst, and dired as described under I, then they were padded with the monoethanolamine and monoethanolamine sesquisulphite solution as described under I, and steamed wet as before to impart a crease.

All the samples were washed after storage for 3 days at room temperature.

The results obtained were Area Crease Catalyst Treatment Shrinkage retention 5 l2 1 7.9 good 2 7.4 very good I! 1 NJ very good 2 8.3 good We claim:

1. Process for modifying fibrous keratinic textile material, which comprises treating the material with 13 i. a resin having a molecular weight between 400 and 10,000 of the general formula wherein n is l or 2, m is an integer of at least 1, p is 26,

p q is 3-7, R is an aliphatic hydrocarbon radical with ii. a curing catalyst selected from the group consisting of a. dithiocarbamates of the general formula 1. wherein X, and X are the same and each represents an alkyl group of one to four carbon atoms, M'representssodiurn, nickel, copper or zinc. and complexes of these compounds with secondary alkylamines and b represents the valence of M;

2. or wherein b represents 2 nd the two groups X, together denote and ethylene group, the two groups X each represent a hydrogen atom and M represents zinc or manganese; or

3. wherein M represents a piperidinum group, X, and X together denote a chain(CH,) to form ith the indicated nitrogen atom a piperidino group;

b. thiuram sulfides of the general formula N-C s-s .0 S-N 1. wherein X, and X, are the same and each represents an alkyl group containing from one to four carbon atoms and w represents an integer of from one to four or 2. wherein X, and X, together represent a pentamethylene chain and w represents 1, 2 or 4;

c. thioureas of the general formula 1. wherein X, nd X. together represent an ethylene group and X, and X, each represent a hydrogen atom;or I

2. wherein X nd each represent an alkyl group of one to four carbon atoms and X, each represent a hydrogen atom; or d. alkylxanthogen disulphides of the general formula.

wherein X, represents an alkyl group containing from one to four carbon atoms; and y iii. curing said resin. on the textile material. 2. Process of claim 1 wherein the resin is selected from theclass of thiol-terminated poly(alkyleneoxides) of the formula:

wherein sai resin has a molecular weight between about 1,000 and 5,000.

3. Process according to claim 1 wherein the resin is selected from the class of thiol-terminated poly(akyleneoxides) of the formula having a molecular weight between 700 and 3,500.

4. Process according to claim 1, wherein there is applied from 0.1 to 20 percent by weight of the catalyst, calculated on the weight of the polythiol resin.

5. Processraccording to claim 1, wherein there is applied from' 0.5 to 15 percent by weight of the polythiol resin calculated on the weight of the keratinous material treated.

6. Process according to cliam l, in which the treated keratinous material is heated to a temperature in the range 30+ to C to cure the polythiol resin.

- 7.'Process according to claim 1,. in which the keratinous fibres are treated with the polythiol resin a a pH of from 7.5 to 12.

8. Process for subjecting fibrous keratinic textile material to a. shrink-resist treatment which comprises applying to the material a polythiol. resin as specified in claim 1 and a catalyst as specified-in claim 1.

9. Process for flat-setting and shrinkproofing a keratinous fabric, comprising treating it with a setting agent and setting it in a flat configuratio'mby heating the fabric while. wet, impregnating it withra polythiol resin as specified in claim. 1,. and a catalyst-as specified in claim I drying the fabric, and curing the; polythiol resin.

10. Keratinoun material bearing thereon a polythiol resin as specified in claim I and which has been cured in the presence of a catalyst as specified in claim i.

ll. Keratinous material bearing. thereon a polythiol resin as specified in claim 1 in the still curable state and a catalyst as specified in claim 1.

12. Process for subjecting keratinous material in fabric form to a durable press treatment which comprises applying a polythiol resin as specified in claim 1 and a catalyst specified in claim 1 to at least a portion of a garment already set in the desired configuration.

15. Process according to claim 14, wherein the garment portion has been set in the desired configuration by treating the material with a setting agent maintaining the treated area in the desired configuration, and

applying heat and pressure thereto.

* III l 1;itlli'ilF-HIA'IE UF CORRELHION Patent No. I 3,753,649 Dated August 21, 1973 Inventor-( BRYAN DOBINSON ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: I

Column 13, claim 1, line 33, change "2 nd" to" 2 and line 3 change "and" t an I line 38, change "form ith" toform with line 6 1 chan e "X to." X and X g 5x7 5 7 Column 1 claim 2, line 15, change "sai resin" to-' said resin Column in, claim 6, line +3, change "30+" to-- 30 Signed and sealed this 18th day of December 1973.

(SEAL) Attest;

EDWARD M .FLETCHER,,JR. g RENE D. TEGTMEYER Attesting Officer Acting Commissioner of Patents

Claims

2. making up the fabric into at least a portion of a garment, and
2. ProcesS of claim 1 wherein the resin is selected from the class of thiol-terminated poly(alkyleneoxides) of the formula:
2. wherein X4 nd 6 each represent an alkyl group of one to four carbon atoms and X5 X7 each represent a hydrogen atom; or d. alkylxanthogen disulphides of the general formula (X8OCS2)2 wherein X8 represents an alkyl group containing from one to four carbon atoms; and iii. curing said resin on the textile material.
2. wherein X2 and X3 together represent a pentamethylene chain and w represents 1, 2 or 4; c. thioureas of the general formula
2. or wherein b represents 2 nd the two groups X2 together denote and ethylene group, the two groups X3 each represent a hydrogen atom and M represents zinc or manganese; or
3. wherein M represents a piperidinum group, X2 and X3 together denote a chain-(CH2)5 to form ith the indicated nitrogen atom a piperidino group; b. thiuram sulfides of the general formula
3. setting the fabric in the desired configuration.
3. Process according to claim 1 wherein the resin is selected from the class of thiol-terminated poly(akyleneoxides) of the formula
4. Process according to claim 1, wherein there is applied from 0.1 to 20 percent by weight of the catalyst, calculated on the weight of the polythiol resin.
5. Process according to claim 1, wherein there is applied from 0.5 to 15 percent by weight of the polythiol resin calculated on the weight of the keratinous material treated.
6. Process according to cliam 1, in which the treated keratinous material is heated to a temperature in the range 30+ to 180*C to cure the polythiol resin.
7. Process according to claim 1, in which the keratinous fibres are treated with the polythiol resin a a pH of from 7.5 to 12.
8. Process for subjecting fibrous keratinic textile material to a shrink-resist treatment which comprises applying to the material a polythiol resin as specified in claim 1 and a catalyst as specified in claim 1.
9. Process for flat-setting and shrinkproofing 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 resin as specified in claim 1, and a catalyst as specified in claim 1, drying the fabric, and curing the polythiol resin.
10. Keratinous material bearing thereon a polythiol resin as specified in claim 1 and which has been cured in the presence of a catalyst as specified in claim 1.
11. Keratinous material bearing thereon a polythiol resin as specified in claim 1 in the still curable state and a catalyst as specified in claim 1.
12. Process for subjecting keratinous material in fabric form to a durable press treatment which comprises
13. Process according to claim 12, wherein the garment portion is set in the desired configuration by treating the material with a setting agent, maintaining the treated area in the desired configuration, and applying heat and pressure thereto.
14. Process for subjecting keratinous material in fabric form to a durable press treatment which comprises applying a polythiol resin as specified in claim 1 and a catalyst specified in claim 1 to at least a portion of a garment already set in the desired configuration.
15. Process according to claim 14, wherein the garment portion has been set in the desired configuration by treating the material with a setting agent maintaining the treated area in the desired configuration, and applying heat and pressure thereto.