NO131946B - - Google Patents

Description

The present invention relates to a method for making keratin-containing fiber material or textiles shrink-resistant and giving them permanent pressure retention.

A number of methods for making keratin-containing materials shrink-free are known, and some of these involve the application of a resin to the material, which may be in the form of a fabric or cloth, or in the form of fibres. Processes that result in freedom from shrinkage stabilize the dimensions of the keratin-containing materials against shrinkage as a result of felting.

Processes which impart permanent pressure to keratin-containing materials are also known, and in several of them use is made of the same resins or of similar resins. In certain processes to impart permanent pressure to the materials, the keratin-containing material is given the desired shape before the resin is cured, after which the curing is allowed to take place while the material is held in the desired shape, e.g. with folds or pleats. In other processes, the resin is applied afterwards

that the material is given the desired shape. Processes for imparting permanent pressure to a material stabilize the material's shape and surface softness, so that these properties are not lost in the presence of aqueous solutions. The material can be given the desired shape before or after the resin treatment using well-known methods which involve the use of fixing agents such as water, reducing agents and bases.

A desirable, although not absolutely necessary, feature of processes for imparting freedom from shrinkage and lasting pressure is that the keratin-containing material treated in this way should be washable in household washing machines. To be machine washable, the finish of the treated material must be able to withstand vigorous agitation in lukewarm or hot water containing detergents, and this requirement puts the treatments to achieve lasting pressure and freedom from shrinkage to a strict test.

One of the advantages of keratin-containing fibers, and wool in particular, is their excellent grip, and a significant disadvantage associated with many of the resins that have been used in processes for imparting shrinkage freedom and permanent pressure is the rough grip imparted to the fibers and substances containing the fibers. Attempts have been made to overcome this disadvantage by using plasticizers, but this has not been shown to give satisfactory results, as the plasticizers reduce the effect of the resin.

A class of resins has now been found, comprising certain poly-(oxyalkylene) resins with thiol end groups, which can be used with good results in processes for imparting permanent pressure and freedom from shrinkage, and which do not give the treated material an unappealing grip. These resins are cured, i.e. undergo a reaction, on the keratin-containing fibres, and it has also been shown that the curing rate can be regulated to a large extent by choosing a suitable catalyst.

The present invention thus relates to a method for making keratin-containing fiber material or textiles shrink-resistant and giving them permanent pressure retention, in that a polythiol resin is placed on the fiber or textile and cured on it, and the method is characterized by the use of a polythiol resin containing 3-6 thiol groups per . molecule bg has a molecular weight between 400 and 10,000 and has the formula:

where m, p and q each denote an integer,

m is at least 1,

p is 2 - 6,

(p + q) = 3 - 7,

in that each "alkylene" group contains a chain of 2-6 carbon atoms between successive oxygen atoms and they may be substituted with phenyl or chloromethyl groups,

R is an aliphatic group with at least 2 carbon atoms, and

X is an alkyl or alkanoyl group containing at least one thiol group.

Preferably, according to the invention, a polythiol resin with the formula is used:

where R2 is an aliphatic hydrocarbon group with 3-6 carbon atoms, "alkylene" and m is as indicated above,

P2 is an integer from 3 - 6, and

u is 1 or 2.

The method according to the invention, whether it is carried out to achieve freedom from shrinkage or to achieve lasting pressure, gives fibers or garments that can be washed in a washing machine and retain the original dimensions and the original shape. In addition to the excellent grip of materials treated by the method according to the invention, the treated material will also be free of wrinkles and creases, which is a significant advantage for fabrics used in legwear, which have a strong tendency to crease in the area at the knees and behind the knees. Of course, freedom from creasing is a characteristic that is desired in many items of clothing.

The term "keratin-containing material" as used herein includes all forms of keratin-containing fibers or fabrics and garments made from these, such as stocking, tops, carding tapes, noils, yarns, threads, worsted fabrics, non-woven fabrics, woven fabrics and stretch fabrics. In most cases, the treatment will be carried out on fabrics or ready-made garments, although it is also possible, and under certain circumstances desirable, to make fibers shrink-free, e.g. fibers in the form of tops. The material that is treated can consist either exclusively of keratin-containing fibers or of mixtures of these fibers with fibers or filaments of synthetic materials such as polyamides, polyesters and polyacrylonitrile, and of materials based on cellulose and regenerated cellulose. Generally, however, the material should contain at least 30% by weight of keratin-containing fibers, and the best results are obtained with materials of 100% keratin-containing fibers.

The keratin-containing material can be a naturally occurring material or a regenerated material. Sheep's wool is preferably used. However, alpaca, cashmere, mohair, vicuña, guanaco, camel hair, silk and llama or mixtures of these materials with sheep's wool can also be used.

The polythiol resin used in the method according to the invention contains 3-6 thiol groups per molecule. Particularly good results have been achieved with resins containing 3 or 4 thiol groups per molecule.

The oxyalkylene units in the individual poly(oxyalkylene) chains can be different. If desired, they can be substituted, e.g. with phenyl or chloromethyl groups.

One can thus use the partially or fully esterified compounds of the formula:

where R, "alkylene", m, p and q have the meanings given above, and r is an integer which can be as high as 18 or even 24.

Other preferred compounds are esters of the formula:

where "alkylene", m, u, p, q and (p + q) have the meanings given above, and

R^ denotes an aliphatic group with 2-6 carbon atoms.

Other compounds which are also preferred are esters based on glycerol, hexane-1,2,5-triol, or hexane-1,2,6-triol and ethylene oxide and/or propylene oxide, i.e. compounds of the formula:

where m and u have the meanings given above, and t is 2 or 3.

These poly(alkylene oxide) ester resins with thiol end groups can be easily reacted by reacting a polyhydric alcohol with an alkylene oxide with subsequent esterification of the hydroxyl end groups with a

mercaptocarboxylic acid.

Suitable polyhydric alcohols include ethylene glycol, poly-(oxyethylene) glycols, propylene glycol, poly(oxypropylene) glycols, propane-1,3-diol, poly(epichlorohydrin)ers, butane-1,2-diol, butane-1,3-diol , butane-1,4-diol, butane-2,3-diol, poly(oxy-1,1-dimethylethylene) glycols, poly(tetrahydrofuran)ers, glycerol, 1,1,1-trimethylolethane, 1,1, 1-trimethylolpropane, hexane-1,2,5-triol, hexane-1,2,6-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, to a lesser extent, the butylene oxides, epichlorohydrin and tetrahydrofuran. If desired, the polyhydric alcohol can be treated with 1 mol of alkylene oxide, e.g. propylene oxide, and then another alkylene oxide, such as ethylene oxide, is added.

The preferred me^captocarboxylic acids for the esterification reaction are thioglycolic acid (2-mercaptoacetic acid) and 2-mercaptopropionic acid, but other mercaptomonocarboxylic acids can also be used, such as mercapto-undecylic acid and mercaptostearic acid.

The polythioesters that are preferred in the method according to the invention are those obtained from glycerol, propylene oxide and thioglycolic acid, i.e. those of the formula:

where m has the meaning given above, the esters having a molecular weight between 1000 and 5000. Such resins are commercially available.

The second class of thiol-terminated poly(alkylene oxides) includes the ethers of the formula:

where

R 3 denotes -OH, -(O-alkylene)vOH, -O.CO.CuH2uSH or -(O-alkylene)O.CO.C H„ SH,

'v u 2 u '

R, "alkylene", m, p, q and u have the above meanings and

v is an integer which is at least 1, and which can have different values in each of the p-chains.

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

Preferred among such ethers are those which also correspond to the formula: where "alkylene", Rn, m, R_, p and q have the meanings given above, and particularly preferred ethers are those of the formula:

where R^ and p^ have the meanings indicated above.

The particularly preferred ethers of the formula:

where > t> m and p^ have the meanings stated above, are available commercially. The ethers of formula II, in which R^ denotes hydroxyl, can be prepared in a known manner by reacting an alkylene oxide with a polyhydric alcohol, esterifying the hydroxyl groups of the product with epichlorohydrin and treating the product obtained with sodium hydrosulfide to replace the chlorine with a sulfhydryl group (see US Patent No. 3-258,495 and British Patent No. I,076,625 and No. 1,144,76l). In many cases, the average number of thiol groups per molecule not a whole number, but e.g. 2.6. This is partly due to the fact that the replacement of the chlorine atom with the group -SH does not take place completely, and partly as a result of side reactions. For example, the chlorohydrin ether obtained by the reaction with epichlorohydrin can also react with epichlorohydrin, whereby an ether is formed which contains two exchangeable chlorine atoms per hydroxyl group that was originally present in the polyhydric alcohol.

Ether a<y> formula:

where R , t, m, v and p„ have the meanings indicated above, are likewise particularly preferred. Ethers of formula II in which R^ denotes -(O-alkylene)^OH, can be prepared by treating the product obtained from epichlorohydrin, the alkylene oxide and the polyhydric alcohol, first with an alkylene oxide and then with sodium hydrosulphide (see British patent document no. 1.144-761).

The most preferred ethers are those of the formula:

especially those ethers of the formula which have a molecular weight between 700 and 3500.

The ether esters of formula II in which R^ denotes -O.CO.C^H^SH or -(O-alkylene^O.CO.CM-^SI-^ can be obtained by esterification of the corresponding alcohol with a mercaptocarboxylic acid HOOCC ^H^SH.

The polythiol resins can be used alone or together with other resins or resin-forming materials, such as aminoplasts and preferably epoxy resins (ie materials which on average contain more than one 1,2-epoxy group per molecule) or polyisocyanates. Particularly good results have been obtained with mixtures of the polythiol resins and prepolymers of a polymeric polyhydroxy compound and polyisocyanate. Examples of resins of the latter type are prepolymers of a polyoxyalkylene glycol and an aromatic diisocyanate or of a poly(oxyalkylene)triol and an aliphatic diisocyanate. Particularly good results have been achieved with a mixture of

a) thiol resin A, which is described in detail below, and

b) "Synthappret" LKF, which is described as a polyisocyanate prepolymer.

Many of these polythiol resins are insoluble in water, but can be used in the form of aqueous dispersions or emulsions. Preferably, the resins are applied to the fabrics and garments from organic solvents, e.g. 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 no more than 3 carbon atoms, such as the dry cleaning solvents, carbon tetrachloride, trichlorethylene and perchlorethylene.

The amount of polythiol resin used depends on the desired effect. For most purposes, it is preferred to use from 0.5 to 15% by weight, calculated on the weight of the treated material. Stabilization of knitwear usually requires from 1 - 10% by weight of the resin. Good freedom from shrinkage, good pressing properties and a significant freedom from creasing can be achieved for woven textiles with relatively small amounts, especially with amounts from 1-5% by weight. The grip of the treated material will of course depend on the amount of resin used, and by simple experiments the smallest amount of resin required to produce the desired effect can easily be determined. In addition, the structure of the textile will also have an impact on the amount of resin required.

The desired effects are not fully achieved until substantially all of the polythiol resin on the material has been cured. At normal temperatures, this can take from 5-10 days or even longer. However, the curing reaction can be greatly accelerated by the use of a catalyst, and it is usually preferred to add the catalyst to the material being treated at the same time as the resin is applied, although the catalyst may also be added before or after the application of the resin, if desired. The curing time can be regulated by choosing a suitable catalyst, and the choice of curing time will depend on how the method according to the invention is carried out. The catalysts can be organic or inorganic bases, oxidizing curing agents and catalysts that form free radicals, such as azodiisobutyronitrile, peroxides and hydroperoxides, or combinations of these. As organic bases, primary or secondary amines can be used, such as the lower alkanolamines, e.g. mono- and diethanolamine, and polyamines, such as e.g. ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and hexamethylenediamine. The water-soluble oxides and hydroxides can be used as inorganic bases, such as e.g. sodium hydroxide and ammonia. Examples of siccatives are calcium, copper, iron, lead, cerium and cobalt naphthenates. Examples of suitable peroxides and hydroperoxides are cumene hydroperoxyd, tert.butyl hydroperoxyd, dicumyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide, di-isopropyl peroxide dicarbonate and chlorobenzoyl peroxide.

The fibers and fabrics are preferably treated at a pH value greater than 7> and which in typical cases is between 7.5 and 12. In an acidic environment, the resins tend to harden more slowly.

The amount of catalyst can be varied within wide limits. Usually, however, from 0.1 - 20% by weight, preferably from 1 - 10% by weight, calculated on the weight of the resin, is required, but much larger amounts can also be used.

The curing of the polythiol resin is also promoted by the use of elevated temperatures, and if particularly fast results are desired, temperatures in the range between 30° and 180°C can be used. High humidity also tends to accelerate curing in the presence of catalysts.

The resin, and a catalyst if desired, can be applied to the keratinous material by conventional means. When, for example, tops made of wool or fabrics are to be treated, the impregnation of the material with the resin can be carried out by foulard treatment or by immersing the material in a resin bath. If garments or parts of garments are to be treated, it is appropriate to spray them with the resin and even more conveniently to treat the garments in a drum in the presence of the resin dissolved in an organic solvent. For carrying out the latter method, a dry-cleaning machine using a dry-cleaning solvent is a particularly useful device.

If treatments aim to achieve freedom from shrinkage, it is usually appropriate to apply the resin to the fabric, although as previously mentioned, it can be applied to the fibers when these are present

in the form of tops or carding bands. The fabric can be "flat-fixed" before or after the resin treatment, which means that the fabric, in addition to mainly retaining its original dimensions, also retains its flat, soft appearance during use and after washing. However, it should be noted that the flat fixation or flattening is not always necessary or even desirable for certain types of fabric. Flattening is usually carried out either by treatment of

the substance with water vapor at superatmospheric pressure or by treating the substance with water vapor at atmospheric pressure in the presence of a fixing agent and moisture, the substance being kept flattened. Flattening can also be carried out by applying high concentrations of a reducing agent and a swelling agent, the substance being kept flattened during the washing out of the excess of reagents. In another method, flattening can be carried out by impregnating the material with a swelling agent and an alkanolamine carbonate, e.g. urea and diethanolamine carbonate and then dry the material and semi-decate the dried material.

If it is desired to carry out a treatment that aims to achieve lasting pressure, a number of methods can be used. One method consists in treating the material with polythiol resin, processing the material into garments or parts of garments and inserting folds or pleats into these, using reducing agents, bases or superheated water vapor as fixing agents. The resin can be applied to the fibers at any stage during the manufacture of the fabric, e.g. when they are in the form of tops, in the form of a yarn or in the form of a fabric. If desired, agents that block the wool's thiol groups, e.g. formaldehyde.or higher aldehydes, is applied to the garments provided with folds or pleats after the curing of the polythiol resin.

A preferred method of applying the polythiol resin to achieve permanent pressure involves treating the finished garment or piece of garment, which has been provided with the desired folds or pleats, with the polythiol resin dissolved in an organic solvent. With this method, it is essential that the resin is applied in an organic solvent, because treatment with aqueous systems would entail the removal of the folds or pleats already fixed in the fabric.

An alternative method, which primarily aims to achieve lasting folds or pleats, goes out. on impregnating the fabric in the area where a fold is desired, and inserting the fold and holding the fold in place while heat and pressure are applied.

The fixation of the substance, whether this is carried out before or after the resin treatment, can be carried out using known methods, e.g. using fixatives such as reducing agents, bases, water and superheated steam. The most frequently used fixing agent is monoethanolamine sesquisulphite, which can be used together

with a swelling agent, e.g. urea.

In what follows, the invention will be illustrated by examples. If not stated otherwise, parts and percentage quantities are calculated on a weight basis. Reference is made to various standard tests, which are explained below.

Standard washing

Before surface softness and crease retention were measured, unless otherwise stated, all garment samples were washed for 1 hour in a "Bendix" MRE domestic rotary drum washing machine in a phosphate buffer of pH 7 and temperature 40°C using a weight ratio of 22:1 between the washing liquid and the test pieces. The sample pieces were taken out and dewatered for one minute in a household-type late-refuge dryer. After they had been taken out of the late rifuge dryer, the test pieces were shaken vigorously three times and then hung up to dry at room temperature. Garments with folds were hung so that the folds hung straight down.

Shrinkage

Shrinkage was measured as the difference in the fabric's dimensions before and after washing. The flat shrinkage was calculated from measurements of the linear shrinkage.

Index for surface smoothness after drying

The garment's surface smoothness after the standard washing operation was assessed by comparison with Monsanto's three-dimensional "Wash-<*>n-Wear" plastic standards. These consist of a series of five graduated plastic plates with a surface smoothness that varies according to a scale that extends between 1 and 5. The test plates are illuminated under obliquely incident overhead light (angle of incidence = 16°). A sample of the material whose surface smoothness is to be determined is illuminated under the same conditions, and the surface smoothness is compared with the surface smoothness of the test plates. The value 5 on the scale corresponds to negligible or no change in the appearance of the sample after washing.

Degree of fixation

The garment's degree of pleat retention after the standard washing operation is measured on an apparatus described in Journal of the Textile Institute, 1962, 53, 143. In this apparatus, the pleated sample is placed in the center of rotation of a light source in the form of a slit, as the plane of rotation forms right angles with the fold and the slit is parallel to the fold. The light source is rotated until the shadow cast by the fold almost disappears, and the angle of incidence of the light under these conditions is measured. The fabric sample is then turned until the shadow that is formed on the other side of the fold almost disappears, and the angle of incidence is measured. The degree of fold fixation is then calculated as:

The sharper the fold, the higher the degree of fixation calculated on the basis of the measurements will be.

The polythiol resins used were prepared in the following manner.

Thiol resin A

A mixture of 800 g (0.2 mol) of a triol with an average molecular weight of 4000 prepared from glycerol and propylene oxide, 55.2 g (0.6 mol) of thioglycolic acid, 5 g of toluene-p-sulfonic acid and 350 ml of toluene was boiled with reflux cooling and under stirring in a nitrogen atmosphere. 10.8 ml (0.6 mol) of water formed during the reaction was removed, in the form of its azeotrope with toluene. The mixture was cooled and washed with water, and the organic layer was separated. After removing the solvent from the organic layer under vacuum, 793 g (94% of the theoretical yield) of the desired tris-(thioglycolate)

(thiol resin A) with a mercaptan content of 0.59 equivalents per kg.

Thiol resins B and C

These denote poly-(2-hydroxy-3-mercaptopropyl)-ethers produced from glycerol-propylene oxide adducts with average molecular weight or 600 and 4800, epichlorohydrin and sodium sulphide. The products had a mercaptan content of 3.7 equivalents per kg and 0.32 equivalents per kg.

Thiol resins D- S

These polymer captan esters were prepared as described for thiol resin A, except that in the preparation of resins J-S perchlorethylene was used instead of toluene, and that in the preparation of resins D-I the reaction mixture was not washed with water. Any unreacted mercaptoic acid was removed together with the remaining toluene (or perchlorethylene) by stripping the product under vacuum in a rotary evaporator. In the production of the resin P was

no catalyst used.

The materials used in the preparation of these esters are listed in Table I.

Thiol resins T and U

These denote poly-(2-hydroxy-3-mercaptopropyl) ethers of

similar species to thiol resins B and C.

Thiol resin T contained 2-3 groups -SH per molecule, its thiol content was 1.4 equivalents per kg, and its molecular weight was 1500 - 2000. Thiol resin U contained approximately three groups -SH per molecule, and its thiol content was 0.54 equivalent per kg and its average molecular weight approx. 3000 (cf. the general formula II).

Thiol resin V

A mixture of 500 g of thiol resin B, 218 g (2.37 equivalents) of thioglycolic acid, 1.5 g of toluene-p-sulfonic acid and 500 ml of perchlorethylene was refluxed for 8 hours under a nitrogen atmosphere, while 44 ml of water formed during the reaction , was removed by co-demolition. After washing the mixture with water to pH 5 - 6, the solvent was stripped off in vacuo. The residue, which was obtained in an amount of 640 g, had a thiol content of 5.7 equivalents per kg and contained 5-6 thiol groups per molecule.

Thiol resin W

A mixture of 529 g of thiol resin C, 19.5 g (0.212 equivalent) of thioglycolic acid, 1 g of toluene-p-sulfonic acid and 350 ml of perchlorethylene was heated as above, evolving 4 ml of water. The mixture was stirred with a slurry of 5 g of bicarbonate in 2.5 ml of water, filtered and stripped in vacuo. The residue, which was obtained in an amount of 532 g, had a thiol content of 0.58 equivalent per kg, and contained 5-6 thiol groups per molecule.

Thiol resin X

This was prepared as described for thiol resin V from 500 g of thiol resin T, 89 g of thioglycolic acid, 4 g of toluene-p-sulfonic acid and 500 ml of perchlorethylene, while draining off 23 ml of water. The residue had a thiol content of 1.78 equivalents per kg and contained 5 - 6 thiol groups per molecule.

Thiol resin Y

This was prepared as described for thiol resin X, although 500 g of thiol resin U and 36.4 g of thioglycolic acid were used. The residue had a thiol content of 0.75 equivalent per kg and contained 5-6 thiol groups per molecule.

The polyol used for the production of thiol resin Q was produced in a known manner by reaction in the presence of sodium hydroxide.

Example 1

This example illustrates the improved results obtained by using a non-catalyzed thiol-terminated poly(oxyalkylene) resin to shrink-free woolen textiles.

Solutions of thiol resin A in perchlorethylene containing 2%, 5% and 8% thiol resin A were prepared. Samples of knitwear made from 1.8 ml botany yarn to a coverage factor of 1.1 were impregnated with these solutions using in each case a foulard roll set to 100% liquid absorption. The samples were then dried at 50°C. After storage for 12 days at room temperature, the samples were washed in a washing machine for 30 minutes with a liquid ratio of 25:1, and the percentage area shrinkage by felting was measured.

The following results were obtained:

A far more stringent test was also carried out, using a ratio of 12.5:1 between the liquid and the fabric samples and a wash time of 60 minutes. The following results were obtained:

These results show the high degree of freedom from shrinkage that can be achieved, which is dependent on the amount of resin deposited on the fabric. The excellent freedom from shrinkage is achieved without losing the knitwear's soft grip.

The treatment to make the fabric shrink-free has also been shown to withstand the effects of dry cleaning solvents and repeated washing in aqueous detergent solutions.

Example 2

This example illustrates how a combination of a poly(oxy-alkylene) resin with thiol end groups and a resin with reactive groups capable of reacting with thiols, such as an epoxy resin, can provide. wool fabrics a finish that gives it an excellent degree of freedom from shrinkage.

20 g of thiol resin B were dissolved in 300 ml of trichlorethylene. 10 g of a liquid epoxy resin, namely a diglycidyl ether of 2,2-bis-(4-hydroxyphenyl)-propane which had a 1,2-epoxy content of approx. 5.2 equivalents per kg,, was likewise dissolved in 363 ml of trichlorethylene, and the two solutions were mixed together. The total resin concentration was 3%. The knitwear described in example 1 was impregnated with this solution using a foulard

roller set at 143% liquid absorption, and the sample was dried at 50°C and then kept at rest for 24 hours at room temperature to cure the resin. The sample was then washed for 30 minutes in a washing machine with a ratio of liquid to fabric of 25:1.

The untreated knitted fabric was found to shrink 40% under these washing conditions, while the treated sample with 4.3% of the resin mixture did not shrink at all.

Example 3

A piece of coarse worsted flariel was treated in a dry cleaning machine with a solution of thiol resin A in perchlorethylene, the fabric being treated in this solution for 5 minutes. The fabric was then centrifuge-dried to a residual water content of approx. 30%, which is equivalent to 3% resin, calculated on the weight of the fabric. The fabric was then dried in a drum and cured by storing for 10 days at 20°C and 85% relative humidity. The fabric was prepared into a skirt which was then provided with pleats in water vapor of 1.4 kg/cm, which atmosphere was maintained for 10 minutes. The skirt was then washed for 1 hour under standard conditions and hung up to dry after spin drying.

The appearance of the skirt and pleats was then assessed and found

to exhibit a fixation of 83% and a surface smoothness index after drying of 4 - 5. An untreated fabric subjected to a similar washing treatment was strongly felted and did not retain the folds.

Example 4

A piece of gray worsted serge was flattened by passing it through a foulard bath containing a solution of monoethanolamine sesquisulfite (MEAS) containing 1 g per liters of a non-ionic wetting agent, so that the substance retained 2% MEAS and 60% water, calculated on its weight. The fabric was semi-decatrated (ie treated with water vapor at atmospheric pressure after rolling) for 5 minutes in a wet state and finally dried without stretching. The fabric was processed into a pair of leggings, and the press in the leggings was fixed by spraying the leggings with a 5% solution of MEAS in the areas near the presses, so that the fabric in these areas absorbed approx. 2% MEAS and 40% water, calculated on its weight. The trouser legs were then pressed in a Hoffman press using a press cycle comprising 20 seconds of steam treatment (with the lid closed), 20 seconds of pressing without steam (with the lid closed) and vacuum treatment until the legs are cooled (with the lid open). The legwear was then treated in a dry cleaner with a solution of thiol resin A in perchlorethylene containing 2% (based on the weight of the resin) diethylenetriamine, so that they retained 2.5% resin based on their weight.

Six days later, the legwear was washed according to the standard method. They showed excellent press retention, excellent smoothness and softness after drying and did not shrink.

Example 5

A piece of wool fabric with a recognition pattern was impregnated with a solution of monoethanolamine-S'>sl bisulfite (MEAS) by passing it through a polar bath containing the solution, so that the fabric retained 3% MEAS, calculated on its weight. The impregnated fabric was dried in a flat dryer without stretching and cut into pieces to make a pleated skirt. The pieces were sprayed with an amount of water corresponding to 30% of their own weight, provided with folds using paper fold formers and fixed by steam treatment for 10 minutes in an autoclave at 0.56 kg/cm steam pressure. After drying and removing the pleat formers, the skirt pieces were assembled into a skirt. The skirt was then treated with thiol resin A in a dry cleaning machine in the following manner.

A solution of perchlorethylene containing 4% thiol resin A, 0.08% diethylenetriamine and 0.20% cumene hydroperoxide ("Trigonox" K-70) was prepared in the dry cleaner. The skirt was immersed in the liquid and kneaded in this solution, after which the solution was allowed to drain off the skirt and excess resin solution was removed by centrifugation until the skirt retained 60% resin solution, calculated on its weight, i.e. 2.4% resin and other treatments, in the same ratio as in the solution. The skirt was then tumble-dried in the dry cleaner. When the skirt was taken out of the machine, no new pressing was necessary.

The resin on the skirt was allowed to harden. 7 days later, and after being washed for 1 hour according to the standard method, the skirt had shrunk 1% lengthwise and nothing in width. The pleats showed an average fixation of 89%, and the surface smoothness index after drying for the flat parts of the skirt was found to be 4-5.

Examples 6 - 14

These examples show the degree of freedom from shrinkage and lasting pressure that is achieved with other polythiol resins according to the invention.

The fabric used in these examples was a grey, mixed worsted serge of weight 270 g per m 2 , and the pH value of the aqueous extract was 7.8. The material was flat-fixed using 1.5% monoethanolamine sesquisulfite (MEAS), calculated on the weight of the material, and was semi-decatated for 4 minutes. The fabric was cut up into test pieces, and folds were fixed in these test pieces by spraying the areas where the folds were desired with a 5% MEAS solution to 40% liquid absorption, after which the folds were formed by pressing in a Hoffman press using the following pressing cycle: 30 seconds of steam treatment (lid closed), 30 seconds of pressing without steam (lid closed) and vacuum cooling (lid open).

To these pressed, flat-fixed specimens, polythiol resins were applied from a perchlorethylene solution using polar rollers set so that the specimens took up 3% resin based on their weight. The catalysts were diethylenetriamine (DETA) or calcium naphthenate (CaN), and these were used in amounts corresponding to 1-5% by weight of the resin used. The treated specimens were allowed to cure at 20°C and 65% relative humidity and were subjected to the standard washing method. The sheet shrinkage, the surface smoothness index after drying and the percentage fixation of the press were then measured. The results are given in Table II.

It will be seen from these results that the treatment of the fabric with the resins gave excellent freedom from shrinkage. Furthermore, the fixation of the press was good, as all results show a fixation of 75%

or more, and most of them show an ic ring of 85% or more. These results show that garments can be made fully machine washable using the resins according to the invention, the resin-treated garments do not shrink, retain their surface smoothness, which is indicated by the surface smoothness index after drying, and retain their press after greater washing and drying cycles. .

The grip of the treated fabrics was very good and full and had not become rougher or coarser. The draper:ng properties of the substance were practically unchanged.

The curing time of the resins varied, but it showed

that by choosing the catalysts according to the resins in most cases the desired cure could be achieved:.d. The times given in the examples are not necessarily the times it took the resins to harden. They indicate the intervals between the application of the resin and the execution of the standard washing method, and in many cases the actual curing time will be shorter than the specified interval.

Examples 15 - 25

These examples correspond to examples 6 - 14, except that

other resins were used.

The resins were applied to fabric samples in the same way as in examples 6 - 14, except that the following catalyst systems were used in some cases:

1% DETA + 5% dilauryl peroxide (DP)

1% CaN + 5% dilauryl peroxide (DP)

The treated samples were subjected to the standard tests, and the results are listed in Table III.

These results show once again that the treatment according to the invention gives garments satisfactory machine-washability properties. Moreover, the grip was remarkably good, especially for the fabrics treated with thiol resin A.

Examples 26 - 37

These examples illustrate the use of other thiol resins under other conditions.

The fabric used was a wool flannel weighing approx.

170 g/m . The pH value of the aqueous extract was 3.1 - The flannel was polar treated with a solution of the thiol resin in perchlorethylene, containing 10% by weight of monoethanolamine calculated on the weight of the thiol resin, so that the absorption of the thiol resin was 8% • The flannel was then dried to its original dimensions for 2.5 minutes at 50°C in a fan oven and stored at room temperature for the periods indicated in Table IV. The treated samples were washed in a "Hoovermatic" washing machine at 50°C in an aqueous solution containing 5 g/liter soap flakes and 2 g/liter anhydrous sodium carbonate, rinsed in cold water, dewatered in a household type centrifuge dryer and finally dried at 50°C. The results obtained are listed in Table IV.

Similar results were obtained by pre-reducing or pre-oxidizing the flannel. To reduce the flannel, it was polar treated to 50% liquid absorption with an aqueous solution containing 10 g/liter sodium metabisulphite (^2820,-) and 4 g of emulsifier I (an adduct of nonylphenol and 9 mol of ethylene oxide) and dried at 50°C in a fan oven for 2.5 minutes. To oxidize the flannel, it was polar-treated to 140% liquid absorption with an aqueous solution which per liter contained 20 ml of hydrogen peroxide (30%),

1.2 ml of formic acid (85%) and 1 g of emulsification part I, and which had been adjusted to pH 3.7 with aqueous sodium ionate, after which it was kept for 4 hours in a polyethylene bag and then dried as previously described.

Examples 38 - 46

These examples illustrate how the resins according to the invention make knitwear machine washable.

Polythiol resins were applied from a solution in perchlorethylene by polar treatment to 4% uptake of resin on the knitwear. The knitwear samples were of botany wool, were knitted in a very simple way and had a coverage factor of 1.1. The knitwear's liquid absorption was set to 200%, and after the polar treatment the samples were dried in a tumble drier at 6o°C.

As a preliminary machine washability test for knitwear has

it has been suggested to wash the knitwear in 25 liters of washing liquid for 30 minutes in a "Cubex" washing machine and then for 60 minutes in 12.5 liters of washing liquid in the same machine. The treated knitwear samples were consequently subjected to this washing test, which was carried out after complete curing of the resin. The catalyst used was diethylenetriamine in an amount of 2% by weight, calculated on the weight of the resin.

The results obtained are listed in Table V.

The "Cubex" washing machine is an internationally available machine for carrying out machine washability tests and comprises a cube-shaped container with a volume of 50 litres, which is stored in the diagonally opposite corners and rotates at 6o revolutions per minute. minute, the direction of rotation being reversed at the 5th minute, with a 5-second pause during the change of direction of rotation.

Example 47

An emulsion of thiol resin A was prepared from the following ingredients:

The emulsion was applied by means of a polar bath to a piece of gray serge fabric, which had previously been fixed flat according to the method described in example 4, except that a solution of monoethanolamine was used as fixing agent. The substance retained 100% emulsion, calculated on its own weight. The impregnated fabric was dried without being subjected to any stretching and the resin was allowed to cure. A pair of legwear was made from the fabric, and the legwear's pressers were fixed as described in example 4- After being washed according to the standard method several days later, the legwear shrank 0.7% in width and 0.8% in length, and they had furthermore, an index for surface smoothness after drying of 5 and a fixation of the press of 85%.

In other experiments, an aqueous emulsion of thiol resin A was prepared by mixing 320 g of this polythiol with 144 g of water and 16 g of emulsifier II (an adduct from a mixture of 1 mol of primary aliphatic amines containing 16-18 carbon atoms in the molecule and 70 mol ethylene oxide). 10 g of this emulsion was mixed with 7.5 g of monoethanolamine and 882.5 g of water. Woolen flannel was impregnated with the obtained solution to 110% liquid absorption, dried at 50°C in a fan oven and then stored for 16 days at 20°C. The thus treated flannel was washed for 1 hour in a "Hoovermatic" washing machine at 50°C with a washing liquid containing 5 g of soap flakes and 2 g of anhydrous sodium carbonate per wash. litres. The surface shrinkage was 6.5%, while the untreated flannel shrank 29.7% under the same washing conditions.

Example 48

A piece of shirting containing 50% wool and 50% cotton was flat-fixed with monoethanolamine sesquisulphite as described in Example 4. Half of this piece and a piece of untreated shirting were treated in a dry cleaning machine with thiol resin A to which was added 2% diethylenetriamine (calculated on the weight of the resin), so that the skirting retained 2.5% resin, calculated on its own weight. After the resin had been allowed to cure for 7 days, two skirts were made from these two pieces of resin-treated skirting, while a third skirt was made from the skirting that had only been flat-fixed

and a fourth skirt was made from the untreated skirting.

The four skirts were washed and centrifuge dried according to the standard method. After drying, the properties with regard to surface smoothness after drying were as follows:

The results show the improved surface smoothness of the wool/cotton wool fabric when thiol resin A is used with and without flat fixing.

Examples 49 - 50

These examples illustrate the machine-washability of lambswool and Shetland sweaters.

The sweaters were first rinsed with solvent and then impregnated with a mixture of 4425 g of thiol resin A, 88.5 g of diethylenetriamine and 54.6 liters of perchlorethylene. after being impregnated for 3 minutes, the sweaters were centrifuge dried to 60% liquid content, processed in a cold drum for 3 minutes and then dried at 65-70°C for 10 minutes. The treated sweaters showed little tendency to felt when washed 3 days later in a household washing machine. The results were as follows: Washing test: Two 10-minute washing operations in a "Hoovermatic" washer machine.

Examples 51 and 52

These examples illustrate the use of thiol resin A to stabilize two-ply jersey wool in washing and to prevent shrinkage due to felting.

Two-thread jersey wool was impregnated in a dry cleaning machine with a solution of 9.65 kg of thiol resin A and 195 g of diethylenetriamine in

159 liters of perchlorethylene. The piece of two-ply jersey was treated with the resin solution for 3 minutes in a drum, after which the liquid was allowed to drain out of the drum, and the piece was centrifuged at high speed for 7 seconds to a residual liquid content of 84.5% and then dried at 50 °C for 12 minutes. The treated jersey was found to have a comfortable, soft cre^ and to be well stabilized against shrinkage due to relaxation and excellent anti-felting properties after washing 3 days later.

Washing test:

(a) Relaxation - 15 minutes soaking at rest, then 5 minutes in the "Cubex" washing machine. (b) Washing - 1 hour in the "Cubex" washing machine with 12.5 liters of washing liquid.

Example 53

This example shows the aqueous application of thiol resin A to a knitted fabric to achieve shrinkage freedom.

150 g of thiol resin A and 22.5 g of emulsifier I were mixed using a high-speed mixer, after which 327.5 g of water was slowly added to form a stable emulsion. This 30% emulsion was then diluted to 3%, after which 5% diethylenetriamine, calculated on the weight of the resin, was added as catalyst. A botany fabric with a covering factor of 1.1 was passed through a polar bath of the emulsion and dried in a drum at 6o°C. The treated fabric

was allowed to cure at room temperature. The washing tests carried out 14 days later showed that the treatment provided excellent freedom from shrinkage.

Example 54

A piece of gray worsted serge, which had been flat-fixed with monoethanolamine sesquisulfite (MEAS) as described in Example 4,

was pressed in the warp direction by spraying onto the fabric a 5% solution of MEAS, so that it retained 40% solution in the area where the press was to be formed, folding and pressing in a Hoffman press using the cycle: 20 second steam treatment (lid again), 20 seconds of pressing without steam supply (lid closed) and 10 seconds of vacuum cooling (lid open).

The sample was treated with a solution in perchlorethylene of equal amounts of thiol resin A o<j "Synthappret" LKF. The sample was treated so that 0.75% thiolha: 'p:' xs A and 0.75% "Synthappret" LKF were retained on the fabric. Immediately after that up; the sensitizing agent had evaporated, the fabric was washed under standard conditions and the fabric was subjected to the standard tests. The results were as follows: Shrinkage = 0.5%; index for superfluidity after drying = 5;

fixation = 100%.

The grip of the treated fabric was better than that of the fabric that had been treated so that it held out Closing 1.5% "Synthappret" LKF. The resin cured quickly, and even ] days later the resin bath was still usable and gave similar results.

Claims (2)

1. Method for making keratin-containing fiber material or textiles shrink-resistant and giving them permanent pressure retention, with a polythiol resin being applied to the fiber or textile and cured on this, characterized in that a polythiol resin containing 3-6 thiol groups per molecule and has a molecular weight between 400 and lO.OOO, and has the formula: where m, p and q each denote an integer, m is at least 1, p is 2 - 6, (P <+><q>) = 3 - 7, where each "alkylene" group contains a chain of 2-6 carbon atoms between successive oxygen atoms and they may be substituted with phenyl or chloromethyl groups, R is an aliphatic group with at least 2 carbon atoms, and X is an alkyl or alkanoyl group containing at least one thiol group. 2. Method according to claim 1, characterized in that a polythiol resin with the formula is used: where R2 is an aliphatic hydrocarbon group with 3-6 carbon atoms, "alkylene" and m is as indicated above, P2 is an integer from 3 - 6, and u is 1 or 2.