PL82721B1 - Treatment of keratinous fibers and fabrics [us3645781a] - Google Patents

Abstract

The present invention relates to a process for rendering keratinous material, particularly wool, resistant to shrinkage and for imparting durable press characteristics to the material. The products used therefor are polythiol compounds containing in the molecule (a) a radical of a polyhydric alcohol, (b) poly(oxyalkylene) chains, and (c) radicals of mercapto-ethers or mercapto-esters. [US3645781A]

Description

The holder of the patent: I.W.S. Nominee Company Limited, London (UK) Ciba Limited, Basel (Switzerland) Method of Modifying Keratin Textile Materials The present invention relates to a method of modifying keratinous textile materials, in particular a method of making the material resistant to shrinkage and of imparting to it the property of a permanent press. methods of making keratin materials resistant to shrinkage. Some of them rely on (treating the material in the form of a fiber or a rye fabric. The methods of resistance to shrinkage stabilize the dimensions of the keratin materials against shrinkage caused by felting. There are also methods for the permanent pre-treatment of keratin materials, and many of them are being used for slimming. These sleds are similar to resins as in the methods of resistance to shrinkage. In some methods of permanent pressing, the shape of the keraltic material is obtained before the hardening of the resin, and then the hardening is carried out, making the material in the desired shape, e.g. In other methods, the resins are applied after the material has been given the desired shape. Permanent pressing methods allow the shape and smoothness of the surface of the gland material to be preserved by changes in the presence of aqueous solutions. The desired, although essential, feature of the shrink-resistant and property-enhancing methods permanent ironing is possible in washing the keratin materials treated in this way in domestic washing machines. The finishing finish on the treated material, which is suitable for mechanical washing, must withstand severe deformations in warm or hot water containing detergents. 5 One of the advantages of keraity fibers, especially wool, is their excellent grip, and a serious drawback associated with the use of many resins in the methods of permanent ironing and shrinkage resistance is the sheer squeeze that gives the loosening fibers that contain these fibers ¬ nom. Attempts were made to prevent this rough feel by the use of softeners, but they were not effective as they reduced the effective performance of the resin. It has now been found that a group of resins including certain poly (oxyalkylene) resins with thiol end groups can be successfully used in permanent compression and shrink-proofing methods, without giving the opaque material an unpleasant feel. These resins are fiber-cured and it has been found that the curing speed can be controlled over a wide range by the choice of the appropriate catalysts. The invention relates to a method of modifying keratin materials by treating the material with a polythiol resin having at least two thio groups in molecules and the polyhydric alcohol radical containing the radical, at least two chains (pdKokyalkylene) bonded to this radical and linked to the n-atoms in these poly chains by at least and two resistants in these poly chains by oxygen altoes, selected from the group consisting of the acyl radical of an aliphatic carboxylic acid containing a thiol group or a thiol-containing residue of the aliphatic alcohol after removing the hydroxyl group and hardening the resin on the material. The treatment according to the invention leads to permanent pressing and resistance to shrinkage, clothes resistant to mechanical washing and retaining their originals different dimensions and shape. In addition to the excellent grip applied to the material after the treatment along the length of the machine, the treated material is resistant to crushing, which is an important feature of the fabrics used for the production of pants, in which there is a marked tendency to crush on the knee and under the knee. Of course, crush resistance is an important advantage in many garments. The resin used in the method of the invention protects not only against shrinkage caused by fatigue, but also against relaxation shrinkage, which is an important problem with knitted products. This method according to the invention finds particular application in anti-spinning treatment of anti-spinning articles. The term "keratin material" as used in the description includes all forms of keratin fibers and fabrics and garments made from them, such as fleece, worsted, ribbed yarns, noises, yarns, threads, shaggy fabrics, non-woven fabrics, woven fabrics and knitted products. In most cases, the treatment is applied to fabrics and finished garments, although it is entirely possible and in some cases may be desired. resistant to shrinkage of fibers, e.g. in the form of worsted yarn. The processed malterial may consist either entirely of keratin fibers or a mixture of these fibers with synthetic fibrous materials such as polyamides, polyesters and polyacrylonitrile or with cellulose materials. Regenerated lulose. In general, however, the material should contain at least 30% by weight of keraltic fibers. better results are obtained with a material containing 100% of keratin fibers. The keratin material may be new or regenerated, most preferably sheep wool. It may also be derived from alipaka, cashmere, English goat, charcoal, guanaco, camel hair, silk and llama, or a mixture of these materials with sheep wool. The polyethylene resins used in the process of the invention preferably contain three to six thiol groups in the molecule. Particularly good results have been obtained with resins containing three or four thiol groups per molecule. Polythiols having a molecular weight of between 400 and 10,000, in particular with a formula 1, where m, p and q are positive integers, m is an integer, are preferred. is at least 1, p is 2-6, (p + q) is 3-7, each alkylene group contains a chain of 2-6 carbon atoms between successive oxygen atoms, R is an aliphatic radical containing at least 2 carbon atoms and X represents an alkyl or acyl radical containing at least one thiol group. The oxyalkylene groups in the individual poly (oxyalkylene) chains can be different. They can be substituted if necessary e.g. by phenyl or chloromethyl groups. Thus, it is possible to use partially or fully esterified compounds of formula 2 in which R, "alkylene", m, p and q have the above meaning ar is a positive integer, which may have a value of 18 or even 24. 15 Preferred are esltirs of formula III, in which "alkylene", miq have the above meaning, u is an integer dodaltni equal to at most 2, Px is an integer equal to at least 2, and at most 6, (Pi + q) equal to August 3-7, and Rx is an aliphatic radical containing 2-6 carbon atoms. Esters of formula 4 are also preferred, in which "alkylene" and m are as defined above, p2 is an integer equal to 3-6 and R2 is an aliphatic hydrocarbon radical containing 3- to 6 carbon atoms. Esters based on glycerol, hexanetriol-yl, 2-S, hexanolbriol-yl, 2.6 and ethylene oxide and / or propylene oxide, for example in the weight of 5 and the formula 6, in which the above meanings and t are an integer equal to 2-3. Alkylated polyethoxide ce-esters ending with thiol groups are easily obtained by reacting a polyhydric alcohol with an alkylene oxide with subsequent esterification of the end hydroxyl groups with mercapltecarboxylic acid. As polyhydric alcohols, polyethylene glycol, polyethylene glycol, propylene glycol, propylene glycol are used. poly (polypropylene glycols), polypropylene propane diolHlA, polypyrhydrins, butanediol-1, i2, buytanediolJ, 1,3, butanediol-: 1,4, buitanediol-E ^, poly (14Hdiumeltylyloxide) glycols poly / tetrahydrofurans, glycerin, 1,4-liter tri (hydroxymethyO) -ethane, 14,1ntirochydroxymetyio) propane, 45 hexanetriol-, 1,2,5, hexanetriol-11,2,6, pemtaerylthrite, diphen Itaer, tryite, mannitol, sorbitol, and adducts of alkylene oxides with ammonia or amines such as diethanolamine and teitracio diamine. The alkylene oxides are ethylene oxide, propylene oxide and preferably butylene oxides, epilchlorohyidrin or tetrahydrofuran. The polyhydric alcohol can be treated with an alkylene oxide, such as, for example, propylene oxide, and then with another alkylene oxide, such as, for example, ethylene oxide. As mercaptocarboxylic acids for esterification, thioglycolic acid (2-mercapto-2-mercapto acylic acid) can be used. However, other mercapto-monocarboxylic acids, such as mercapltoundeicylic acid and mercaptositearic acid, may also be used. The most preferred polythiol esters used in the process of the invention are those obtained from glycerol, propylene thiolate and 65 gflylic acid. , for example, Formula 7, in which m is as defined above and the molecular weight is 1,000 to 5,000. Such resins are commercially available. The second class of alkylene polymers) terminated with thioHorvine gnups includes with visor 8, where R3 is -OH, -i (O-alkylkylene) y OH, -O.GO ^ CuH2uSH or - <O-alkylene) vCMOO.CuH2uSH, R, "alkylene", m, p , q and u have the meaning given above, av is a number an integer equal to the cheapest 1 and may have different values in each of the p-strings. Oxyalkylene groups in the plurals of the main poly (oxyalkylene) chains may also be different, but the usage is the same and, if necessary, may be substituted with njp. by phenylene or chloromeltyil groups. Also, the esters of formula 9, in which "alkylene", Rlfm, R8, px and q mafia are given above, and esters of formula 10, in which R2 and p2 are Particularly preferred are esters of the visorize 11 in which R2, t, m and p2 have the meanings given above. These are commercially available. Ethers of formula 8 in which R3 is -OH, can be obtained in a known manner by reacting alkylene oxide with a polyhydric alcohol, ethersifikaoje, g) hydroxyl rupees of the product with epichlorohydrin and treatment with sodium bisulfide to replace the chlorine with a hydrogen sulfide group (see US Pat. No. 3,258,495 and British Patent Nos. 1,076,725 and 1,144 7,1). In centuries, the average number of thiol groups in a molecule is not an integer, but is, for example, 2.6. Replacement of chlorine atoms by -SH groups, a in part by side reactions, e.g. cniorohydrin ether obtained by reactions with epiichllorohydrin, can also react with epichlorohydrin, thus forming an ether which contains two capable of exchanging an amount of chlorine into one hydrogen oxygen group present on the polyhydric alcohol poresitic . Especially conspicuous seers of formula 12 in which R2, t, m, v and p have the meaning given above. The ethers of formula 8 in which R 3 is - (O-allkylene) vOH can be separated by treating the product obtained from ejpyichlorohyridine, aflkylene oxide and polyhydric alcohol, first with alkylene oxide and then with sodium bisulfide (see British Patent No. 1144 701). The ethers of the formula 13 are most preferred, in particular those with a molecular weight of 700- (3500. Ether-esters of the formula VIII in which R3 is -O.CO.CuH2uSH or -i (O-aakylene) vO.CO.CuH2uSH, is obtained by esterification of the corresponding alcohol with mercaplutoxy acid HOOC- .CuH2uSH. Polythiol resins can be used alone or N60 in combination with other resins or resin-forming materials, such as aminoplasts and especially epoxy resins (epoxy resins). substances with an average of more than one 1,2-epoxy group in the molecule or polyisocyanates. Particularly good results have been obtained with mixtures of poly / thiol resins and polymeric prepolymers. ch polyhydric compounds with polyisocyiaaiianeim. Examples of the latter type of resin are polyoxyalkylene glycol and aromatic diisocyanate prepolymers or polyoxyalkylene diisocyanate prepolymers (oxyalkylantriol and aliphatic diisocyanate). Particularly good results have been obtained with a mixture of thiol resin A, especially LK and Napph. supplied by Farfoen Fabrik Bayer and labeled Polyisocyanate Prepoimer. Many of these polyflthiol resins do not dissolve in water but may be used in the form of aqueous suspensions or emulsions. It is preferable to apply the resin to differently dispersed fabrics or garments. - organic pulverizers, e.g. lower alkanes, such as ethyl alcohol, lower ketones, such as methyl ethyl ketone, benzene and chlorinated hydrocarbon solvents, especially chlorinated and / or fluorinated hydrocarbons, containing no more than three carbon cleaning atoms - carbon tetrachloride, trichlorethylene and tetrachloroethylene. The amount of polyethylene resin used depends on the desired effect. In most cases, it is preferable to use 0.5 to 5% by weight based on the material being processed. The stabilization of carpets usually requires 1-1% by weight of resin. A higher degree of shrinkage resistance, edge fixation and significant crease resistance can be achieved in relatively smaller amounts in woven fabrics, in particular 1-5% weight. head. The speed of the material processed will of course be dependent on the amount of resin used. The smallest amount of resin required to obtain the desired effect can easily be determined by simple experiment. In addition, the amount of resin needed also depends on the fabric construction. The desired effects will not be fully obtained unless essentially all of the polythylene resin is cured on the fabric. At ordinary temperatures, this may take five to ten days or even longer. The curing reaction can, however, be greatly accelerated by the use of a catalyst, and it is generally advisable to add the catalyst to the treated material simultaneously with the application of the resin, although it may be added as needed at random. The curing time can be adjusted by the choice of the appropriate catalyst and the choice of the quench time depends on the particular application of the process according to the invention. The catalysts can be organic or inorganic bases, siccatives, oxidizing quench agents, and hydroperiodic catalysts such as azodiisobutyric acid nitrile, peroxides and hydroperoxides, or combinations thereof. As organic bases, primary and secondary amines, such as lower atlphcanamines, such as mono- and diethanolamine, and polyamines, for example, ethyene diarriine, diethylene tetraimdine, triethylene tetramine, aateroethylene diethylamine and hexamethylene diamine, can be used. As inorganic bases, water-soluble oxides (7-8W21) and hydroxides, such as sodium hydroxide and ammonia, can be used. As syphosphates, for example calcium, copper, iron, lead, cerium and cobalt natrophylates are used, Jaiko peritilenkd, and hydroperfenides are used, for example, peroxide hydroperoxide, tertiary butyl hydroperoxide, dicunnyl peroxide, dimethylethyl peroxide, imetethyl ketanethylene peroxide Diisopropyl peroxide and cMorobenzoyl peroxide. Fibers and fabrics are preferably processed at a pH value greater than 7, in particular 7.5-12. In acidic conditions, the resins tend to cure slower. The amount of kaititator used can vary within wide limits. However, it is preferably 0.1 to 20%, especially 1 to 10%, by weight based on the weight of the resin used. However, larger amounts can also be used. The curing of the polythiol resin also helps with the use of elevated temperatures, and if particularly fast results are required, a temperature of 30 ° -andiaO ° C can be used. Also, high Moisture contents tend to accelerate the curing in the presence of cartalysts. The resins and possibly the catalyst can be applied to the keraitic material in a known manner. For example, in the treatment of worsted yarn or fabrics, impregnation can be made by applying a resin to the malterial or by dipping the material in a resin bath. When treating garments or parts of garments, it is preferable to spray them with resin, and even better to mix the garment in the presence of resin dissolved in an organic solvent. For this last method, a particularly useful apparatus for carrying out the process of the invention is a chemical cleaning machine using a chemical cleaning solvent. If a shrinkage resistance treatment is required, it is usually preferable to apply a resin to the fabric, although it has been found that that it can be pre-applied in the form of worsted or quilted yarn. The fabric can be "flat-set" before or after the vein / woven treatment and thus the fabric, in addition to essentially maintaining its original dimensions, also retains its flat, smooth appearance when worn and after washing. It must be stated that "smoothing is not always necessary or even desirable for certain types of fabrics. Ultrwaharia is normally carried out either by treating the material with steam at a pressure above the atmospheric pressure or by treating the fabric with steam at atmospheric pressure at the presence of a fixative and moisture and after Zitization of the material in a flat position. Breakdown can also be achieved by the use of high concentrations of reducing agent and slowing agent and leaving the material flat while washing away excess reagents. In another method, smoothing can be achieved by impregnating the material with a blowing agent and an alkanol-anrine carbonate, e.g. with myositis and diethanolamine carbonate, extruding the material and half-lingering / tilting the dry material. performed in various ways. For example, the material can be treated with polyvinyl resin, the material can be made into garments or garments, and the material can be edged and folded, using reducing agents, alkalis or overheated steam as fixing agents. The resins can be applied to the fibers at any stage in the production of the fabric, for example in the form of worsted yarn, thread or fabric. It is also possible to use wool thiol blocking agents, e.g. formaldehyde or higher aldehydes, for garments with fixed irons after the polyethylene resin has hardened. It is advantageous to use polyvinyl resins to obtain a permanent ironing effect by treating with a fleece solution of fleece. organic ready-to-wear garments or garments that have already been given predetermined creases or tabs. In this method it is important to use the fruit in an angainic solvent, since treatment with a water system would only remove the edges and folds already provided on the fabric. For the production of exclusively durable pleats and camels, it is also possible to impregnate the fabric with a resin in the place where the crease or fold is to be made, to make a crease or folds and to hold in this position at increased temperature and pressure. before or after the treatment of the resin, it can be achieved in a known manner, for example by means of ultrafiltering agents, for example reducing agents, bases, water and superheated steam. The monoefcanolaintine hexahydrate is the agent most commonly used and may be used in conjunction with excipients such as urea. The invention is illustrated by the following examples. Unless otherwise stated, all parts and percentages are by weight. The following test methods are referenced in the examples: a. Standard washing. Prior to measuring the surface smoothness and edge behavior, all garment samples, unless otherwise stated, were washed for one hour in a domestic Bendix MRE washing machine with a spinning drum, in a phosphate buffer solution at pH 7 at 40 ° C, whereby the weight ratio of the washing slurry to the samples was 22: 1. The samples were removed and rinsed in home for 1 minute. After removal from the oven, the samples were shaken vigorously three times and hung up to dry at room temperature. Garments with 55 creases and pleats were hung vertically. this. Korczfliwosc. The shrinkage was measured as the difference in the dimensions of the fabric before and after washing. Surface shrinkage was calculated from linear shrinkage measurements. 60 c. Drying smoothness indicator. The surface smoothness of the garment following a standard wash was estimated by comparison with the three-dimensional "Wash-ta-Wear" plastic standards of Monsanto. They consist of a series of • 5 stepped plastic plates 9 82721 solid, whose pvc smoothness varies from 1 to 5. The test plates are illuminated by inclined light (light angle = 16 °). Material sample to be assessed. it is illuminated under the same conditions, and its surface smoothness is assessed by comparison with the test plates. The grade number 5 corresponds to little or no change in the appearance of the sample after washing. d. Degree of pressing. The edge behavior in the garment after standard washing was measured on a device described in Jouirnal otf the Textile Institute, 1962, 53, 143. In this device, the angled sample is mounted in the center of the rotation of the light source, which has an angle of a slit, a plane of rotation it is placed under a right angle to the edge, and the slit is parallel to the edge. Light source • rotates until the shadow formed by the canite disappears, in these conditions the angle of incidence of light is measured. The fabric is then rotated until the shadow formed on the second screen of the edge disappears and the angle of incidence is measured. The degree of edge writing is calculated as follows: (percentage of stress = average angle of incidence * 100 90 The sharper it is (measured canit, the higher the value is of crimping e. Polylithiol resins were prepared as follows: Thiol resin A. A mixture of 800 g (00.2 moles) of trioyl with an average molecular weight of 4000, obtained from glycerin and propylene oxide, 55.2 g (0.6 moles) of thioglitool acid 5 g of toluene-p-sulfonic acid and 350 mL of toluene were heated under reflux under nitrogen while stirring. Water formed during the reaction (10.8 mL, 0.6 mol) was removed as a toluene azeotrope. The mixture was chilled. , washed with water and the organic layer was separated. After removing the solvent from the organic layer under vacuum, 793 g (94% theoretical) of the expected trphis (ti-glycolate) ("Herbal Resin A") with 0 mercaptan content remained. , 59 equivalents / lklg. f. Thiol resins B and C. The poly (2-hydroxy-meiicap (to pTOPyl) ethers determined in this manner were obtained from glycerin products with propylene oxide with an average molecular weight of 500 or 4800, epichlorohydrin and sodium sulphide The product showed a mercaptan content of 3.7 eq / kg and 0.32 eq / kg, respectively. g. Civilian D- ^ S. These poflimercaptan ethers were prepared as described in field resin A, except that, that in the cases of J-S resins, instead of toluene, ethylene chloride was used, and in the cases of D-I resins, the reaction mixture was not washed with water. The unreacted mercapto acids were removed with the remaining toluene (or tetrachlorethylene). by subjecting the product to vacuum distillation in a rotary evaporator. In the case of resin P, no catalyst was used. The materials used for the preparation of these esters are shown in Table 1. Table I Polyitiol 1 DEFGHI JK L. NO Addufct poly Designation a 2 Garadol 3000 Caradol 5001 Polyurax G 1000 PotLyurax G 3KKK) Polyuirax G 3521 Polyurax G 1000 Caradol 5001 Polyurax G 1000 Voranol CP 700 Caradol 3000 Niex DHT 112 Polyurax G 4000 Average molecular weight 3 3000 5000 1000 3000 3000— 4000 1) 000 5000 1000 700 3000 1500 4000 Obtained from: alkylene oxide 4 PO PO with execution EO PO PO EO / PO (10:50) PO PO with execution EO PO PO PO PO PO PO PO Alcohol or amine 5 glycerine 91 l l »» »il hexanetriol- -11,2,6 IgHicerin Esterifying acid 6 (thioglycolic» »i» »I» i "1 2 ^ mercapto-propionic thioglycolic» »l» 1 »i» »2-mercapto-propionic 82721 11 12 cd Table I. 1 p QRS 2 Pluracol EDP 500 - Pluracol TP 4040 Polymeg 1000 3 500 2220 4040 1000 4 PO PO PO Teitrahydrofuran 5 ethylenediurethritol pentaerythritol ltrium (hydro- (pcsymethyl) propane, tailtanodial- -1,4 6 thiogiikolic » »» EO - Ethylene Oxide PO - Propylene Oxide "Caradol", "Polyurax", "Voranol", "Niex", "Pluracol" and "Polymeg" are brand names. "Oaradol" is provided by Shell Chemical Co .; " Polyurax "- by BP Chemicale Ltd;" Voranol "- by Dow Chemical Co;" Niex "- by Union Garbide;" Pluracol "- by Wyendotte Chemical Corp. and" Polymeg "- by The Quaker Oata Co. Polyol used for The preparation of the thiol resin Q was obtained in a known manner by reactions in the presence of sodium hydroxide. h. Itiol veins T and U. This way, determined in this way (pc ^ 2-hydroxy-i3-! meitfkia | p1x) pxxpyl / similar isa for Itiollic resins B and C. The thiol resin T contained 2—13 mg of -iSH dust per particle, the content of Itioll was in the amount of 1.4 eq / kg, weight almolecular I&O — 12000. The thiol cane U contained approximately 3 igruipy -SH per molecule, a thiol content of 0.54 eq / kg, a (average calico weight about 31,000. ((See general formula 8). I. (Phthiol B (500 g), ItiOglycolic acid and (I2.18 g, 2.37 equiv.) Mluenonp-isufiphanoic acid <1.5 g) and tetrahydro moeitylene (500 ml) were heated to a reflux temperature by 8 hours under nitrogen with the amount of water formed during the reaction and (44 ml). After the mixture was washed with water, the solvent was distilled off until a pH of 5-6 was reached, and in a vacuum. The remainder (640 g) contained itliol in a volume of 5.7 liters ¬ nourishing / kg li contains 5-6 thiol groups in the molecule. K. Thiol resin K. Mixture of thiol resin C (529 g), Itioglycolic acid 1 (19.5 g, 0.212 eq.), Itoluene-p- acid sulfonic acid (1 g) and cetitachloroethylation (350 ml) was heated as before (4 ml of water evolved. The mixture was mixed with a suspension of acid carbonate in water (5 g) and water (2.5 ml), filtered and distilled under vacuum. Residual. (53 (2 g) contained thiol in the amount of 0.58 equivalents / klg, and had 5-6 thiol groups with a phyllum. 1. Resin (thiol X. It was obtained as described for the resin (thiol V from thiol resin) T 1 (500 g), 80 g of thioglycolic acid, 4 g of itoluene-p-lsuliphonic acid and 500 ml of tetrachloroethylene ultrafilter 23 ml of water was formed. The remainder had a thiols content of 1.78 eq / kg and was 5— 6 thiol groups per molecule, m. Thiol resin Y. It was prepared as described for resin X, but using U i thiol resin (500 g) and 36.4 g of thioglycolic acid. 75 equiv / kg and contained 5-16 salt groups per molecule. 25 30 35 40 45 50 55 60 Example I. This example illustrates the excellent results obtained by the use of uncatalylized poly (idxyafllkillen) resin terminated with dHa thiol groups. for shrinkage of woolen materials. Solutions containing 12 / o / o, 151% and 8% of the resin (thiol A was prepared in titerolchlorethylene. Knit samples prepared from yarn (worsted 2/128 (Botany) and for the coverage factor Iyl were imbued with these solutions and wrought iron at 100% per receipt in each case. Then they were dried at 501 C. After 1 or 2 days of storage. at room temperature (room temperature, the samples were washed in a washing machine (mechanically)] for 30 minutes with a 25: 1 ratio of liquid ratio and the percentage shrinkage (spilling) was measured. The following results were obtained:% thiol resin A% surface shrinkage 0 40 2 3 and 5 0 8 0 A much greater test was also carried out using a liquid tube for a material of 12.5: 1 for 60 minutes and the following results were obtained: o o thiol resin A * o surface shrinkage and ointment o m 2 29 5 i3 8 0 Results of resistance to shrinkage depending on the load on the resin material. These excellent resistance to shrinkage were obtained without the loss of the soft grip of the knitted fabric. resistant to solvents for chemical cleaning and multiple washing in aqueous deltergenite solutions. 82721 13 14 Example II. (This example illustrates the result of using a combination of a thiol-terminated poly (oxyalkylene) resin with a resin having reactive groups capable of reacting with biologicals, such as an epoxy resin, giving an excellent finish, resistant to shrinkage of a woolen material. (20 g) was dissolved in trichlorethylene (3K) 0 ml). Liquid Epoxy Resin: 2.2% Hydroxyphenylpropane diphyl ether containing about 5% 2 eq per kg 1,2-epoxide (10 g) was also dissolved in 363 ml of distillate chloroethylation, and the two Ite solutions were mixed. The overall resin sieving was 3% The knitted fabric described in Example 1 was impregnated with the said solution using a mangle at 14-3% reception and the sample was dried at 50 ° C and then left for 24 hours at room temperature to harden the resin. The sample was then washed in a washing machine at a liquid-to-fabric ratio of 125: 1 and within 30 minutes. The untreated knitted fabric was found to shrink by 40% under the same washing conditions, while the sample treated with 4.13% of the mixture The resin did not shrink at all. Example HI. A piece of gray worsted wool was processed in a chemical cleaning machine with a solution of jthiol resin A in tetrachlorethylene. The fabric was spun in this solution for 5 minutes. nine was then set to a content of 3% resin based on the weight of the fabric. ny. The fabric was then centrifugally dried and cured by "storage for 10 days at 20 ° C and 85% relative humidity. The fabric was then made into a skirt, which was pressed in steam at a pressure of 1.4 kg / cm 2 for 10 days. The skirts were then washed for 1 hour under the conditions (model and after stitching were hung to dry. The appearance of the skirt and the crease angle were assessed and found to have 83% ironing and a smoothness index of 4 ^ 5. Untreated fabric subjected to similar washing was strongly friable and she kept the pleat. Example TV A piece of gray twill worsted fabric pressed flat by stretching in a monoethanolamine (MEAS) semi-sulphite fabric (MEAS), containing 1 g per liter of Joaneweigo's wetting agent, 2% of its weight MEAS and 001% water. The fabric was then semidecatized <[that is, steam treated under atmospheric pressure in the developed state) within 5 minutes when it was damp and finally dried without stretching. Trousers were made of the fabric and the hems of the trousers were hardened by spraying the trousers with a 5% MEAS solution in the area of the cuffs, so that at this point Ifcamine contained about 2% MEAS and 401% water. Then the sipodins were ironed on a Hoffman press, using an ironing cycle: 20 seconds of steam (head closed), 20 seconds of ironing without steam (head closed), vacuum until cool (head open). The pants were then treated in a dry cleaning machine with a solution of thiol resin A in tetrachlorethylene containing 2% amine such that they contained 2.5% resin based on their weight. After six (days), the trousers were washed in an exemplary manner. They showed excellent edge behavior, smooth drying characteristics and did not shrink * Example 5 A piece of woolen Ithane in a checkerboard pattern (in kralfka) was impregnated with a solution of monoethanolamine sesulfite (MEAS) by milling yes that (the fabric contained 3% MEAS based on its weight. The impregnated fabric was dried on the stretcher frame without tension and cut into strips to prepare a pleated skirt. These strips were sprinkled with water to a content of 30% per weight. were pressed between paper templates for ironing and hardened by steaming in an autoclave for 11 minutes at 0.56 kg / cm 2 of steam pressure. After drying and removing from the template, skirts were made of straps. These skirts were then treated with resin, thiol And in the chemical cleaning machine as follows: An ozterchloroethylene solution containing 4% thiol A resin, 0.08% diethylene triamine and 0.20% fcumene hydroperoxide (TrigonoxK-70 supplied by Novadel Limited). The skirts were soaked and spun in this solution, allowed to drain, and the excess resin solution was removed by centrifugation until the skirts retained a resin solution of 60% of its own weight, that is, 2.4% of the resin and a proportion of the others. ingredients. The skirts were then blender dried in a dry cleaning machine. After removal from the machine, the skirt did not need to be ironed again. The resins on the skirt were left to harden and after seven days after 1 hour of washing, the skirt shrunk 1% per length in an exemplary manner and did not change width. The pleating had an average degree of compression of 89% and the rate of smoothness of drying of the flats of the skirt was found to be 4-6. 45 Examples VI — XIV. The Ite examples show that the shrinkage resistance and permanent pressing were obtained with other polythiol resins according to the invention. The fabric used in these examples was diagonan gray meHange wool wool with a weight of 270 g per (square meter and water pH). of a solution of 7.8. The fabric was flattened with 1.5% manodanolamine sesquasulfite (MEAS) per fabric weight and was semidecatized for 4 minutes. The fabric was cut into samples and edges were made on these samples by spraying a 5% MEAS solution near the edge of the fabric. up to 40% of the collection, folding and ironing on a Hoffman press, using an ironing cycle of 30 seconds of steam 60 (head closed), 130 seconds of ironing without steam (head closed) and vacuum to cool (head open). These are calibrated and stabilized on the flat samples were treated with polythiol resins by mixing them from a tetrachlorethylene solution using the concentration and milling conditions required to obtain 3l% of resin per fabric weight. The catalysts used were diethiflenoltrijamMie <(iDRTA) or the calcium naphthanate 16 of the medium used. Samples treated and left to zero at 65% relative humidity and (temperature <20 ° C and subjected to standard washing. Then the surface shrinkage was measured, Table 2 Example VI VII VIII IX X XI XII XIII XIV LIVING DEEFFGGHI Catalyst 5 © DETA l »/ o DETA 5% BETA il% CaN We CaN 1% OaN 5« / o CaN and f% OaN 0 ° / o CaN Time 8 28 8 28 8 14 14 21 14 Sample untreated - Shrinkage of surface 1 area - y * Jq 0.0 4.0 1.0 0.0 1.0 0.0 5.5 0.0 1.5 14.0 Smoothness index 4—6 3 4 4 ^ 5 4 4 3 4 4 1 'i Canite durability 99 75 96 87 100 97 77 86 75 17 1 smoothness index after drying and percentage of edge retention. The obtained dimensions are given in Table 2. The obtained results indicate that the treatment of the woven fabric with resins has excellent resistance. Further, the durability of the canite was in good order, as all results gave a percent life of 75% or more, and most of them showed 85% more. These results indicate that by using resins according to the invention The garment can be fully machine washable as the treated resin garment does not shrink, retains the smoothness of the surface as indicated by the smoothness of drying index, and retains the edges after repeated washing and drying cycles. The grip of the treated fabrics was very good, no roughness visrosft (fabrics. The folding ability (the fabrics were practically impaired. The hardening of the resin was carried out at different times and it was believed that by selecting individual catalysts for individual resins, the desired curing time could be achieved in most cases. These examples do not necessarily cure the resin. They only indicate the length of time between the application of the resin and the performance of the reference wash. In these cases, the actual curing times are shorter than the period given. Examples XV - XXV. These examples are similar to those listed in (VI ^ XIV except that (different resins were used. The resins were applied to the samples (fabrics as in the previous examples VI-0CIV with Itym, with the following catalyst systems being used in some cases: I * / o DETA) + 5% diOauryl peroxide (DP) 1 * / o OaN + and 5% -Duilaiuryl peroxide (DP). The treated sample was subjected to standard tests. The results are given in Table 3. Table 3 Example XV XV I -XVII XVIII XTX XX XXI XX3T XXIII XXIV xxv Living thiol- | wa JJKKLLAAMNN Catalyst 1% DETA / 5% DP 1V # CaN / 5% DP 1% OaiN! »/ • CaN / 5% IP 1% CaN Wt CaN / 5% DP 1% DETA l» / o DETA / 5% DP ! • / • CaN l «/ o DETA l» / o CaN Untreated sample Time (days) 1 14 1 14 14 14 14 14 7 7 21 21 21 - Surface shrinkage * / by 1.5 0, 5 0.5 1.5 0.0 3.0 0.0 0.5 0.0 and 1.0 0.5 14.5 'Speed indicator * 4 4-5 4- ^ 5 4- ^ 5 4— 5 4—5 4- ^ 5 4- ^ 5 3—4 4—5 '5 1 Canite stability ° / o 89 100 88 89 75 80 94 88 76 90 ai 1517 The results show that the treatment according to the invention allows the production of Garments with satisfactory washable properties. In addition, the grip was strikingly good, especially on fabrics treated with thiol resin A., Examples XXVI ^ XXXVII. These examples illustrate the use of other resins under different conditions. As a fabric, a wool ilanel was used with a grammage of about 170% per square meter, the pH of the aqueous extract was 3.1. The flaneie was impregnated with a solution of thiol resin in tetrachlorethylene containing U0% of cylindrical monoethanolamline with respect to the weight of the thiol resin such that the thiol resin uptake was 8%. Then the flannels were dried to their initial dimensions within 2.5 minutes at 50 ° C in a blown oven and stored at room temperature for the time periods indicated in Table 4. The treated samples were washed in a Hooverma1fic washing machine at 50 ° C. IC in an aqueous solution containing 5 g per liter of soap flakes, 2 g per liter of anhydrous calcium carbonate, rinsed in cold water, drained in a domestic centrifuge dryer and finally dried at 50 ° C. The results are given in the table. 4. 82721 i * Example XXVI XXVII XXVIU XXIX xxx XXXI XXXII XXXIII XXXIV xxxv XXXVI XXXVTI untreated Table: Thiol resin BCPQRSTUVWXY - te a 4 Time (days) 1 '9 1 9 1 5 1 8 8 6 1 6 9 1 8 1 5 18 1 8 1 8 - Post-eastern curriculum (* / o) 12.3 '3.7 1 (2.2 5.5 11.7 10.5 '11, 3 7.0 12.5 12.3 12.5 W * 8.7 7 7 9.3 e ^ 5.5 6.5 5 '5.5 4.5 23.5 Similar results were obtained when the flamel was pre-reduced or pre-oxidized. I to be taken up to 5 times with an aqueous solution containing 10 g of sodium metabisulfosin (Na2SO5) and 4 g of Emulsifier I (nonylphenol adduct and 9 molar proportions of ethylene oxide) per liter and dried at 50 ° C in an oven with a blow in the diag 2.5 minutes. In order to oxidize the fabric, it was saturated up to 140% with an aqueous solution containing 20 ml of hydrogen peroxide (30% per volume per liter), 1.2 md of formic acid (85%) 10 15 25 30 40 45 50 55 and 1 g of Emuteifier I. The pH of the solution was adjusted to 3.7 with an aqueous solution of sodium carbonate, kept for 4 hours in a polyethylene bag and then dried as before. Example XXXVUI- XLVI. This group of examples illustrates the extent to which the resins according to the figure render knitted fabrics resistant to mechanical washing. Polyethylene resins were used in a tetrachlorethylene solution by applying 4% / t of resin to the fabric until it was obtained. The material samples consisted of a simple botany knit with a coverage factor of 11.1. The material intake was adjusted to 200% and after application, the samples were dried in a tumble dryer at a temperature. As a trial test of mechanical washing resistance for knitted products (it was proposed to wash the products in 25 liters of washing liquor for 30 minutes in a Cubex machine washing machine, after which in 60 minutes in 12.5 liters of washing fluid in the same machine. The treated samples were subjected to the washing test which was carried out after the resin was completely hardened. The catalyst used was 2% by weight of diethylene triamine "per weight used" Wyrm is given in the Reference Table 5 Example XXXVIII XXXIX XL XLI XLII XLIII XLIV XLV XLVI untreated DEHJKAMNO resin ^ ~ Time (days) 22 22 5 2 25 7 10 2 24 -1 Surface curvature {%) 4 3 - <3 1 5 Jl 12 1 1 712 The Cubex washing machine is a machine for testing the capacity for machine washing and contains a cubic vessel with an internal capacity of <50 liters, supported on a different length. and rotating at 60 revolutions per minute, the direction of rotation being reversed every 5 (minutes with a 5-second pause when changing the direction of rotation. Example XLVII. Emulsions of thiol resin A were prepared containing the following ingredients: Thiol resin A Emulsifier I monoethanolamine water 3.00% / t 046% / t to 100% 55 These emulsions were applied by milling to a piece of gray diagonal fabric which was previously it was flat-fixed by the banding method of Example IV, except that a monoethanolamine solution was used as a fixing agent. The fabric kept the emuflsje in the amount of lOOP / f19 82721 20 swelgo weights. The saturated fabric was dried without tension and the resin was allowed to harden. Several trousers were removed from the fabric and the hems of the trousers were fixed as described in Example IV. After washing after seven days with the standard method, the pants shrunk by 0.7% in width and O ^ / o and in length. They had a smoothness factor of 5 and a corner durability of 85%. In other experiments, an aqueous emulsion of thio resin A was prepared and by mixing 320 g of this polythiol with 144 g of water and 16 g of Emulsifier II (adducts of immixainin of primary aliphatic amines {1%) - 18 carbon atoms in the molecule and ethylene oxide (70 moles). A HO g portion of this emulsion was mixed with 7.5 g monoethanolamine and 882.5 g water. Wool filanels were impregnated with the resulting solution for collection, dried at 50 ° C in a blown oven and left for 16 days at 20 ° C. The thus treated Itkanine was washed over a 1 hour period in a Hoovermatic machine washing machine at 50 ° C with washing liquor containing 5 g of soap flakes and 2 g of anhydrous sodium carbonate per liter. The surface shrinkage was 6 g5%, while the untreated flannel shrank 29.7% / d under the same washing conditions. Example XLVIIfI. The piece (shirt fabric containing & () "/" wool and 50 * / abavel was flat fixed with motioethhenolamine sesulfite as described in Example IV. Half of the fabric and the previously untreated Ithane cloth were ground Chemical cleaning rail thiol resin A, catalyzed by the addition of 2% diethylenetriamine (based on the weight of the resin), so that the fabric 10 15 contained 2.5% of resin based on its weight. After allowing the resin to cure. Within 7 days, two shirts were made from the two pieces of resin-treated fabric, and the third shirts were made of untreated fabric. The four shirts were washed and pressed in a standard centrifuge, and after drying, smooth drying characteristics were obtained. Table 6 25 30 35 Processing It cloth untreated only flat set resin A Ityliko and flat set and thiol resin A 'Dryness index | 3 2 ^ 3' 4 4- ^ 6 Results show improved gladkos drying of woolen (cotton) fabrics using thiol A with and without flat fixing. Examples IL and L. These examples illustrate the ability to machine wash lamb and Shetland sweaters. The sweaters were first washed in a solvent and then a mixture of thiol resin A (4425 g), diethylene triamine 1 (88.5 g) and ozterochlorethylene (54.6 liters) was impregnated. After impregnating for 3 minutes, the products were frozen for collection, centrifuged for 3 minutes in the cold, and then dried at 65 ° -0 ° C for 10 minutes. After washing three days later in a domestic washing machine, the treated sweaters were found to have excellent anti-dusting properties. The results are as follows: Example IL 1 L Shetland lamb wool sweater Table 7 '/ o feeding 3.08 2.85 * the area of relaxation shrinkage -12.0-3.2 M of the shrinkage area of the filament -3.7 -h6.9% of the total shrinkage dry / dry -0.7-3.2 Washing test 2 times 10 minutes in a Hoovermatic washing machine. Examples LI and DII. These examples illustrate the use of thiol resin A to fix the double woolen jersey in the wash and to prevent shrinkage caused by spitting. The double woolen jersey was impregnated in a dry-cleaning machine with a solution of thiol A resin (9.65 kg) and diethylene triamine (diethylene triamine). 105 g) in tetrachlorethilene (159 liters). The double jersey pieces were centrifuged in the resin solution for 3 minutes, the liquid was drained into the reservoir, the pieces were centrifuged at high speed for 7 seconds to obtain a 84.5lD / draw, and dried at 50 ° C for 112 minutes. After washing three days later, it was found that the treated jersey had a pleasant soft hand, and showed good retention for relaxation shrinkage and excellent anti-chafing properties. Washing test: relaxation - 15 minutes of static soaking followed by 5 minutes in CubeK. e; washing - 1 hour in Cubex, with 12.5 liters of washing solution. Example LI LII untreated Taibld • / resin 3.2 2.8 0.0 ca 8%, relaxation shrinkage 5, 4 5.6 13.2% by area of swollen contraction 1.6 16.321 82721 22 Brown clade LIII. This example illustrates the use of an aqueous solution of thiol resin A in knitted garments for the production of shrink-resistant articles. The lithium resin A (ISO g) and Emullsiifier I (22.5 g) were mixed with a high speed stirrer after 327.5 g of water was slowly added to form a stable emulsion. These 3K)% emulsions were then diluted to 3% and 5% diethylene triamine based on the weight of the resin was added as the catalyst for the table. The emulsion was impregnated with botany wool material (coverage factor 14) and dried in a rotary drum at 60 ° C. Treated (the material was left to cure at room temperature. A wash test was done and after 14 days it showed that the treatment perfect finish, resistant to quenchiness, whole Example LIII, untreated resin 3.0 0.0% of the surface of the joint shrinkage 30 minutes Cuibez (25 liters of washing solution) 0.4 38.3 / 30 minutes. Cubex (2 and 5 liters of washing solution) + 2 hours Cubex and (12.5 liters of washing solution) 24.72.0 Example LIV Piece of gray twill brocade fabric which was fixed to the surface with monoethanolamine bisulfite - (MEAS) according to the method described in Example IV, the fabric was angled in the warp direction by spraying the fabric with a 5% solution of MEAS so that it retained the 40% solution in the area of the intended edge, folded and pressed on a Hoffman press using the cycle: 20 seconds of steam (head closed), 20 seconds ironing without steam (closed head) 30 and 10 seconds vacuum until cooling (open head). The sample was treated with a solution of equal amounts of thiol A resin and "Synthalppreit LKF" in tetrachlorethilene. The sample was treated in such a way that it retained 0.75% of Thiol Resin A and 0.75% of "Synthappret LKF". Immediately after evaporation of the solvent, the fabric was washed under normal conditions and subjected to reference tests. Surface shrinkage = 0.5%. Index * with ease of movement = 5, durability = 100%. The grip of the treated (the fabric was better than the grip of the fabric treated exclusively with "Synthappref LKF" up to 1.5% of the picking. The resin cured immediately and after 7 'days of the resin bath "it was still to be used, with similar results PL PL

Claims (8)

1. Claims 1. A method of modifying keraitin fiber materials by treating these materials with a resin and then hardening the resin on the material, characterized by the fact that a polythiol resin having at least two thiol groups is used as the resin. in a molecule and containing a polyhydric alcohol radical, at least two poly (oxyalkylene) chains attached to this radical and linked by oxygen atoms to carbon atoms in poly (oxyalkylene) chains at least two acyl radicals of thiol-containing aliphatic canboxylic acid or thiol-containing acyl radical of aliphatic alcohol), in the form of an aqueous emulsion or solution in an organic solvent and optionally in the presence of a catalyst. 2. The method according to claim The method of claim 1, characterized in that a polythiol resin of formula 1 is used, in which im, p, and q are positive integers, m is at least 1, p is equal to 2-h6, p + q is equal to 3 - ^ 7, each of the alkylene groups contains a tance composed of 2 to 6 atoms between consecutive oxygen atoms, R is an aliphatic radical containing at least 2 carbon atoms, and X is an alkyl or acyl radical containing at least one Itio group low. 3. The method according to p. A polyethylene resin of formula IV in which R2 is an aliphatic hydrocarbyl radical of 3-6 carbon atoms, each of the alkylene groups contains 2 to 6 carbon atoms between the oxygen atoms, m is a positive integer, p2 is an integer equal to 3-16, and au is 1 or 2. 4. The method according to p. The process of claim 1, wherein the polythiol resin has 3-6 thiol groups in the molecule and has a molecular weight of 400-110,000. 5. The method according to p. The process of claim 1, wherein the polythiol resin is used in the presence of a basic free radical or siccative catalyst. 6. The method according to claims A method as claimed in claim 1, characterized in that the polythiol resin in the stack is consumed and in the form of a solution in chlorinated, fluorinated or chlorinated hydrocarbons, containing no more than 3 cyohn carbon atoms. 7. The method according to p. 3. A method according to claim 3, characterized in that a polythiol resin containing a glycerin radical is used for the treatment of wool, bonded to three polypropylene oxide chains and three acyl radicals of thioglycolic acid linked via oxygen atoms to the propylene oxide chain. 8. The method according to p. 8. A method according to claim 6 or 7, characterized in that the polythiol resin is used in the environment of carbon tetrachloride, trichlorethiene or tetrachlorethylene. 82721 (O-alkyl) mOH] rl rO-alkylene) mOx] p FORMULA 1 fo-dlklleii) mOH] qH ( O-alkylcn) m0.C0.CrH2rSH] p FORMULA 2 VO-olkylene) mOH] r1 70-alkylene) m0 £ 0OH2oSH] Pj FORMULA 3 fO-alkylene) mO.CO.CuH2oSH1 p FORMULA 4S2721 CH2 I CU I CHo ^ t ^ m 0-CO.CuH2uSH (OCtH2 +) mO.CO.CuH2uSH (° ctH2t) mo.cacuH2uSH H2OD 5 CH2— (OC.H ^ O.CO.C ^ H ^ SH CH— (OCtH2t) mO.CO .CuH2uSH (CH2) 2 "CHl-fH LCH2j f (OCtH2t) mO.CO.CuH2uSH FORMULA 682721 CH2— (OC3H6) mOCOCH2SH CH - (OC3H6) mOCOCH2SH CH2— (OC3H6) OCOCH2SH FORMAT. ] vf [(O-olkyl) mOCH2CHCH2SH] WZOB 8 [(O-alkyU ^ OH] ^ [(O-aikaen) mOCH2CHCH2SH 1 D3 3 P1 FORMULA 9 D2] | (O-alkiler) mCX: H2CHCH2SH1 D3 WZOD 1082721 [p2 ] [(OCtH2t) mOCH2CHCH2SH] OH FORMULA 11 (O ^ H ^ OCHJCHCH6SH (OCtH2t) vOH FORMULA 12 CH2- (OC3H6) mOCH2CHCH2SH OH CH- (OC3H6LOCH2CHCH2SH OH CH2- (OC3HZCH2SH OH CH2- (OC3HZCH2)