PL27694B1 - A method of treating natural or artificial fibrous materials. - Google Patents

Description

It has been found that natural or artificial fibrous materials or other formulated products consisting wholly or partly of protein substances, their derivatives or substitution products, or also of non-protein substances with a large particle which can be alkylated. with basic groups, treated with alkylating agents which do not react with the carboxyl groups or react not only with them, they acquire new properties without changing their original form and structure. The ability to absorb or fix substances with acidic groups, possibly associated with bases, is improved. By alkylation, substitution takes place in the basic or basic groups, for example in the methyl sulfide group or in the rest of the thiourea, and in the acid groups. Both alkylation in basic groups and alkylation in acidic groups causes the enhancement of the alkaline properties. So if even in amphoteric bodies the basic groups are no longer capable of reacting, the desired affinity change may occur by alkylation of the acid groups. Wool, chrome-plated wool, chlorinated wool, wool can be treated according to the invention. pretreated with bases or basically reactive salts, e.g. sodium tetraborate, sodium thiosulphate, sodium sulphite, rhodiums, or hydrogen peroxide, then wool treated with alkyl mustard oils, natural silk weighed or unloaded, rayon, casein, rayon, protein-animated rayon, horse hair, feathers, bristles, fur, horn, hardened and unhardened casein masses, gelatine foils, untanned and mineral or ro tanned animal skins Saliva, formed cellulose derivatives containing basic nitrogen in ether, ester or amide groups, for example by halogenoalkylamine or alkyl enominim for cellulose, and finally artificial fibers of cellulose or rayon of cellulose acetate, containing either alkaline artificial resins mixed in the form of a physical mixture or rendered alkaline by alkylation. As an example of a basic synthetic resin which may be mixed with cellulose acetate, there may be di-ethylaminoethylamide of polyacrylic acid (French Patent No. 789,460) and numerous products described in Polish Patent No. 23,940. As artificial resins that become alkaline, there may be mentioned e.g. artificial with urea, mercapto or sulfide groups. The first of them changes as a result of alkylation with alkyl halides into isourea ethers, while both other types transform into sulfone compounds. Various types of alkylating agents can be used to treat the products according to this method. They can be divided into ester-type alkylating agents, meaning here being understood to be the reactive organic esters of inorganic acids or their organic substitution products, and into alkylating additive agents which do not have this reaction-capable ester group of this type. They are primarily compounds which react with the simultaneous cleavage of the ring compounds or with the indirect formation of the ring. Then, mention should be made of bodies that have double bonds that can easily be attached to primary amino groups, e.g. a - f unsaturated carbonyl compounds and their derivatives. For the last mentioned particularly important group of alkylating agents with additive action are, for example, the following compounds: ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin, epifluorohydrin, epidichlorohydrin, glycide, butadiene dioxide, phenoxypropene oxide, 1 - methyl - thio - 2,3 - propene oxide, acids glycide and their salts, 1,2 - oxypropylene - 3 - sulfonic acid salts, 1 • diethylamino - 2,3 - propene oxide, 1 - piper- to - 2,3 - propene oxide, N - chloride triethyl - 2,3 - oxypropyl - 1 - ammonium of formula I, 1,2 - propylene sulphide and its iodomethane, 1 - chloro - 2,3 - propylene sulphide, ethyleneimine, N - butylethyleneimine, diethylethyleneammonium chloride ( formula II), NN 'chloride - diethylene piperazine (formula III), pentomethylene - phi - oxytromethylene - ammonium chloride (Nimilowicz Mon. 15, 119) (formula IV), methyl- [y - chloro-phi - oxypropyl) - ph - oxytrimethyl- ammonium chloride, NN '- bis - phi - oxy-trimethylene piperazine chloride (formula V), product of action 2 molecules of potassium hydroxide per cyclohexyl chloride - tri (γ-chloro-β-oxypropyl) - ammonium chloride, diazomethane, acrolein, as well as any mixtures of such bodies, e.g. β-chloroethyl-ethylammonium, ethylbenzylenammonium chloride or dubenzyl-ethyleneammonium chloride and epichlorohydrin. I: (C, HJ3 N (Cl) -CH2 — CH-CH2 II: CH2. ^ (CoHb) 2 N cHy ^ ci - 2 -III: CH2. / CH2-CH2. / CH2 NN Cl Cl IV: CH2-CH2., CHnK Cfl2 N CHOH CH "—CH /! \ Cff / C / V: yCl2 \ / CH? - CH, / \ / HOCH N \ CH 2 \ y ^ "2v AT CffOff 2 and CH« - Ci // i \ Ctf2 c / ~ c / The group of ester-type alkylating agents includes, for example, the following compounds: bromide, methyl iodide, bromide, ethyl iodide, n-butyl iodide, benzyl chloride, p-nitrobenzyl chloride, ethylene chlorohydrin, methyl chloroacetate, chloroacetate lde- hyd, chloroacetone, 1,3 - dichloroacetone, 1A - dibromodiacetyl, sodium chloromethylbenzenesulfonate, salts of xylene-sulfenic acid halogenated in the side chain, alkyl esters of alkylsulfonic and toluenesulfonic acids, naphthalenesulfonic acids, salts of carboxylic sulfonates , sulfite /? - chloro-ethylmethyl, di - /? - chloroethylmethylamine, sodium dimethylaminoethanol sulfate. These compounds can also be mixed with one another at will, or used in a mixture with the alkylating agents of the first group. For example, mixtures of alkylene oxides and easily reacting halogen compounds are very active. The products obtained according to the present process react more easily with dyes and their derivatives, natural or artificial tannins, dressing agents, weighting agents and reductants. , moth-protecting agents, acylating agents, e.g. acetic anhydride in the presence of sulfuric acid (see Miintz and Haynn, Chemiker-Zeitung 1922, p. 945), especially when alkylene oxides are used Hydroxyl groups were introduced into the products. The material to be treated can be treated with alkylating agents in the liquid state, in the state of solution or suspension in water or organic solvents, or in the gaseous state at normal or higher temperature and under normal, reduced or increased pressure. in the gas phase, it is best carried out in closed apparatuses, whereby good mixing should be used, especially for The reaction is very uniform, especially when the gases or vapors are operated under a pressure that varies rhythmically, for example with pressure fluctuations from 40 to 250 mm in the height of a water column. It is also advantageous to use closed apparatuses with constant circulation in the bath, for example known dyeing apparatuses, especially when the treatment agents exhibit a greater vapor pressure at the operating temperature. A simple method of treating textile materials, namely wool, is to place the material in loose form or as a comb or strand in the rotary boiler after it has been moistened in such a way that it cannot move anymore. Then, the treatment agent is added, the vessel is closed and at a suitable temperature it is allowed to rotate completely slowly. The upper temperature limit depends only on the strength of the material to be treated. In the case of sensitive products, for example wool, it is preferable to use average temperatures, for example 40 to 80 ° C. The fabrics can also be printed with a thickener containing a slightly volatile or completely non-volatile alkylene oxide, a salt of glycidic acid or another with of the above-mentioned materials. Special catalysts are not generally required for the reaction. When using alkylene oxides and alkylene sulphides, the conversion rate sometimes increases when the process is carried out in the presence of basic substances, e.g. triethylamine, diethylaniline, pyridine or in the presence of other known agents accelerating reactions with alkylene oxides, e.g. in the presence of sodium acetate, chloride or fluoride, calcium chloride, magnesium chloride, magnesium perchlorate, tetramethylammonium chloride. It is also possible to use products that influence the surface tension with advantage, for example, trihydodecylammonium chloride. Small amounts of such substances, for example 1 to 5% of triethylamine (relative to the amount of material treated), suffice to achieve a positive effect. The processed material can also advantageously be treated with slightly acidic alkylene oxides and their derivatives, or in a slightly acidic environment, for example in the presence of acetic or formic acid. When using slow reacting halogen compounds, the conversion can be accelerated by the addition of a small amount of iodide, for example potassium iodide or trihydodecylammonium iodide. Along with the reactive alkylating agents of the ester type, inert or basic acid binders or buffer agents, for example sodium bicarbonate, potassium acetate, borax, sodium phosphate, sodium silicate, magnesium oxide, calcium carbonate, can be used. The rate of the reaction is also influenced to a large extent by the deformation state of the processed material. For this reason, in most cases the reaction is accelerated very much by the presence of water or water vapor; a certain amount of moisture is especially important in the treatment of hydrophilic fibers, for example wool, which are treated at as low a temperature as possible to protect the processed material. Completely dry ordinary sheep wool reacts at lower temperatures, e.g. at 40 ° C, very slightly, or very slowly, even with relatively reactive alkylating agents, e.g. with ethyl bromide, as a result of which, e.g., within 2-3 hours practically no satisfactory results are obtained. When operating in the gas phase, for example in the processing of wool, the air should contain 50 to 100% relative humidity. The presence of special swelling agents or the pretreatment of the treated material with such agents causes a significant increase in its reactivity. Suitable agents for inducing the swelling of protein materials, eg wool, include, for example, formamide, acetamide, thiourea, phenol, resorcinol, methanol, glycol, salicylates, cresol sulfonates, rhodides. These measures should be used with care in all or four times, because when used in too large amounts or under inappropriate working conditions, they may damage the treated material. For the products of cellulose and its derivatives, it is possible to use the agents mentioned frequently and, moreover, the already known special agents, for example, alcohols for the treatment of cellulose acetyl. It is also possible to use oxidizing or reducing bleaching agents, as well as known preservatives for the bottom of animal fibers, e.g. sulfite waste liquor, condensation products of phenol sulphoric acid and formaldehyde, followed by aldehyde and agents that release these compounds, antioxidants and other tyn * like. The treated materials may be pre-treated with agents that produce chemical changes. For example, the reactivity of wool towards alkylene oxides and other alkylating agents increases significantly under the influence of mild chlorination. The processed materials can be treated not only with ready-to-use agents, but also with the raw materials, from which they can only be re-formed by regrinding, condensation or cleavage; in this way they operate to a certain degree in statu nascendi. For example, alkylene oxides are formed from halohydrins when heated in the presence of moisture by the action of metal oxides or hydroxides such as magnesium oxide or lead hydroxide. Quaternary salts having γ-chloro-groups on the nitrogen. - oxypropyl, epichlorohydrin is formed by the action of alkaline agents. On the action of 1,2-propylene oxide on the materials deposited with a thiourea solution, first 1,2-propylene sulphide is formed. On thermal cleavage of unstable halogenalkylates or salts of iminoethers, halogenalalkyls are released. For the purposes of the invention, it is also possible to take advantage of the easy cleavage of quaternary polyalkylene polyamine salts, for example polymerization products obtained from haloalkylamines. When treating with alkylene oxides and their derivatives, it is advantageous to carry out or at least start the reaction in in a slightly acidic environment, for example in the presence of acetic, formic, lactic or oxalic acid. The use of strong acids which do not esterify as easily with alkylene oxides, such as those of the hydrohalide group, oleylmethyltaurine, isobutylnaphthalenesulfonic acid, is generally only expedient when very vigorous action is not required. When choosing the working conditions, it should be remembered that in the presence of moderate amounts of stronger acids, wool can withstand higher temperatures and longer treatment periods than in the neutral or basic state. When the residues introduced into the processed materials still contain easily reacting ester groups, e.g. halogen in the chloroxypropyl group, then these products can be treated later, especially simultaneously with the dyeing or printing process, with agents that increase the affinity for dyes in the desired direction. As agents to increase the basic character, mention must be made of amines, especially tertiary -, for example, trimethylamine, pyridine, isoquinolines, then thiourea. Other bodies suitable for substitution are as follows: sulphites, thiosulphates, salts of mercapto or mercaptosulphonic acids, hydrosulphides of amines or weak inorganic bases. By treatment with alkylating agents or their mixtures, the affinity of the treated materials for the treated materials is significantly increased. acid dyes, unless acid groups are introduced at the same time. The results are especially pronounced on wool and other animal hair. As a result, according to the invention, wool can be treated in the presence of non-boiling artificial, acetate fibers, dyed at low temperatures (below 85 ° C), not harmful to artificial fibers, the dye being equally well used, and the dye fastness does not deteriorate. On the contrary, even with the usual equalizing dyes a greater wash and water fastness is achieved than with the simple dyeing of untreated wool in a boiling bath. Subsequently, for example, when using epichlorohydrin, the addition of acid can be significantly reduced during dyeing, or even dyed without the addition of acid, so that in the case of mixed fabrics made of wool and pre-dyed artificial acetate silk, acetate dyes which give a not very durable dyes are less damaged, thanks to which a purer bicolor effect is obtained. When dyeing a half-whale or a mixture of wool and synthetic fibers with acid or direct dyes in an neutral bath with Glauber's salt, it is of great importance to improve the dye drawability. the affinity for dyes is of great importance in printing in particular. In this case, usually by means of chlorination, the absorption capacity of the dyes by the wool fibers is increased, but the fibers may easily be damaged, in particular, with a detrimental reduction in their resistance to moisture. The treatment of wool with epichlorohydrin as described in Example VI results in a greater increase in affinity than does mild chlorination. In the case of a particularly strong action, the wool may be previously chlorinated and additionally treated with the agents according to the invention. An increase in the affinity for acid agents corresponds to a decrease in the affinity for alkaline substances, provided that together with the agents used for treating The acid residue has not yet been introduced or the acid residue has not been formed, as is the case with sodium propyleneoxide sulphonate. On wool that has been treated, for example, with epichlorohydrin, or on natural silk, with basic dyes such as methyl violet (Schultz, 7th edition, vol. I, page 327), much less dyeing is obtained. The basic properties increase even more if, for the same degree of substitution, the reacting compound - for example, N - diethyl - ethylene ammonium chloride - still contains basic nitrogen. On the other hand, by treating wool with sodium propyleneoxide sulfonate, the ability to absorb acid dyes is significantly reduced, while the affinity for alkaline bodies increases accordingly. Various valuable effects can be obtained by jointly processing treated and untreated fibrous protein or fiber materials. Those that have been treated or treated with unequal power, or with measures having the opposite effect. For example, strong effects can be obtained with the same shade, and the difference in shade depth can be varied by the choice of dyeing temperature or by the type and amount of acid added. Bicolor effects can also be obtained by covering or pre-dyeing with basic dyes, or by the simultaneous use of several acid dyes of relatively different tensile strength on the treated and untreated fibers or treated fibers having the opposite effect. For example, extremely strong differences are obtained when dyeing with homogeneous dyes or mixtures of dyes, since ordinary wool and velvet which has been treated with epichlorohydrin after chlorination are processed together. This method is not limited, of course, to the treatment of homogeneous products. In the described manner, it is also possible to change the properties of mixtures of fibers, e.g., mixed yarn of acetate rayon and wool, mixed yarn of viscose and wool fibers, mixed fabrics. can also be used in conjunction with the washing, dyeing or printing process, or in conjunction with the fixation of other agents used for the treatment of fibers, e.g. fixation * For example, printing pastes containing acid dyes are easily added with easily reacting binders, for example haloalkylamine or polyhaloalkylamine, the evaporation time being extendable as required. After printing and drying or evaporation, the goods are left at appropriate air humidity and temperature for some time, until the alkylation process is sufficiently advanced. Wool fabrics, felt cloths and other dense surface products can also be padded with strong dye solutions at ordinary or slightly elevated temperatures, and then fixed by keeping them wet while warm in the presence of an alkylating agent, e.g. epichlorohydrin. it may immediately find itself in the soaking bath, as long as it is not too volatile. In this way, it is possible to obtain exceptionally uniform and permanent dyes on dense material. Particularly important is the additional treatment with alkylating agents or any combination thereof, of products dyed with water-soluble dyes. The practical implementation of such additional treatment is that dyed textiles, fur, leather or the like are rubbed with a solution of an alkylating agent and left at the appropriate air humidity and temperature until the reaction is completely complete or far enough of it. It is clear that also in these cases the process can be accelerated or directed in a specific direction by means of swelling or reaction accelerating additives, by pretreatment, as well as by appropriate adjustment of the pM value. Particularly advantageous is the use of pairs of reacting bodies, as this completely avoids the risk of "bleeding", eg in the case of colorful mixed fabrics or printed articles. The revitalizing agents, possibly on the material, remain intact under these conditions, while they partially cope with wet treatment or move to adjacent places. In both cases, it is necessary to bear in mind at all times, that some dyes change their shade, which is especially important when dyeing; Particularly, p-oxyazo dyes change the color of the dyes with the hydrogen of the hydroxyl group undergoing exchange, for example the dye Orange I (Schultz, 7th edition, volume I, page 84), and dyes with amine groups capable of for reactions, especially primary ones, eg Alizarinsaphirol. Depending on the type of dye change, a hypsochrome or batochromic phenomenon may occur. The discoloration can be prevented by appropriate adjustment of the pH value. In general, the changes are the more severe the more alkaline the reaction becomes. In such cases, reactions with alkylene oxides should be carried out or at least initiated in a slightly acidic environment. In the presence of strong acids which do not react at all or do not react poorly with alkylene oxides, e.g. sulfuric acid, the result obtained, for example, with epichlorohydrin, is worse, and the course of the reaction deteriorates not only quantitatively, but also qualitatively. Alkylating agents with one active group, for example, propylene oxide, ethyl iodide, ethyl bromide, benzyl chloride, methyl ester of haloacetic acid, chloroacetone, react less well with wool and chemically similar natural or natural products. artificial and under mild conditions, for example at a temperature of 50 ° to 60 ° C, do not improve strength in the same way as alkali containing more than one active group, for example epichlorohydrin, butadiene dioxide and others. On the other hand, a significant enhancement of the effect is obtained if simple ester-type alkylating agents are combined with simple alkylene oxide alkylating agents and analogous compounds, for example with equimolar mixtures of 1,2-propylene oxide and ethyl iodide, methyl ester of chloroacetate acid. In general, the ultimate dye resistance is better when the treatment is carried out after dyeing, because after treatment with the alkylating agent, the dye may migrate to sites of greater alkalinity, or with the greatest affinity. This dye migration corresponds to a slight decrease in dyeing strength, which can also be seen in cases where chemical alteration of the dye is completely ruled out. The additional treatment is essentially the dyeing obtained with any dyes containing acidic groups. and above all with wool and silk dyes, and from them with so-called "equalizing" dyes, especially valuable representatives of this class resistant to the action of light, for example, products on the market under the name Anthra lanfarbstoffe fi. G.). Also materials on which it is difficult to obtain even dyes can be dyed evenly with "equalizing" dyes and only then additionally treated with epichlorohydrin to increase resistance to water and washing. The change of shade, which is slight with the appropriate selection of the dye, is of no importance in view of the significant change in the shade of color which occurs after customary chrome-plated. The method according to the invention may also be of great importance in dyeing with more dyes. water-resistant and washable, for example, those commercially available under the names Supraminfarbstoffe (IG), Supranolfarbstoffe (IG) or Palatinechtfarbstoffe (IG). Even with the use of dyes requiring additional chrome plating and metachromium dyes, an improvement is achieved. Although the additional improvement of dyes dyed with alkylating agents is of importance in the first place when dyeing with acid dyes, or dyes with acid groups, this method can be used. also for basic dyes, but using agents which introduce acid groups together, for example the already mentioned sodium 1,2-propyleneoxide-3-sulfonate. The materials to be treated additionally may be pretreated before or during dyeing with alkylating agents, possibly of a different kind. For example, raw wool, preferably deacidified, is first treated with propylene sulphide, after it has been processed into textiles, it is dyed with acid dyes and, in order to improve its porn performance, it is subjected to additional treatment, for example with epichlorohydrin. Products altered by alkylation, especially wool and other keratin materials, show significantly increased chemical resistance. In the case of wool, this phenomenon is particularly pronounced when it is treated with substances capable of reacting with at least two groups to be changed or substances that convert into compounds containing at least one variable group, e.g. butadiene dioxide, sulfide 1,2 - propylene, epichlorohydrin, 1 - chloro - 2,3 - propylene oxide, tetrachlorooxypropylammonium chloride. Wool treated with such or similar substances dissolves in the bases much more slowly, so that the materials thus treated are particularly well suited for the manufacture of articles that are to be subjected to an alkaline dyeing process, e.g. with sulfur dyes, with vat or naphthols AS, or any other basic treatment, e.g. alkaline washing, mercurization or shrinkage. When dyeing with AS naphthol, it is also important that wool pre-treated with alkylene oxides, e.g. epichlorohydrin shows, to a lesser extent than the untreated material, the undesirable phenomenon of bonding wool with diazone salts. As a result, cleaner shades are obtained. For example, wool pre-treated with epichlorohydrin and then bleached with hydrogen peroxide is obtained with 2,3-oxynaphthylaminobenzene and a diazone salt made from the dye Echtblau BB Base (Schultz, 7th edition, vol. II, page 91) a good garnet, while on ordinary wool only a greenish blue-gray color is obtained, It has been found that many of the above-mentioned alkylating agents, in particular aikylene oxides and alkyleneimines, or their derivatives, as well as haloalkylamines and hypochlorousaikylamines reacting analogously to them have been found in this way protein, that they are much less damaged by microorganisms. Under certain conditions, complete and permanent protective immunity can be obtained. In this respect, for example, epichlorohydrin gives very good results, which has the advantage that in the gaseous state it can also be used for treating articles which cannot be wet treated with solutions of known anti-moth protectants; as such items, mention may be made of carpets, ready-made goods, uniforms and other similar articles. Objects that are destroyed by moths, such as upholstered furniture with wool or hair, bedspreads, pillows, can be easily cleaned and protected from moths. In addition to the mentioned alkylene oxides or alkyleneimines, e.g. epichlorohydrin, epifluorohydrins, butadiene dioxide, butylethyleneimine, dialkylethylene ammonium halides and the like, and reactive heterocyclenes containing residues affecting surface tension, e.g. compounds with carbon chains from 8 to 14 carbon atoms alkaline, water-soluble, e.g. halogenated-tri-phenylmethanesulfonic acid propylene oxide derivatives. All the above-described additional operations, e.g. addition of swelling agents, catalysts, bleaching agents and fibrinoprotectants, can be to be used according to the invention and when it is only a matter of protecting the finished products against pests. In the case of sensitive products, work in the gas phase at high air humidity requires caution. Avoid condensation with o- -? -cooling; for this purpose, it is preferable to remove moist air before opening the chamber with warm and dry air, or at least to remove most of the humid air by applying a vacuum. Example L A wool grain is treated for 8 hours at 40 ° C with a one-percent solution propylene oxide in water, the bath ratio being 1:40. The wool on the outside does not change completely and only slightly yellows. In this state, especially in an neutral or slightly acid dyeing bath, it has a much greater affinity for acid dyes, e.g., Alizarindirektblau A (Schultz, 7th edition, Supplementary Volume, page 62) than a comparative sample treated in a similar manner. only water. If 2% more triethylamine is added to the propylene oxide solution (relative to the amount of wool), an even deeper dyeing is obtained. Example II. Wetted grain wool is heated to 50 ° C for 8 hours in propylene oxide vapors (25% by weight of wool) in a closed vessel with a capacity of 100 volumetric parts (in relation to 1 part by weight of wool). Oxypropylated wool has a neutral behavior with respect to stretch dyes, similar to wool treated in the manner described in Example L. In a similar manner, yarn rolls, for example woolen spools, can be refined. The strength of the yarn in the dry and wet state after the treatment has not changed. By joint processing of curled untreated and treated yarns, shrinkage and effects of similar shades ("Toft-in-Ton") can be obtained simultaneously. EXAMPLE III, A mixed yoke, consisting of 50% wool and 50% wood fiber, is left for 16 hours at 40 ° C in an air containing propylene oxide. dyed with 1% of Pegubraun dye (Schultz, 7th edition, vol. II, page 173), already at a temperature of 50-85 ° C, gives much stronger and more even dyeing than before untreated. Example IV. The loaded one is heated to 50 ° C for 14 hours in a closed chamber with a capacity of 160 parts by volume with 20% ethylene oxide at 92% relative humidity. Silk treated in this way, externally unchanged, shows a markedly increased volume. guilty for acid dyes such as Eosin S {Schultz, 7th Edition, Vol. I, page 375), Azowollblau (Schultz, 7th Edition, Vol. I, page 55), Alizarindirekt blau A (see above), Amidonaphtolrot BB ( Schultz, 7th edition, volume I, page 58). These dyes are much more resistant to the effects of water. Outwardly, silk does not change. The breaking strength decreases slightly, while the limit elongation increases correspondingly. Example 5 Woolen fabric is soaked in a 10% glycide solution in water and spun. The material treated in this way does not change externally when heated to 50 ° C for 9 hours, but has an enhanced ability to absorb numerous acid dyes, e.g. Alizarindirektblau A (see above). Example VI. Long wool is wetted thoroughly with water containing 1% dodecyltrimethylammonium iodide, thoroughly centrifuged and suspended at 30 ° C for 12 hours in a sea containing 20% epichlorohydrin (for the weight of wool). 100 volumetric parts of the chamber correspond to 1 part of wool. Affinity of wool treated with epi-10-chlorohydrin to dyes or dye components with acid groups, e.g. Alizarindirekt Wau A (see above), Thiazinrot (Schultz, 7th edition, Volume I, page 121) or the Indigosolgriin JBA (Schultz, 7th edition, supplementary volume, page 109), increases significantly. A similar, though not as clear, result is obtained when dry wool is treated in a similar manner with a mixture of air and epichlorohydrin at 75% relative air humidity. It should be assumed that after the absorption of chloroxypropyl groups, further secondary transformations take place, enhancing the result. It is difficult to determine whether and what other groups on the side of the amino groups are still changed. As soon as the wool is sufficiently substituted, the reaction of the amino groups is still slightly positive or ceases at all. For example, wool treated with epichlorohydrin in the gas phase up to an increase of about 11% by weight no longer exhibits a quinhydrone reaction after a brief boil, unlike the starting material. This wool has increased resistance to the action of ultraviolet rays, even after bleaching with hydrogen peroxide. For this, the bleaching effect is relatively permanent. Even after a fairly short exposure to light, ordinary wool shows a clearly stronger reaction to unbound sulfur. Dyes with acid dyes, for example Amido-naphtolrot BB (see above), obtained in the presence of sulfuric acid on the previously treated fibers, are then significantly more resistant to the action of water and washing than such dyes on ordinary wool. It should further be noted that the treated woolen cloth shrinks much less, making it suitable, for example, for the production of strips in woolen cloths. So avoiding the danger of faster or stronger joining of these strips than the material itself. Example VII. 10 kg of loose wool, well washed and conditioned at 95% relative air humidity at room temperature in batches of one kg, is whipped into a loose layer and placed in a 100 liter vessel. Then, 1 kg of epichlorohydrin is added, the vessel is closed and turned very slowly, initially for 6 hours at room temperature and then for 10 hours at 55 ° C. The wool is then processed into a comb in the usual way. Example VIII. 1 part by weight of an acid-resistant fabric made of blended threads, consisting of 70 parts wool and 30 parts polyvinyl chloride synthetic fibers, are treated at 50 ° C for 14 hours 15% epichlorohydrin in a vapor state in 100 parts by volume of air at 92% relative air humidity. The fabric can then be dyed with stretch dyes on wool at a temperature of 60 - 75 ° C without damaging the synthetic resin fibers sensitive to heat. Example IX . A mixture of fibers consisting of a percentage of shimmering acetate silk and a percentage of wool is treated at a temperature of 20 ° - 50 ° C with a fine emulsion of molten olein containing 50% epichlorohydrin. The fibrous mass, freed by pressing from excess but still containing 10% oil, is heated from 40 ° to 60 ° C for 12 hours in a closed vessel, after which the material is further processed in the usual manner. One obtains a head which, despite the low content of wool, after dyeing with acid dyes at a relatively low temperature, does not disturb the acetate silk, and with good use of the dye, strong melanic effects are obtained. shrinkage and is especially suitable for knitted products. Example X. Welne is filled with a 5% solution of piperidyl propene acetate, then centrifuged and heated to 40 ° C for 16 hours. The affinity for the dyes of wool so treated increases significantly. An even better result is obtained with the use of the free base, but a highly basic reaction is generally undesirable. Instead of acetate, the product of combining dimethyl sulphate with piperidyl propene oxide can also be used. Example XL Welne is treated at a temperature of 40 ° - 50PC with a 3% solution of acetate 1 - N - perhydrocarbbasolyl - 2,3 - propene oxide, and then it is heated to 60-65 ° C for 16 hours. The affinity for acid dyes increases. Example XII. The porridge is boiled at 50 ° C with a 3% solution of 1 - decylmethylamino - 2,3 - propene oxide methyl sulfate *, containing 5 g of dodecyl trimethylammonium iodide per liter, and after centrifugation it is heated to 50 ° C. within 16 hours. Dyes with acid dyes, especially when dyed in an inert environment, are much deeper. At the same time, a softening of the wool is obtained that is resistant to washing. Example XIII. 1 kg of wool is filled with a 15% solution of thiourea, centrifuged and then treated at 50 ° C with 25% propylene oxide in a 100 liter vessel for 14 hours at 75% relative humidity. it is windy. Alkylated wool is then grounded at 30 ° C within 1 hour of a suspension of 2,3-oxynaphthyl-1-aminobenzene (Naphtol AS) alkaline (solution I), then centrifuged and no rinsing develops at room temperature within a% of an hour with a solution of the diazonium salt obtained from the dye Echtblau BB Base (see below) (Solution II). A navy blue of a red shade is obtained, while on untreated wool only a dirty and weaker greenish blue is formed. Solution I. For 100 parts of wool, 1 part of Naphtol AS dye, dissolved in 2 volumetric parts of alcohol, is used. 0.5 parts by volume of soda ash 34 ° Bc and 1 part by volume water. This solution is poured into a bath containing 850 parts by volume of water at 35 ° C, 12 parts by volume of 50% Turkish oil and 8 parts by volume of soda ash of 34aBe strength. By careful gradual addition of 300 parts by volume. A 20% sodium chloride solution increases the dye's ability to pull the dye onto wool. Solution II. For 100 parts of wool, 5.4 parts of the Echtblau BB Base dye are used, which is diazotized with 6t2 cm3 of hydrochloric acid of 20 ° Be and 1.4 parts of sodium nitrite. Then dilute to 2,000 parts by volume with water containing 4 parts of sodium acetate. Example 14. Undyed woolen wool is heated in a closed vessel to 55 ° C for 14 hours with 20% 1,2-propylene sulphide and 75% relative air humidity. The unaltered externally material shows a markedly increased resistance to the action of alkalis. If wool had been saturated with 0.2% borax solution and centrifuged prior to treatment, then testing the dissolution rate in n / 2 liquor at 95 ° C shows even greater alkali resistance. Example XV. The wool material is heated with a separately evaporated mixture of 10% epichlorohydrin and 10% propylene sulphide in a closed vessel with a capacity of 50 parts by volume within 12 hours to a temperature of 50 ° - SS ° C at 75% relative humidity. it is windy. Wool treated in this way shows a significant increase in affinity for acid dyes. Example XVI. The woolen woolen are treated for 20 minutes at room temperature with a 10% solution of sodium 1,2-propyleneoxy-3-sulfonate, freshly prepared from γ-chloro - sodium oxypropane - a - sulfonate and an equimolar amount of potassium hydroxide, then centrifuged and heated to SO ° C for 12 hours. As a result of the presence of the sulfone group, the affinity for acid dyes decreases, while the affinity for basic dyes, e.g. methyl violet, increases significantly. The wool treated in the above way shows an increased ease of wetting and can be dyed at relatively low temperatures to very deep shades. This behavior shows that when treated in the manner according to the invention, a chemical change occurs as a result of substitution and not as a result of a possible change of the physical surface. A similar, although less effective effect is obtained by replacing sodium propylene oxysulfonate with potassium salt of glycidic acid. Example XVII. Unloaded, refined natural silk was treated in the same way as wool in Example XVI. In terms of dyeing, the same result is obtained. The affinity for the acid dyes is decreased, while the affinity for the basic dyes is significantly increased. Example XVIII. The fabric for women's dresses, made of a blend of 50% wool and 50% common viscose, is saturated at room temperature with a 10% solution of ammonium salt of formula IV, obtained by rearrangement of chloroxypropylpiperidine, after then, after 20 minutes, it is uncoupled and held for 16 hours at 50 ° C. The affinity of the material, especially its wool component, to dyes with acid groups, e.g. to Alizarindirektblau A (see above), Orange II (Schultz, 7th edition, vol. I, page 86), Thiazinrot R (see above) and Pegubraun (see above) significantly increase. The yarn components can be dyed at relatively lower temperatures, which largely protects the textiles. The same effect is achieved when a quaternary ammonium salt is used instead of the piperidine derivative. of formula II, obtained from / - chlorodiethylamine by intracranial alkylation. Example XIX. The swarf is heated with a 10% aqueous propylene oxide solution to 60% in a closed vessel for 10 hours. Washed water and dried filings were dyed with Alizarindirektblau A dye (see above) deeper than horn filings heated in the same way only with water. Example XX. Alumina tanned leather is hung in a wet condition for 8 hours at 50 ° C in air containing ethylene oxide. The treated leather is dyed deeper with acid dyes than untreated leather. Example XXI. The pressed plates from hardened casein are placed for 10 hours in a 10% aqueous solution of propylene oxide at 309 ° C. The objects treated in this way, even after thorough washing with water, are dyed with acid dyes much deeper than plates placed in water at 30 ° C for the same period of time. - 13 - Example XXII. The wool is saturated at room temperature with an anti-oxidation solution containing 3% mannitol and 1% sodium sulphite, then centrifuged and treated in the absence of air with 15% propylene sulphide for 14 hours at 50 ° C and 75 ° C. % of relative air humidity. After the excess propylene sulfide has been removed, an additional 10% of methyl iodide is treated, with the formation of sulfo groups likely. Wool treated in this manner has a high affinity for acid dyes. Example XXIII. 1.7 parts of wool are heated with 0.5 parts of ethyl bromide vapors for 14 hours at 80 ° C in 1,000 parts by volume of air at 75% relative air humidity. The wool, which has slightly changed on the outside, pulls the dye Alizarindirektblau A (see above) or Orange II (see above) from the neutral bath (see above) (2% each) significantly more than untreated wool from the same quilt. dyeing. These dyes are more washable than dyes of the same depth obtained on untreated wool. The same difference with regard to dyeing is obtained when the wool is treated with soap before dyeing. Example XXIV. Veneers dyed with 2% Orange II dye (see above) are treated with ethyl iodide vapor for 16 hours at 50 ° C and 75% relative air humidity. The wash resistance of this dyeing is much greater than usual. Similarly, the washability of a 2% dye of Azofuchsin G (Schultz, 7th edition, vol. I, page 87) on wool can be improved. Xxv. The wool is heated at 75% relative air humidity with 20% benzyl chloride (based on the weight of the wool) for 16 hours, at a temperature of 80 ° C. The treated strand is still pure white. In dyeing, the Alizarindirektblau A dye (see above) pulls very strongly on the treated material already at a temperature of 60 ° G. Intermediate treatment with ammonia also gives almost the same relative differences. Example XXVI. Welne is saturated with a 10% reactive solution of sodium chlorobenzylsulfonate with the addition of 1/10 mol of potassium iodide (in relation to the amount of benzylchlorosulfonic acid salt), then centrifuged and heated for 16 hours at 70 ° C at 92% relative air humidity. Basic dyes, such as methyl violet (see above), are fixed much more in the presence of sodium acetate than on untreated wool. Example XXVII. Welne is drenched with the n / 5th solution of tetrachloroxypropylammonium chloride and, after centrifugation, heated for 16 hours at 80 ° C. The treated wool, after thorough washing, stains the dye Ali¬ zarindirektblau A (see above) much more strongly than the untreated material. Example XXVIII. 10 parts of a marshmallow yarn are carried out within 1 hour at 65 ° C and within 1 hour at 75 ° C by an aqueous suspension of 5 parts of slime chalk and 5 parts of toluenesulfonic acid methyl ester (both of these compounds are ¬ put in suspension with 20% oleyl-polyglycol) at a bath ratio of 1:20. Then rinses are rinsed thoroughly and treated with soap. The treated wool will dye with acid dyes, such as Alizarindirektblau A (see above), much more strongly than the starting material. Example XXIX. The porridge is dyed in the usual manner with a pump of 3% Amidonaphtoirot SJB (Schultz, 7th Edition, Vol. I, page 58) and then heated for 12 hours at 50 ° C with 8% propylene oxide and 20% iodide. in a closed vessel with a capacity of 100 parts by volume at 92% relative air humidity. Treated wool can be treated with soap at 80 ° C without significant discoloration and without discoloration of the white material. Dyes that are not subjected to additional treatment disappear most of the time under the same conditions, and the white goods are discolored very clearly. Example XXX. Fibrin rayon is heated in the presence of methyl iodide vapors for 16 hours at 80 ° C and 75% relative humidity, thereby increasing the affinity of the fibers to the dyes. Treated artificial silk is dyed with Orange II dye (see above) in the same bath, not darker than untreated. Example XXXI. Artificial vinegar silk, containing in admixture an alkaline artificial resin of the vinyl series (the fibers contain 0.4% tertiary basic nitrogen), is dyed with 2% Alizarindirektblau A (see above) in the presence of acetic acid . Dyed rayon is suspended in the presence of ethyl iodide vapors for 14 hours at 80 ° C and 75% relative air humidity. The fastness of dyeing to washing increases quite significantly. Example XXXII. The heavy wool material is soaked in a concentrated solution of Patentblau V dye (Schultz, 7th edition, vol. I, page 349) containing a small amount of inert thickener and sodium oleyl methyl taurate, and then squeezed out so that the about 2% of the dye remains in the fiber. After the material has passed through the drying kilns relatively quickly, it is rolled up at 90% relative air humidity and 60 ° C for 8 hours with 15% epichlorohydrin. Finally, the goods are evaporated and finished in the usual manner. Example XXXIII . Wool material, which has been treated for 14 hours at 75% relative air humidity and at 50 ° C with 25% epichlorohydrin vapor, is printed in the presence of ethylene thiourea with acid dyes, e.g. Brillantwalkblau B (Schultz, 7th edition, volume II , page 41) or 5% of Nolol TL (Schultz, 7th Edition, Volume I, page 237). Very deep, complete prints are obtained. Example XXXIV. Wool fabric, previously padded with n / 5 solution of tetrachloroxypropylammonium chloride and after centrifugation, heated for 16 hours to the temperature of 80 ° C, is dyed in the presence of 7.5% pyridine bases with a boiling point of 125 ° - 150PC in an inert bath of 4% Alizarindirektblau A dye (see above). The dye is fixed on the fibers already at a temperature well below the boiling point. Example XXXV. Long wool, previously treated with 12% epichlorohydrin in a vessel with a capacity of 25 parts by volume within 14 hours at 50 ° C and 92% relative air humidity, is dyed in the presence of 10% puff pyridine bases. boiling 125 ° - 150 ° C without the addition of acid 4% Alizarindirektblau A dye (see above). In the presence of pyridine, the dye pulls onto the fiber much faster. Example XXXVI. The woolen fabric is printed with a printing paste of the usual composition below, which, in addition to the Nerol TL dye (see above), contains tetrachloroxypropylammonium chloride, is steamed in the usual manner and then left for a further 10 hours at a temperature of 15 - 60 ° C at 92% relative air humidity. Even without this treatment, an improvement in the resistance of the fabric is achieved. Water. The obtained print is very durable. Composition of the printing paste: Nerol TL extra thiodiethylene glycol water thickening of British rubber and tragant chloride tetrachloro - /? - oxypropylammonium 5 parts by weight ^ 11 in 22 '60, ^ 11 11 Example XXXVII. 100 g of dyed wool with 3% Alizarindirektblau A dye are treated at 55 ° C for 8 hours with rhythmic pressure fluctuations from about 60 to 100 mm of water column 15 g of epichlorohydrin in 10 liters of air at 90% relative air humidity. Dyeing is very resistant to washing. White goods after washing with soap (according to the standards of the Strength Commission of the Union "Verein deutscher Chemiker", 5th edition 1931) practically do not get dirty, and the soap bath stains very weakly, while the dyes previously untreated to a large extent They "let go" and the white areas of the goods are very strongly discolored. Analogous results are obtained when dyeing with Alizarincyaningrun G (Schultz, 7th edition, vol. I, page 532). Example XXXVIII. Instead of the epichlorohydrin given in the preceding example, the same amount of 1,2-propylene oxide is used. The improvement in resistance, especially in water resistance, is also very significant in this case, although not as much as before. Example XXXIX. A wool dyed with Orange II dye (see above) is rubbed with a 5% solution of the two quaternary trimethylene ammonium salt of dichlorooxypropylpiperazine. The slightly dried material curls and heats for 14 hours at 75% relative air humidity at 80 ° C. Considerable improvement in water resistance is achieved. Example XL. A wool dyed with 3% Amidonaphtolrot BB dye (see above) in a formic acid solution is heated to 50 ° C in a 25 parts by volume vessel with 12% epichlorohydrin in 10 hours at 92% relative air humidity. The dyeing practically unchanged becomes completely resistant to the action of water, and washing with soap and soda according to the standards of the Strength Commission barely weakens them. The white areas of the material do not get dirty. Similar significant improvements in properties are achieved by acid dyes with the following dyes: Flavazin S Viktoriascharlach 3 R Radiorot VB Supranolbrillantrot 3B Azowollviolett 7 R Sulfosaureblau R Amidoblau GGR Naphtalingriin V (Schultz., 7th ed. Schultz, 7th ed. Vol. I., p. 143) (Schultz, 7th ed., Vol. II, p. 180) (Schultz, 7th ed., Vol. II, p. 204) (Schultz, 7 additional ed. vol. I. p. 70) (Schultz, 7th ed., vol. I, p. 110) (Schultz, 7th ed., vol. II, page 15) (Schultz, 7th ed., vol. I, p. 322). Example ftLL Wool felt, tanned with 3% of Anthralanrot G dye (Schultz, 7th ed., Add. I, p. 68) is heated in a closed vessel with a capacity of 50 parts volumetric in 15 hours from 20% epichlorohydrin to a temperature of 50 ° C at 75% relative air humidity * The felt treated in this way is very resistant to the action of water. When washing with soap and soda at 50 ° C in accordance with the regulations of the Standards Commission, the dyed and white goods remain unchanged at the same time. heated with 20% epichlorohydrin at 90% relative air humidity for 15 hours at 60 ° C. The dyeing is water-resistant, while before that. after treatment, the white goods were discolored quite strongly. Example XLIII. A wool fabric dyed with 7% Amidoschwarz A2G is heated to 50 ° C with 15% epichlorohydrin in a 25 volume vessel for 15 hours at 90% relative air humidity. The resistance to washing and the effects of perspiration increases greatly. Example XLIV. Veneers dyed with Amidonaphtolrot BB dye are filled with a 10% solution of thiourea and treated with a mixture of 10% propylene oxide and 10% epichlorohydrin for 12 hours at 55 ° C. The tanning resistance increases considerably. A similar result is obtained with a mixture of 1,2-propylene sulfide and epichlorohydrin. Treatment can be carried out over two periods. Example XLV. Vellum dyed with Amidonaphtholrot BB dye in the presence of sulfuric acid and rinsing out, while untreated felt tints the bath and stains the white wool very much. The 9% dyeing with the same dye on hair fiber is also significantly improved by this treatment. Dyeing is practically water-resistant and, when treated with soap at 50 ° C, behaves similar to a weaker dyeing on wool felt. Example XLII. The rope is a light cream dyed deep red with dyes: with a thin solution of sodium acetate, heated in a closed vessel with a capacity of 25 parts by volume to a temperature of 50 ° C with 15% butadiene dioxide for 14 hours. The resistance to dyeing against water and washing is significantly increased. Example XLVI. The dyed wool material is impregnated with a 5% solution of N - diethylene ammonium chloride in a padding pad, pressed, slightly dried and, in the rolled state, heated to a temperature of 70 ° C for 8 hours at 75% relative air humidity. The fabric is mothproof. Example XLVII. White rabbit fur is heated in a closed tank with a capacity of 50 parts by volume to 55 ° C with 15% epichlorohydrin in 15 hours and at 92% relative air humidity. The outer fur, which is almost unchanged, is dyed darker with Ursolagu B dye, and above all it gives a dye more resistant to friction than untreated fur. In this case, the preparation of the fur with an alkaline bath and no dressing becomes unnecessary. Example XLVIIL Acetate silk, obtained by dry cleaning with 0.5% Palatinechtblau RRN (Schultz, 7th ed., Supplement. P. 116) 5% Palatinechtbordo N (Schultz, 7th ed., Supplement. P. 117 ) 2% Palatinechtrosa GEN (Schultz, 7th ed., Tsup. P. 118) - 17 - a solution of methylene chloride and alcohol and consisting of 80 parts of cellulose acetate combined with 54% acetic acid (in the form of acetyl) and with 20 parts of cellulose isoninotin ester, obtained according to French patent no. 644 480 and its additional patent no. 38 195, are dyed for one hour at a temperature of 50 ° - 75 ° C with a suspension of 10% of methyl toluenesulfonate and 3% of Alizarindirektblau A dye (see above) in the presence of chalk slime May. The bath is almost completely drained. It is advisable to add toluenesulfonic acid ester mixed with emulsifiers to the bath in small doses. In order to make better use of the dyes, sodium sulphate may be added to the bath in an amount of up to 50% of the weight of the fiber. Silk can be dyed with acid dyes in a similar manner. PL

Claims (14)

Patent claims. 1. Process for the treatment of natural or artificial fibrous materials, e.g. wool, and other similar materials containing substances with a large molecule with alkaline residues or which become such by alkylation, meaning that these materials are treated with alkylating agents to amino groups, and possibly also to carboxyl groups. 2. The method according to claim The method of claim 1, characterized in that alkylene oxides, sulfides or imines and their derivatives are used as the alkylating agent. 3. The method according to p. The process of claim 1, wherein the alkylujacies are reactive esters of inorganic acids or their organic derivatives. 4. The method according to p. Reactive and alkylating bodies are used which contain at least two groups capable of reacting with amino groups, at least one of which has the character of an alkylating agent. 5. The method according to p. 1-4, characterized in that ester-type alkyls are used simultaneously with heterocyclic bodies which react with ring cleavage. 6. The method according to p. 1-5, characterized in that the use of alkylating agents or mixtures thereof, in which at least one component has a five-valent nitrogen. 7. The method according to p. 1-6, characterized in that the treatment is effective in the presence of moisture. 8. The method according to p. 1-7, characterized in that the treatment is effective in the presence of swelling agents. 9. The method according to p. 1-8, characterized by the fact that the treated material is pretreated with agents that revitalize or cause swelling. 10. The method according to p. 1-9, characterized in that the alkylujace agents are used in the form of a pair. 11. The method according to p. 10, characterized in that the pressure changes rhythmically during the treatment in pairs of alkylating agents. 12. The method according to p. A process as claimed in any one of the preceding claims, characterized in that the treatment is effected in the presence of acid binders. 13. The method according to p. A method according to any one of the preceding claims, characterized in that the treatment is effective in the presence of bleaching agents. 14. The method according to p. A process as claimed in any one of claims 1 to 13, characterized in that the treated products, which still contain reactive ester groups with alkylating function, are additionally treated with alkali, acidic or basic agents, for example with amines, thioureas, thiosulphates. Aceta G. m. B. H. Zastepca: Inz. J. W ^ gaiiow &ki; ^ rzni | kk ^ 'atefrtó \ tfy / Oiruk L. Boguslawski i Ski, Warsaw. PL