BE419841A - - Google Patents

Description

       

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    II Process for the treatment of products formed naturally or artificially ".



   It has already been proposed (Belgian patents? 411,266 of September 13, 1935, 412,588 of December 3, 1935, 413,289 of January 14, 1936 and 413,751 of February 11, 1936), to vary natural or artificial products, in particular fibrous materials with basic groups and also acidic where appropriate, by treatment with alkylating agents, in their electrochemical character, in particular to strengthen the

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 - basic properties.



     The Applicant has found that, in an analogous manner, the chemical properties and therefore also the affinity of products formed naturally or artificially, in or with protein substances or their derivatives or other substances of molecular weight, can be considerably influenced. high still containing basic amino or imino groups, for the various treatment agents such as dyestuffs, dye components, mordants, loading agents, antiparasitic agents, etc ...., if substances which are capable of reacting with basic amino or imino groups are made to act on them, forming radicals with the
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 group C <, in which a bond between a and N- must have an unsafe character.



   These are substances which, together with amino or imino groups, can give rise to the formation of cyanamides or amidines or guanidines. In a corresponding manner, one can envisage in a very general way the use of substances which, by simple addition to the amino or imino groups or by condensation, with the separation of hydrohalic acids from sulfo groups, alcohols, mercaptans, d 'ammonia or
 EMI2.2
 amines, are capable of forming the group 0 <partially unsaturated, therefore, for example, substances such as dicyan, halogenated cyanes and their polymerization products, cyanamide, its alkyl derivatives and their tauto - mothers, dicyanediamide and other derivatives of guanidine, alkyl sulfocyanides,

   earbylamines and their halogen adducts, isourea ethers and cyolic and acyclic isothiourea ethers, disulfides dissociable by amines with the group -N = C - S - S -, imino ethers ot des imino thioethers, particularly alone with a cyclically linked imino group, cyclic amidines

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 and acyclic with easily exchangeable amino or imino groups. Many such substances are given in detail below.



   As these are reactions in the heterogeneous system, the onset of the reaction and its more or less easy progress are dependent to a considerable extent on the conditions.
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 at work H1oVtôofj, clci 1, i pc, irurcr r1tJrJ ootn [) Of! fU) tn, do .rctr; r le) swelling, the presence of substances activating the reaction, the solubility of the active substances in the solvents used and of their tendency to side reactions, in particular to polymerization. It is therefore necessary to check, in each particular case, by preliminary tests, the usefulness of the substances capable of forming amidine or cyanamide for the materials to be treated, and to determine the most suitable reaction conditions. more favorable.

   Even relatively small differences in the constitution of the active substances can considerably influence the effect.



  Thus, for example, the 2-amino-5-methyloxazoline which is easily obtained by adding 1, 2 oxides of propylene to cyanamide, only gives a relative effect on the wool.
 EMI3.2
 t, all fnlhlo t mulu 001) UI) CIUllb rc3el, LI..t1JLl1IJ qua lu: J-ulIJ1xlo-u-ùhlo-romethyloxazoline, obtained in the same way by means of 1,2-epichlorohydrin, exerts a very intense action.



   In addition to the specific group for the formation of cyanamide and amine, the active substances can carry any further substituents, for example hydrophilic groups causing solubility in water, or groups.
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 which increase the affinity or the I :: Jl1bstl..Intivity for the support or product to be treated, or which, in addition to a hydrophilic effect of
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 the reactive agent, also usefully influence the affinity conditions of the material treated by the specific electrochemical character of the substituent group, or, finally, also of the radicals

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 which still allow subsequent modifications, for example substitutions on the trout material. It is possible to envisage the use, for example of oarboxyl groups or of sulfo groups,

   of amine or ammonium radicals, of halogenalkyl groups or of halogenalkoxyl groups, of thiooarbamides, of thiourethane, of alkoxyl radicals. The input substituents may also contain any ohromophores or chromogens, for example enoles or aromatic rings capable of. passive copulation, or also radicals which exert a specific protective action against the parasites of textiles, for example against the larvae of the moths, the mucedinea, etc.



   When the substituents still contain atoms or groups of atoms capable of reacting, these may be subjected to any other reactions, for example exchange against basic or acidic radicals, radicals of components of dyes, or of dyes. In the latter case, shades are obtained showing particularly good solidity properties. Further treatment, for example with amines or amino acids, can also be envisaged when the amidine group, although it is also already formed, is however not yet contained in a pronounced basic state in the primary products of the reaction, for example in the case of the action of polymeric dicyane or dihalocyanin.

   The products thus obtained are, however, already frequently capable of being transformed, by secondary reactions, into basic substances. The cyanamide groups can also be converted, by treatment with ammonium sulphide, into thiourea groups, and it can then be advantageously dyed according to the method of the Belgian patent. 413,751 mentioned above, in the presence of alkylating agents, in the formation of groups of isothiourea ethers.

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  . When the substances capable of reaction in the spirit of the invention are strong bases, it may be advantageous or also necessary to cause them to act in the state of their salts with organic or inorganic acids, for example with hydrochloric acid, hydrogen sulfide, acetic acid, tartaric acid, citric acid, salioyl acid or toluolsulfonic acid. Instead of the so-called acids, it is also possible to use those with an anion with capillary activity, for example tetrahydronaphthalinesulfonic acid, dodecylsulfuric acid. If desired, the bases can also be only partially saturated with acid.

   The support or material to be treated can also be subjected to a preliminary treatment with acids or acid salts, such as trichloroacetic acid, hydrochloric acid, zinc chloride ,. tin tetrachloride, aluminum chloride or borofluoride, optionally in the absence of water, for example in the reaction with cyanamides.

   Depending on the stability and the reactivity of the active substances, it can also be advantageous, for example when the amidine formers or the basic groups of the support, capable of reacting, are present in the form of an incoming salt. difficult to react, to carry out the reaction in the presence of acid combining agents or neutralizing substances, for example sodium acetate, sodium borate, disodium phosphate, alkali salts, dialkylaminoacetic acids.



  In most cases, such additions are not necessary. In addition, the reaction can be more or less considerably enhanced by the pre-treatment of the supports with reactivating, structure-releasing or swelling agents. as well as, if necessary, by adding swelling substances to the treatment chamber, thus, for example, the reactive power of the wool

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 can be considerably increased by mild chlorination, by pre-boiling with solutions of sulfoyanates, or by prior oxidation with hydrogen peroxide.



   As swelling agents, the use of, for example: urea, thiourea, formamide, resorcinol, metha-
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 1101,: 7.; acxl, 1! 1rull "'" tl ul.rû tJ J:!. TlJU "6 t: l or U tH.111 oy 11.1 tElt: l U loulllJi: I.



    The swelling state can also be influenced by an appropriate choice of anions in the use of salts of the amidine formers. The use of swelling agents is especially indicated when the reacting substances have a relatively high molecular weight and are not suitable. therefore not directly able to penetrate into the material to be treated. for some
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 reactions, the use of oatalysts epéoifiquos aonnafi have recommendable, for example copper salts in the reac-
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 tions with dioyanediamide.



   The products can be treated, before or after dyeing, if necessary also simultaneously with the action of a dye, with solutions of the active substances in water or in organic solvents and, in the latter case Preferably, closed apparatuses are employed, for example dyeing apparatuses or apparatus such as are usually employed for chemical washings.

   one can also, more simply, impregnate the goods with solutions of the reagents in water or in organic solvents, for example methanol, butanol, carbon tetrachloride, toluol, cyclohexanone, epichlor - hydrine, then wring it out or squeezing it and then, in the case of fabrics, for example in the rolled state, let them stand at a suitable temperature and, where appropriate, in the humidity of the air, or spin slowly on rollers or in drums, until the desired effect has been achieved

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 duit. Generally, temperatures between 40 and 90 C are suitable.

   In the case of heat-resistant products, for example artificial fibers based on cellulose, or natural silk, the reaction temperature can also be higher than 100 ° C. The wool can also be heated, without disadvantage, at temperatures above 1000 C, in particular in the acid state or in the presence of agents becoming acidic, particularly in the absence of humidity. However, temperatures above 140 0 must be avoided; at least in these cases, the reaction time should be shortened as much as possible.

   Substances which are sufficiently volatile, for example halogenated cyanes, imino ethers capable of reacting, etc., can also be made to act in the vapor state, if necessary under reduced pressure or under rhythmic fluctuations of. pressure.



   In order to avoid damage to the fiber, fiber protecting agents of known kind may be present, provided that they do not enter into an undesirable side reaction with the active substances. The exact setting of the degree of swelling is also important in this connection. When working with alkaline substances, the degree of swelling should be kept low, for example for wool. In addition, it is possible to work in the presence of bleaching agents, in particular reducing agents, to prevent a tendency to yellowing which may occur in certain cases, or else to obtain, simultaneously with the improvement, a bleaching of the color. the raw material.



   A local application of the agents according to the methods used for printing is obviously also possible. In addition, general treatment, or only local treatment, can be carried out also in the presence of dyes, dye intermediates and / or other processing agents.

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 for example gnawing. Likewise, all other methods used in the textile industry for obtaining special effects, for example reserving methods, can be rationally applied.



     The process is applicable in the first line for products formed from raw animal material, in particular for natural or artificial fibrous materials. We can mention for example: wool, chromed wool, chlorinated wool, wool preliminarily treated with an alkali, salts with an alkaline reaction, sulphocyanates or with hydrogen peroxide, natural silk loaded or not char- age, artificial fibroin silk, artificial casein silk, feathers, hair, furs, felts, horn, tanned or untanned animal skins.

   it can also be applied directly to any other products of a synthetic or semi-synthetic nature which contain radicals with amino or imino groups capable of reacting, for example with cellulose derivatives or with compounds. polymerization products, into which radicals containing nitrogen have been introduced, with mobile hydrogen on basic nitrogen, for example in the form of basic groups of esters, ethers or amides.

   It is also possible to use substances which, in addition to cellulose for example, still contain proteins or protein derivatives, for example casein or basic artificial resins, such as polyamines of alkylene, the products of the reaction of polyglycidetoluolsulfoesters with univalent or polyvalent amines, and other known products, for example the basic resins mentioned in the Belgian patents? 412046 of October 31, 1935 and 413.751 of February 11, 1936, in order to obtain animalization. This not only increases the dyeing effects, but also improves the fixing.

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 additional substances.

   This is particularly the case when the reacting components simultaneously contain atoms or groups of atoms capable of exerting an action in the cellulose molecule. When the incoming groups oon-
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 o) 1TT =! n RA rndiqnug ral 9 '/ 7hcfir, nara, prçll 1 -plinl-i ri il pp OR 1 Inyclic, with more than 8 carbon atoms in a chain, can be obtained simultaneously with varying conditions affinity, a permanent softening effect or a hydrophobic effect.



   It is not absolutely necessary that the active substances be introduced in the previously formed state. They can also be produced on the -products or in the presence of the products to be treated by chemical reactions or doublings. Thus it is possible to treat, for example wool, with an alkyl thiourea in the presence of a desulphurizing agent giving rise to the formation of cyanamide.

   wool, which is impregnated with an alkyl thiourea, with aloylants such as sodium ohloroetate, ethyl bromide, the methyl ester of ethanesulfonic acid, the methyl ester of sodium chloride, can also be treated as a supplement. acid
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 toluolsulfonate monochlorohydrin or dichlorohydrin or, simultaneously, imprint on the fiber a mixture of a thiourea and a halogen compound capable of reacting. It is worth mentioning here the treatment of wool with a thiourea of the fatty series, for example with dodecylamine thiourea
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 ut due to the essenae of methyl mustard or allylic mustard, followed by further treatment with an alkylating agent, such as ethyl bromide.

   Easily dissociable compounds, the use of which is envisaged for the process, are, in addition, the substances obtained by the action of essences of mustard or dlisooyanates on cyanamides, or also the products of condensation of cyanamide with carbon compounds

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 acetyls for example the ester / acetic. Finally, it is also possible to treat products capable of reacting simultaneously with essences of mustard, for example the essence of mustard.
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 thyltC110 nn pràsnnnn (1 tnllJoyllJ.ntl.1 tt11n quo 1a bonzyle chloride, or use mustard essences which themselves possess alkylating functions, for example J3 -bromethyl mustard or petroleum mustard of / 3
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 dibromopropyl.

   The additional formation of tamidines or guanidines groups, for example on wool, also allows a complementary (more intensive) treatment with agents which act exclusively or predominantly on the modified basic groups, for example condensation with carbonyl compounds such as formaldehyde, chloral,
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 chloroacetic aldehyde, al - O {'-dichlorodimethyl ether, heptyl aldehyde, dodecyl aldehyde, glyaxal, diacetyl, benzoins, acetyl-acetone, aoetaoet1 ester and derivatives of such substances, besides the condensation with methylol compounds of amines and amides, by
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 example with dimeth: laminomethanal, diaethylolurea, methylol derivatives of eyanuric acids and amino -1-3-5-triazines.

   Such condensations can also be carried out in the presence of other reactants with carbonyl compounds, in particular of amides or phenols, for example.
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 rie 4iarée, 11'1 i.oyaz9i: nidn, c3c thionr'Ín, clo tolnolc: ulPeui-. de, phenol etc ... and / or in the presence of basic or acidic, organic or inorganic substances. The amidine formator can also be made to act in the simultaneous presence of such substances.



   Also in the case where one cannot expect a
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 direct reaction with diamidine formers, it is possible to react simultaneously, previously or subsequently,

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 Any alkylating agents or substances which form alkylating agents under the reaction conditions, in particular also those which contain basic radicals.

   Mention may be made of: ethyl bromide, ethyl iodide, p-toluosulfonic acid methyl ester, allyl bromide, 1,4-di-ohlorobutene 2.3., Chloroacetate vinyl, [alpha] - ss - dichlorodiethyl ether, chloroacetone, 1.3-dichloroacetone, tetrachloroxypropylamrnonium chloride, the fixing product, which dissociates during heating with rupture of the nucleus, of 2 molecules of ethyl bromide on N-N'-dioxyethylpiperazine, diazoparaffin, ethylene oxide, 1.2-propylene oxide, 1,2-propylene sulfide, epichlorohydrin, epibromhydrin, ltepidichlorohydrin,

     1,2-epoxy-butene 3,4-piperidopropene oxide, 2,3-epoxypropyletrimethylammonium bromide, N-butylethylenimine, diethyl-ethyleniminium chloride, the quaternary salt of 1 molecule of pipereine and 2 molecules epichlorohydrin, as well as mixtures of such substances, in so far as they do not mutually reinforce each other giving rise to the formation of inactive products.

   by processing, which is applicable not only to homogeneous materials, but also to mixed articles, generally to materials in any state of processing and improvement, the chemical properties of the materials are varied according to the choice of agents and working conditions, to a greater or lesser extent. The affinity for dyes, dye derivatives or dye components with acid groups, as well as for all other acid treating agents, is generally increased considerably.

   When the active substances contain acid groups, the absorbency for basic dyestuffs can also be increased, particularly in the case of sulpho groups, without any action taking place.

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 the reservation itself. The elimination of basic groups which occurs when reacting wool, pre-treated
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 Also with aqueous alkali, with cyanuric chloride or polyhalogen compounds of similar constitution, does not form the object of the invention. The increase in the reactivity of the treated products allows the dyeing temperature to be lowered, which is very desirable, for example in mixtures with artificial fibers of cellulose derivatives.

   In most cases, it occurs simultaneously
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 With affinity, a considerable improvement in color consistency. The same is true for the fixing of tannins, moth protectants, reserving agents and preservatives. charge. Resistance to
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 Alkaline agents can therefore be improved considerably, more particularly when the active substances or certain components have two or more positions capable of reacting in the molecule. The variation in chemical properties can be used to advantage for the production of effects, by the joint treatment of treated and untreated material, a good match in color or color can be obtained. good color effects.



   A series of substances whose use can be envisioned
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 DILP-t1 for 10!) Roo6d6 cl 'nprèn the invention are confined dfinel the list below and in the examples which follow. These statements are, however, in no way limiting, and are intended only to show that the method may be widely generalized. listing . -
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 clilorocyanin, bromocyanin, ayanaric chloride, ayanuric bromine, cyanide aiahloromonoamiàe, dichloropyridazine, diohlorophthalazine. cyanamide, ethylecyanamide, butylcyanamide, cyclohexyleoyanamide, dodeyleoyanamide, abi ethyl cyanemi-

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 cN-cyanetaurine, 3-ayanamidobenzo acid: que, 4-cyanamide-bUlJ; H: JJjulrlJ.! Vbu from ucndu, oul: 3 (lu cuuullcarexi.tillar;

  c, ü-ùluu-- thylaminophenylecyanamide (azo compounds), dicya, nedia- mide, cyanurea, dipropyleoarbodiimide, combination of bromo-cyane and diethylaminoacetonitrile, combination of bromo-cyane and N-NI-di-j-oh-zerahylethylpetylate of methylisotnioarea, reaction products of 2 molecules of N-trimethylethiouxea and 1 molecule of 1.4-diohlorobntnp -?., No-climethylamino-p-phenyl-ITT-allyl-methyl-isothiourea methosulfate, fixing product of ethylene chlorohydrin on
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 thiocarbaminylemethyletaurine, a binding product of bro-
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 ethyl mide on guùnylethiourea, combination of S-methyl-, T-, rt¯trimethylethiourea, guanidinesulfocyanide, J9 phlox- 'ethylulfocyanide, (-chloropropylesu7.ocyanide, benzylesul- focyan ure, m-xylyloynea product of the reaction do dl1:

  1-ohlorethylethy14illin and 2 moléoules of potassium sulfocyanare, dôdeoylesulfooyanide. ethylisonitrile, fi - '0 -dibromopropyl mustard oil. 11 - lY -dibromopxopyle-.
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 thiourea and its transposition product, etheraoetiminoethyl-
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 ic, acetiminothiooxyethyl ether, g7ztaric acid riminoethyl ether, lucide terephthalic rlliminoethyl ether, 2-oxymethylethiazol, bonzothiazol-2-sulfonic acid, halopyridine sulfonic acids, 2-methoxypyridine-diohlorohloride N-methylpyriàiniùm-2-acia saltoniquebetaine, txiahlor aaetonitrile, raalonitxi7.e, formaldehyde and dimethylamina and its iodomethoxide.



  The amount of substances or mixtures of sub-
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 Reactive stances can vary within wide limits. She is,
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 of course, essentially dependent on the nature of the sup-
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 port, nature and reactivity of active substances, special working mode, temperature and duration of action. Due to the large differences that arise

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 present here, it is not possible to give general indications. With substances of high activity, relatively low molecular weight, it is already possible to obtain. with very small amounts, for example 3 to 5% of the weight of the goods in the case of chlorocyanin, intense effects.

   When working with solutions, it is preferred to
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 ble, bll general,, l 't.'111.!:. loY6 r of gr1.nd surpluses, or, in this case, the parts which entered into reaction can be easily recovered. It is also possible to lower the reaction temperature and reduce the duration of the reaction to spare the material to be treated.
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  The li-dtation of working conditions by the power of resistance of the support to heat, acids or al- injin n op.j? 1. been inrHCI1 (to be sure. For sensitive fibers, for example wool, certain reactions, for example those which lead to a strong alkaline reaction, are not applicable or are only so in a limited measure, while conversely reactions which take place in a strongly acidic medium, for example which may
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 cause damage to the cellulosic material, under dpn.ol1blomnnt and 0.0ir10 ohlorhyr1riquo, they should only be oxidized with caution, if necessary in the complete absence of water. In doubtful cases, it can be easily ascertained by preparatory tests.



   EXAMPLE 1;
Zephyr wire is impregnated for 20 minutes at the temperature
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 temperature fi'appartement, aven a flolntion n'1ltn ltf1Q 4 la 5µ (the 8-OXéthyl- / 1-mercapto-àihyàro-glyoxalineahlorhyàrate, the skeins are drained and suspended for 16 hours at 70 C and at a relative humidity of the air 75% The yarn, unmodified in appearance, absorbs dyes with acid groups, for example direct blue alizarin A (Schultz Farbstoffta-

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 bellen 7. Ed. Vol. II, p. 9), thiazine red R (Schultz part- stofftabellen 7. Ed. Vol. I, p. 121) etc ... much stronger than untreated yarn. It is remarkable and important that the effect is also manifested in the bath dye
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 nout; rer quo clrarin lti i: aWuturn on bnin 90140.



  EXE1 \ I ± P LE 2:
A mixed fabric of wool and artificial silk is impregnated with acetate with an 8% solution of 2-amino-5-ahloro-.
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 methyloxazoline- (2,) in 50 ml of methanol and the material is allowed to stand tightly, in the rolled state, for 16 hours, at 70 ° C, and at a relative humidity of 75%.
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 The aff'r.1nit6 for los oolorunts aoidoa otit oOrH.1ic1.ôrnblof! Wnt increased, so that the fabric can be dyed in dark tones, in neutral bath, with dyes which otherwise are unsuitable or are not suitable for wool, without en-
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 damaged artificial acetate silk at low temperature. Instead of the free base, it is also possible to use salts, but the effects are then less intense than with the free base.
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  EXE1 \ D? L "S 3: Wool is impregnated with a n / 1 solution of the reaction product of N-CO-diethylamino-n-propyl-N'-allyl-thiourea hydrochloride and ethylene chlorohydrin and, after spinning, it is heated for 14 hours at 60 ° C. at a relative humidity of 75%. The wool, which is yellowish a little.
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 barely visible after trÜternent, e: ..; t tinted in neutral buin,. at 90, with direct blue alizarin ii (ûahultz Farb- stofftabellen 7. Ed. Vol. II, p. 9), together with untreated wool. The treated material receives a darker color than the untreated material.



     EXAMPLE 4:
We heat at 100 for 6 hours, in the wool

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 dried with a 5% solution of acetiminoethyl ether in batanol. The commodity treated in this way receives direct blue alizarin A (Schultz Farbstofftabellen 7th Ed.



  Flight. II, p. 9) a shade darker than the untreated merchandise, especially in neutral color.



     EXAMPLE 5:
Wool is impregnated with a hot aqueous solution of ± ethylene thiourea and the material is treated, at 60, and at 90% relative humidity, with 15% bromide vapor. 'ethyl. Wool already absorbs many acid dyes in a neutral bath under considerably better conditions than untreated wool. The fastness of the dyes, for example with Amidonaphthol BB red (Schultz Farbstofftabellen 7. Ed. Volume I, p. 58) is markedly improved.



   EXAMPLE 6:
A woolen fabric is impregnated with an equimolecular solution of ethylene thiourea and ss-chlorethyl diethylamine hydrochloride; it is squeezed, rolled up and left to stand overnight at 75 ° C. and a relative humidity of 92%. The tinctorial properties of the film are improved in a similar manner only in the previous example.



   EXAMPLE 7 Wool is impregnated with the ether-isothiourea salt of 1 molecule of propylene 1,3-bromide and 2 molecules of ethylene thicure in 10% aqueous solution. The impregnated material is heated for 12 hours at 60 ° C. at a relative humidity of 75%.



   EXAMPLE d: Natural silk is treated as described in Example 2. Dye affinity is improved.



   EXAMPLE 9:

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Wool is boiled for 3 hours with 8% malonitrile in methanol, in the presence of 2% acetate
 EMI17.1
 by potal3oEJ. Lu oondonuation confesses the rnl.:tlon1 trilo, I? Robftblornont to the arginine radical, is easily detected with reagents, which react with active methylene groups,
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 for example with dirnethylaminobenzaldehyde. an intensive yellow color is obtained with these, resistant to washing.
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  E.XEl # LJ la Do la soio artifloio11Q vi.f) Qonn, <1l1i It (té ea, xrim: .3.rFc5c. By the action of $ thyleneimine, is treated as described in example 2. L The dye affinity and color fastness are improved In dyeing matter, the product has become analogous to wool.



   EXAMPLE 11:
Cellulose-methyl-p-nitrobenzyl ether films are, after reduction of the nitro groups, suspended for 12 hours,
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 at 0 0, above 15 5 of benziminomethyl ether, at 35% relative air humidity. The affinity for acidic dyes, which was initially very low, is now strongly pronounced.
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  EXE1, 11? LE 12;
Wool, which has been pre-dyed with 3% starch-phthol red BB (Sohultz, Farbstofftabellen 7. Ed. Vol.



  I, p. 58), is impregnated with a 10% aqueous solution of S-oxyethyl-meroapto-dihydroglyoxylin hydrochloride, drained and left to stand for 12 hours at 50 ° C. in the presence of 10% deoxide. propylene (vapor). The color fastness is considerably improved.



     EXAMPLE 13:
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 Do lu lei.r7 tà4hw 01; 1 ohniitidv invou lu -; tu lIt; <J1JlO.ru.X't1 oyanuric in acetone (bath ratio 1: 20), pen-

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 for 6 hours, in a closed vessel, at 60 ° C. After cooling, the acetone is removed by pressing and the remainder is expelled by hot air. The commodity, which is still rinsed with water if necessary, can be dyed in a normal way, but shows a considerably increased resistance to
 EMI18.1
 rilonlin, L'ttdblon pDltL 01100.1 ';' 1.'1 ô'Lrtl uligmo11t, 6 if we flee. at the same time add an alkylating agent, for example butadiene dioxide or also epichlorohydrin. Other suitable solvents are dioxane or carbon tetrachloride.

   The temperature can be raised to 100 0.



   EXAMPLE 14:
An artificial silk in cellulose-ethyl-p-nitro-benzyl-ether is treated, after reduction of the nitro group, with a dye bath with a neutral reaction, which contains, in addition to 3% of direct blue alizarin A (Schultz, Farbstofftabellen , 7.



  Ed. Vol. II, p. 9), 10% benziminomethyl ether, dispersed with oleylpolyglycol. It is first treated for 1 hour at 60 to 85 C, and then gradually added a little acetic acid. We get an intense blue tint.



   EXAMPLE 15:
Italian casein wool (lanital) is heated with a 4% solution of bromooyan in diisopropyl ether, in a closed vessel, for 5 hours at 70. The affinity of the material for acid dyes and chro- tz dyes, acid matting, for example for starch-naphthol red BB (Schul Farbstofftabellen, 7.; d. Vol. I, p. 58) or anthra- KE acid cene (Schultz, Farbstofftabellen, 7. Ed. Vol. II, p.



  1870 is increased and the color fastness to water, washing and crushing is improved.



   EXAMPLE 16:
Casein wool suspended in 10% epichlorohydrin vapor in a closed container with a capacity of 40 cm3

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 per gr. of fibrous material, for 14 hours, at 50 and at a relative humidity of the air of 35%, is additionally treated as in the previous example with bromocyanin in isopropyl ether. The tints produced on this material, for example amidonaphthol BB red (Schul
 EMI19.1
 "" Farbstofftabellen, 7th. Ed. Vol. I, p, 53) are greatly improved in their strength. As the resistance to breakage of wet lanital is increased by processing, the commodity withstands the dyeing process better than untreated commodity.



   EXAMPLE 17:
Viscose artificial silk, which contains 6% of the
 EMI19.2
 ethyl: nlr, lÜJ \: J volatile polymer rtv3altuiit Or .Lu rJ-al1un inlru ammonia and ethylene chloride, is heated in 15 parts of carbon tetrachloride with 20% by weight of the
 EMI19.3
 merchandise of di -, / 3-ehlorethyloyanamide, for 6 hours, at 100.

   The basic character of the material is considerably increased and the color fastness is improved. good results are also obtained if the di-ss-chloroethyloyanamide is completely or partially replaced by dodecyloyanamide or methyledodecyleoyanamide. The cyanamides can be easily obtained according to the conventional method by desulfurization of the corresponding thioureas or according to the halocyanin method.



    EXAMPLE 18;
Wool is heated for 6 hours at 70 0 in a vacuum vessel with a capacity of 50 cm3 per gr. of wool with 20% by weight of the wool of the mixture of the reaction products of N-di-n-propylebenzylamine and bromocyanin (from Braun and Rover, Berichte der Deutschen Chem. Gesellsch.



  36, 1198). By inaction of the vapors of the reactant substances, the dyeing properties of wool are considerable-

 <Desc / Clms Page number 20>

 improved.



   EXAMPLE 19:
 EMI20.1
 Do la ininn ocst clh.lif f6o 1 mss uno solution 8 (1 lo-xfna for 6 hours, with ethyl-C.-bromine-n-'j.oyl-oy & namide (from Braun, Berichte der Deutschèn Chem, Gesellsch 42, 2053) in 100 ° butanol. The treated wool is intensively dyed with acidic dyes.



   EXAMPLE 20:
Wool is heated for 8 hours at 50 C. with a 5% ethyl alcohol solution of the product of the action
 EMI20.2
 of bromooyan on α1 - / 3-bromethylamine, in aoetone. After pressing and evaporation, it is still vaporized for 20 minutes.



     EXAMPLE 21:
Chloroxypropylepiperidine is combined with bromayan. Wool is heated with a 4% solution of the reaction product in dioxane for 12 hours at 70 ° C. After removing the solvent by pressing, it is still vaporized for a very short time.



     EXAMPLE 22:
An artificial viscose silk, which has been aminated with
 EMI20.3
 The ethylaminimine, is cold soaked with a 30% solution of potassium cyanide, and is then treated additionally, by retro-weighting, with a solution of bromine combined with carbon tetrachloride, at 5 ° C. The amount of bromine is measured so that the fibrous material remains permanently alkaline. the silk is then additionally treated with a 1% aqueous solution of / 3 -aminoethylaminoacetic acid, for half an hour, at 20 - 50 C.



    EXAMPLE 23;
 EMI20.4
 Diethylaminoacetacetonitrile is combined with the equivalent amount of bromooyan, and the mixture is allowed to act.

 <Desc / Clms Page number 21>

 reaction products (methyl bromide, diethyloyanamide, bromacetonitrile) in a closed container (container capacity: 40 cm3 per gr. of wool) at 70 0, for 14 hours, on the quintuple quantity of wool at a relative humidity of 1 45% air. The treated material absorbs acid dyes much more easily.



     In connection with diethylaminoacetonitrile, one can employ, with a similar result, the methyl ester of diethylaminoacetic acid.



  EXAMPLE 24;
A mixed fabric of wool and oellulosic wool of amino visoose with ethylenimine is impregnated with a solution containing 60 grams per liter. of quinoline yellow S extra (Schultz, Farbstofftabellen, 7th, Ed. Vol. I, p. 392), and 100 grs of thiourea. The previously dried goods are then exposed to the steam action of 15% benzyl chloride or 1,5-dibromopentane or 1,4-dichlorobutene-2,3, for 14 hours, at 70 0, and at a relative humidity of 35%. Finally, we spray for 20 minutes. The colors are uniform, perfectly solid in washing and very solid in water.



   EXAMPLE 25:
Viscose artificial silk, which has been aminated with ethyleneimine according to the process of Belgian patent 410,661 of July 30, 1935, is heated for 14 hours at 80 C in steam of 15% O- ethyl-N-N'-di-n-propylisourea in a container in which a vacuum has been made before the introduction of the base. more solid and more intensive hues: :) are obtained with acid dyes, particularly with chromating dyes.



   EXAMPLE 26;
Wool treated with 3% alizarin cyanine green G

 <Desc / Clms Page number 22>

 extra (sohaltz, parbstofftabellen 7th Ed. vol. I, p. 532) is heated with 5% bromocyan (steam) in a container with a capacity of about 25 om3 per gr. of wool for 8 hours at 60 ° C. The washfastness of the color is improved.



     EXAMPLE 27
After its vaporization with carbon tetrachloride for the elimination of humidity, wool is impregnated, in a closed apparatus, with a solution which contains 10% of propylieonibrile, relative to the wool, and the equivalent quantity of bromine (1 molecule for 1 molecule of nitrile). this solution is first allowed to act for 1 hour at room temperature, then heated to 80 ° C. and treated for 3 hours at this temperature. After removal of the solution by squeezing, oomplementarily treated with fresh carbon tetrachloride, which contains 1% cyclohexylamine, for 1/2 hour at room temperature.

   The fiber freed from the solvent and rinsed out is improved in its dyeing properties.



   EXAMPLE 28:
Viscose artificial silk, which contains a mixture of ethylenamine bases with a high degree of polymerization, in an amount such that the nitrogen content is 1.5 is heated in a solution of carbon tetrachloride, in a ratio. bath port of 1:20, with a mixture of 10% diphenyl-carbodiimide and the% 1.4-dichlorobutadene-2.3, for 12 hours, at 80 C. Fixation of basic components is improved and affinity for dyes acids is increased.



   EXAMPLE 29:
Wool yarn is, after drying, heated in a bath ratio of 1:20, with a 5% solution of benzyl-focyanide in butanol, for 6 hours, at 100. There is then only a minimal change in color. Thread,

 <Desc / Clms Page number 23>

 then dyed with 3% amidonaphthol BB red (Schultz, Farb-stofftabellen. 7th Ed. Vol. I, p. 58), with the addition of acetic acid, at 85 - 950 C, has better fastness to water and washing than a material dyed in the same way, without the pretreatment with benzylsulfocyanide. an improvement in solidity is also obtained when the action of
 EMI23.1
 benzylesalfocyanide is exerted after dyeing.



     EXAMPLE 30:
A wool containing approximately 1% of aluminum chloride is introduced, in the water-free state, into a 2% solution
 EMI23.2
 of dipropyleoarbodiimide in Ei-n-batyl ether. This solution is heated for 6 hours at 90-100 C, then pressed and washed with water which contains, per liter, 2 grams. sodium dtoleylemethyletaurine. The dyeing properties of the fiber are improved.
 EMI23.3
 s + Edilà? L31 1:
Wool, which contains 1% aluminum chloride, is heated, at 70 0, for 3 hours, and at 1000 C for 3 hours, in 20 parts by weight of dioxane, with 15% of the
 EMI23.4
 weight of 1,4-disu wool, looyanabuene 2.3, obtained by heating 1 # 4-dichlorobatene 2.3 with potassium sulfoyanide in alcohol.

   Shades produced with acid dyes, for example with Amidonaphthol BB red (Schultz,
 EMI23.5
 Farbstofftabell, 7th Ed. Vol. I p. 58), on the material so treated show improved water fastness and wash fastness.



     EXAMPLE 32:
Artificial viscose fiber, which has been aminated, according to the process of Belgian patent 410 661 of July 30, 1935, with ethylenimine (nitrogen content approximately 2%) is, after pretreatment with washing powder dilute oaustic soda, treated with 20% aoetone solution of

 <Desc / Clms Page number 24>

 bronmocyanin, relative to the weight of the fiber, first for 1/2 hour at room temperature, then for 2 hours at 40 C. The silk which was then rinsed thoroughly, shows an increase in affinity and a considerable improvement in strength properties.



   The dye affinity of silk can be further altered by further treatment of the fiber with a 5 ci 'solution of ammonium sulfide in a closed vessel, for 2 hours, at 60-70. 0. The product then contains, in addition to basic groups, thiourea groups. The strength of acid tints, for example with 3% brilliant red Supranol 3 B, (Schultz, parbstofftabellen, 7th Ed. Vol. II. P.



  204) on this fiber is very satisfactory. In this case, it is also possible to apply the process of simultaneous dyeing and alkylation described in Belgian patent 413751 of 11 February.
 EMI24.1
 February 1936. As an alocylant, bromaoetyl-3-methyl-piperidide, for example, is suitable.



   The color fastnesses on silk treated with bromooyan as indicated above can be further improved if the goods treated with an acid (oxalic acid are treated additionally with trimethylol-1.3.5.-triaminotriazine , tartaric acid or sulfuric acid). the goods are impregnated with a 5 / Cl aqueous solution of this body, dried at 60 - 80 C and lasted for a few minutes at 120 - 1300 C. The fiber can also be impregnated with a solution of formaldehyde and one can then print an acidic solution of triaminotriazine, dried and heated.
 EMI24.2
 î: Ck -. "t1 '>>' 3: Wool dyed with 3% anthracenacid red 5 BL
 EMI24.3
 (Schultz Farbstofftabellen 7th Edition, Vol.

   II, p lZa), and dried, is heated, for 6 hours, at 1000, in 15 times the amount by weight of a 2 1/2% solution of gasoline

 <Desc / Clms Page number 25>

 
 EMI25.1
 3 - 1-dibromopropyl mustard in dioxane. then press and rinse, at 40, with 2 grs. of oleylpolyglyool per liter. The treated shade withstands vigorous washing with soap and soda ash at 80, while the same shade is largely removed on ordinary wool.
 EMI25.2
 



  TI8.nf1 ZR n-nn ep, e] AT118n1; or 4th in 1., ll1n not 1; mi, 1> lin n "+ 'treated as above and is dyed only afterwards, a considerable improvement in washfastness is also obtained.



   It must be assumed that bromopropyl mustard oil first binds to amino groups, forming the corresponding thiourea, and then subsequently occurs the known transposition to bromomethylaminothiazoline. . Whether and to what extent still other reactions occur, for example with the bromomethyl group or reactions with the carboxyl groups of wool, may remain uncertain.



   The effect is further enhanced, when the essence of soft
 EMI25.3
 dibromopropyl tarda exerts its action, in admixture with l1ÓpiohlorhYdrino.



    EXAMPLE 34;
A wool yarn dyed with 3% oyanine green alizarne G extra (Schultz, Farbstofftabellen, 7th Edition, Vol. I, p. 532) is heated in the dry state for 5 hours at 100 in 18 parts. by weight of butanol which contains 3% gua-
 EMI25.4
 nidinesulfooyanide and 1% d -J3d1ChlorethYliq ether; e.



  The solidity of the color is thus improved.



   EXAMPLE 35:
Wool yarn dyed with 3% green ayanine alizarine G extra (Schultz Farbstofftabellen, 7th Edition, Vol. I, p.
 EMI25.5
 



  532) is heated in butanol with 20% of diayanediamide and the% 0 - ((- 1 -diohlorodimethyl ether, d, = first for

 <Desc / Clms Page number 26>

 2 hours at 40 - 50, then for 4 hours at 80 - 100 C.



  The strength of l. hue is improved.



   EXAMPLE 36:
Dry wool, which contains about 1 ci '. of zino chloride, is heated for 6 hours at 60 - b5 C with a 20 d solution of trichloracetonitrile (based on the weight of the wool) in dioxane, avoiding the admission of water. Wool previously treated with epichlorohydrin can also be treated in the same way.



   EXAMPLE 37:
Artificial casein fiber which, after acidification with dilute hydrochloric acid, has remained in a closed container (capacity 40 cm3 per gr. Of artificial fiber) for 14 hours, at 70 0 , and at a relative air humidity of 75 in steam of 25% epichlorohydrin (based on the weight of the artificial fiber), is placed, for 1/2 hour, in a 1/2 / n solution of sodium cyanamide, at ice temperature. It must be assumed that the ohloroxypropylamino groups are thus converted into aminooxazoline groups.



    EXAMPLE 38: An acetate artificial silk, which contained spinning 10% benzolsulfopolyglycide and was aminated by treatment with 12 "% ethylenimine in the gas phase (process of French Patent No. 795,699 of September 14th). 1935), is first treated in a bath made alkaline with triethanolamine, with 5% of the divalent 1.5-diaminopentane mustard oil, at 60 ° C. After that the mustard oil has been used mainly 4 of ss -bromethylaminhydrobromide are added and at the same time 3% of green oyanine alizarin G extra (Schultz Farbstofftabellen, 7th Ed., Vol. I, p. 532) are added.

   The dyeing is completed at around 75-80 C

 <Desc / Clms Page number 27>

 by adding formic acid. intensive shades are obtained in this way. Amine formation therefore takes place in this case by two reactions taking place in the same bath partly simultaneously. It first forms a thiourea which still contains a group of free mustard essence. by subsequent addition
 EMI27.1
 of chlorâcoylamine, this group reacts in part with -rou- pe thiourea, in part with the mustard essence group, so that in both cases - in the first case directly, in the second case secondarily - it can form isothiourea groups.



   Instead of bromethylaminhydrobromide, one can use
 EMI27.2
 also bromacétaiethylamide or bronaoét-03'-3-àié-thylminoethylaminhydrobromide or its adduct of di.nethylsulfate.



   EXAMPLE 39:
A viscose artificial silk, which has been aminated with ethylenimine and has a total nitrogen content of 1.8% in the primary part, in the secondary part and in the tertiary part, is treated, at 40 C, with 5 % of the mixture of essences of partially hydrolyzed casein mustard, obtained by the action of thiophosgene in an alkaline medium. To an alkaline reaction which is still weak, one then adds 5%
 EMI27.3
 of ohloraoet-di-J3 -piperidoethylamine and the temperature is gradually increased to 50-75 ° C. Then rinsed and dyed with acid dyes in the usual manner. Depending on the nature and amount of the reacting components, and depending on the duration of the action, the effect may be modified.

   The colors are considerably stronger than those produced.
 EMI27.4
 on the starting mrati3r4, you can n.nsfdi use mixtures of different essences of mustard, one or the other component can be added first, and then the other

 <Desc / Clms Page number 28>

 component.



   An increase in solidity is obtained, for example, if, before the action of the mixture of mustard essences and peptides, a dispersion of 3% mustard essence is used.
 EMI28.1
 oyalohexyl or dodecyl.



     EXAMPLE 40:
The same silk as in Example 39 is treated with 3% cyclohexyl mustard essence and 3% dichloroacetyl-piperazine, for 1 hour, at 40-65 C. then dyed with 4% direct blue alizarin A (schultz, Farbstofftabel- len, 7th Ed. Vol. II, p. 9), without the addition of acid, at 60-70.



  The bath is completely exhausted.


    

Claims (1)

ABSTRACT . EMI28.2 jj'iuveuLiou u for objut a process of trultuwent products formed naturally or artificially in or with protein substances and their derivatives or other substances containing imino or basic amino groups of high molecular weight, this process having the following characteristics : 1) Substances which are capable of reacting with amino or imino groups are allowed to act to form substituted amidines. 2) The active substances contain, in addition to the reacting groups, radicals causing solubility in water. 3) The active substances contain, where appropriate, in fractions, aliphatic or alicyclic radicals with more than 8 carbon atoms. 4) The active substances contain, in addition to groups forming amidines, still other radicals capable of reacting which allow other reactions of substitution or addition or condensation. 5) The products are pre-treated, simultaneously <Desc / Clms Page number 29> ment, or subsequently to the action of amidine formers, with other substances suitable for substitution with nitrogen or carboxyl. 6) Before, simultaneously or after the action of the amidine formers, the products are further treated with alkylene oxides. 7) Amidine-forming substances are produced in the presence of the material to be treated. 8) The material is treated with thioureas in the presence of alkylating agents. 9) The action of amidine formers takes place before tincture. 10) The action of amidine formers takes place at the same time as a tincture. II) The action of amidine formers takes place after tincture. 12) for the formation of amidines, sub- EMI29.1 ! Í1.tl1lHH! which contain chromophore! ::> or chromogens. 13) The products are further treated oomplementarily with condensing agents, in particular carbonyl compounds or their derivatives.