BE607179A - - Google Patents

Description

       

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  Process for dyeing nitrogenous fibers
It has been found that it is advantageously possible to dye nitrogenous fibers when an aqueous preparation is applied to these fibers comprising a wool dye and an auxiliary agent capable of forming with water and, if necessary, with adjuvants, a system consisting of two liquid phases with a mixing interval, the quantitative proportion between the water, possibly containing adjuvants, and the agent

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 auxiliary being within the mixing interval or in the vicinity thereof, the mixing interval being already present for a relatively low content of the auxiliary agent, and the phase richer in auxiliary agent constituting a large fraction in a large area of the mixing interval,

   and then subjecting the fibrous material provided with the aqueous preparation to a heat treatment.



   As nitrogenous fibers, for example, in the present process, polyamide fibers, regenerated albumin fibers, silk, but in particular wool, optionally mixed with other fibers such as rayon-acetate fibers, are envisaged. , polyester fibers or cellulose fibers (semi-wool). In addition, nitrogenous materials of fibrous structure which are not textiles, such as leathers and skins, should be mentioned.



   As the dyes, any wool dyes can be used, preferably water soluble dyes which are useful for dyeing wool by the exhaustion dyeing process. As examples, we will mention:
Acid dyes for wool,
Chromable dyes,
Complex chromium compounds of dyes

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 containing sulphonic groups and containing a chromium atom bound in a complex manner to a dye molecule,
Complex chromium or cobalt compounds which are free of sulfonic groups and carboxyl groups not participating in complex formation and in which two dye molecules are intricately bonded to a chromium or cobalt atom;

  water-soluble dyes are also contemplated here, for example dyes containing
 EMI3.1
 sulfonamide groups or alkylSJ1fone groups, as difficultly soluble to insoluble complexes in water, the latter having, for the present process, to be converted into a fine dispersion,
Complex chromiferous or cobalt-rich compounds containing in the complex molecule a single sulphonic group or a single carboxylic group which does not participate in the formation of the complex, and in which two dye molecules are complexly linked to an atom chrome or cobalt,
Complex chromium-containing or cobalt-bearing compounds which contain in the complex molecule more than one aquasolubilizing group (sulphonic and / or carboxylic groups),

   and wherein two dye molecules are intricately linked to a chromium or cobalt atom,

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Cuprophthalocyanines containing sulfonic groups,
Reactive dyes, for example those comprising
 EMI4.1
 both mono- or d1-chlorotriazin groups or -CH2-CH2-O-SO3H groups.



   Sulfuric esters of vat leuco-dyes,
For the dyeing of mixed fabrics of wool and other fibers, besides wool dyes, the dyes which are customary for other fibers, for rayon-acetate and polyester fibers, for example dispersive dyes, are used. , or for cellulose fibers, dyes rising directly
In addition to the dye, there is a need for the present process an auxiliary agent having the properties indicated at the beginning. A condition which this auxiliary agent must fulfill is that it must be capable, at least with adjuvants, of forming together with water a system having a mixing interval.

   As usual, a system comprising a mixing interval is understood to mean two substances, each of which is soluble in the other to a limited extent, that is to say up to a determined percentage content, while that between these limits there is a two-phase domain consisting of two liquid phases. In this case,

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 a certain amount of the auxiliary agent must therefore be soluble in water and a certain amount of water must be soluble in the auxiliary agent. At least one of the limits of the solubility, in particular that of the solubility of the auxiliary agent in water, must not be too high.

   It should not, for example, reach more than about 2% (the percentage means the number of parts of the auxiliary agent in 100 parts of the solution). In this case, such a limit of solubility can exist in and for itself, that is to say that allé exists only for a solution, consisting only of water and of the auxiliary agent, or it can be brought about by suitable adjuvants and / or by suitable measures, for example by neutralization of acidic or basic auxiliaries, by addition of electrolytes envisaged in the dyeing of textile materials , such as for example acetic acid, sodium sulphate or sodium chloride, thickeners, hydrotropic substances, etc.

   In these cases the system can be viewed as a modified two-substance system the additional substances allow or promote the formation of a system having a mixing gap between water and auxiliary agent, but they are generally sufficiently soluble or dispersible in water not to condition

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 themselves of mixing interval, even if they are liquid substances.



   Within the mixing interval, there is, on the one hand, the phase leaner in auxiliary agent and, on the other hand, the phase richer in auxiliary agent.



  With an increasing quantity of auxiliary agent, relative to the whole of the two-phase system, the quantitative proportion [(phase richer in auxiliary agent): (phase lower in auxiliary agent) ¯7 also increases.



  For the present process, then, only those auxiliary agents are considered as auxiliary agents for which, over a wide range of the mixing range, the phase richer in auxiliary agent constitutes a significant fraction of the two-phase system. and is advantageously of the order of at least 20%. It follows that when the limit of the solubility of the auxiliary agent in water is exceeded, there must already be, for a relatively small increase in the auxiliary agent content, a system with. two phases in which is present a relatively large fraction of the medium richer in auxiliary agent and where necessarily also this phase richer in auxiliary agent consists mainly or at least for a fairly large part of water.

   (The theoretically correct designation of "water-in-auxiliary agent phase" is in the case

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 of such a quantitative proportion in a certain opposition to the usual expression, because in a usual way the dissolved substance is quantitatively less important than the solvent).

   Substances which, such as for example methanol or benzyl alcohol, do not fulfill this condition, because for an increase in the quantity above the saturation point, the fraction of the phase richer in agent Auxiliary on which the total system grows only slowly over a large area, for example following an approximately linear flat progression, is not contemplated for the present process. ;

   
One class of compounds which meet the conditions described above, and which are preferably used for the present process, are hydrophilic, preferably surface-active substances which form colloidal solutions. and are suitable for coaservation. The term preservation used in colloid chemistry means the demixing of a colloidal solution of a hydrophilic colloid into two phases, the richer phase in body being called coaservate and the leaner phase in body being called liquid. balancing. Demixing can be brought about by the addition of electrolytes or other suitable substances.



  The coaservate is then characterized by the fact that few

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 colloid contains a relatively large quantity of water in the dissolved state. A ccaservable system is a two-phase system modified according to the definition given above.



   In general, it is advantageous to work in the vicinity of the saturation point mentioned above. For example, the amount of the auxiliary agent can be increased so as to be in a region of the mixing interval where the layer richest in auxiliary agent reaches 20 to 60% of the substance. two-phase system. It is also possible to work in a limited range below Dani the saturation point, but still in the vicinity of the mixing interval, that is to say with an aqueous solution, approximately to completely saturated, of the auxiliary agent. .

   As such a saturated solution, the phase richest in auxiliary agent of a two-phase system of the mixing interval, for example coaservate, can also be used after separation.



   If the dye is incorporated into a two-phase system within the mixing interval, then, when agitated, it is substantially all absorbed by the phase richer in auxiliary agent and at least. partially dissolved, because this phase has for this dye a significantly higher dissolving power than for water alone, while the poorest phase

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 as an auxiliary agent hardly absorbs any dye. In the case of very hydrophilic dyes, rich in groups
 EMI9.1
 ........ -..'- rt-. ,, 1 '... sulfonic acid, this optimal state can be brought about by the addition of small amounts of acetic acid.

   This two-phase system which is essentially; made up of
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 ....... :: ... (. (!, ... .T: w¯ .., water, by the auxiliary agent and by the dye, can in general be homogenized by stirring, without the addition of emulsifiers, so as to provide a statistically uniform preparation which is sufficiently stable for the service life and which can then be suitably supplied to the fibrous material. By the addition of a small amount of A thickener, preferably sodium alginate, the stability of the preparations can be increased with respect to a homogeneous mixture through the core.



   As examples of auxiliary agents fulfilling the above conditions, which are suitable for coas vation and therefore particularly suitable for the present process, there may be mentioned the products resulting from the reaction of fatty acids of high molecular weight and
 EMI9.3
 of hydroxy-alcQ7le1ll1nes, as well as, where appropriate, ethylene oxide. For example, without using ethylene oxide together, it is possible to prepare such products from fatty acids of high molecular weight, preferably from those comprising about

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 12 carbon atoms, and hydroxyalkylamines such as trietbanolamine or, preferably, diethanolamine,

   the reaction taking place so that the mol-
 EMI10.1
 cular quantitative between the h7 ... alc011a1D1ne and the fatty acid is greater than unity and reaches approximately 2: 1. Such compounds are described in U.S. Patent 2,089,212 filed June 8, 1936.



   Also when preparing auxiliary agents from fatty acids and hydroxyalkylamines, together using ethylene oxide, it is generally advantageous that the quantitative proportion.
 EMI10.2
 The difference between the reacting hydroxyaloyiamine and the reacting high molecular weight fatty acid also is greater than unity and, for example, about 2: 1.

   The ethylene oxide is advantageously determined so that the quantitative molecular proportion between the fatty acid entering into the reaction and the ethylene oxide entering into the reaction is of the order of 1; 2 to 1; 15 ,
The order of the reactions of the three starting substances, in particular of the fatty acid, of the hydroxyalkylamine and of the ethylene oxide is in itself immaterial. it is possible, for example, to obtain interesting results by subsequently adding ethylene oxide to one of the products resulting from the reaction of a fatty acid and

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 of an alkylamine which were indicated above.



   However, it is also possible to add oxide
 EMI11.1
 ethylone to a fatty acid y8rozyalkylamide as obtained by reacting a fatty acid with an alkylamine in the molecular ratio of 1: 1, then reacting the resulting adduct with a hydroxy- alkyllamine, again preferably in the 1: 1 molecular ratio. Good results can also be obtained when, instead of carrying out the reaction indicated last (this is advantageously carried out in the hot state, for example at a temperature of 130 to 160, for a few hours), everything is added. simply a hydroxyalkyllamine to the adduct obtained from a fatty acid alkyllamide and ethylene oxide.



   Also in the case of the auxiliary agents to be prepared with the joint use of ethylene oxide, fatty acids, for example caprylic acid, stearic acid, oleic acid and in particular coconut fatty acid, are envisaged, and suitable hydroxyalkylamines are triethanolamine, dihydroxyethylethylenediamine and in particular diethanolamine, as well as mixtures of these amines.

   As particularly preferred auxiliary agents, there will be. take out the product obtained from one mole of coconut fatty acid and 2 moles of diethanolamine with elimination of a

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 mole of water approximately, and the product which is obtained by adding 2 moles of ethylene oxide to one mole of coconut fatty acid dihydroxyethylamide, then by reacting the product d addition to diethanolamine in the 1: 1 molecular ratio.



   In addition, the auxiliary agents used in the present process are products resulting from the addition of ethylene oxide to fatty acids of high molecular weight, to aliphatic alcohols of high molecular weight, to fatty acids. alkylphenols, high molecular weight alkyl mercaptans or high molecular weight aliphatic amines.



   Auxiliaries which exhibit any of the compositions described above tend in and of themselves to form a two-phase system with water, and this property can still be significantly promoted by adjuvants. suitable such as acetic acid and / or sodium chloride, so that a system having an advantageous mixing range in the sense of the above indications is easily obtained.



   The preparations to be used in accordance with the invention can then be applied to the fibrous material in a manner known per se, advantageously continuously, for example by printing, or

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 in a particularly advantageous way with the scarf, which requires only a very short time. 0 'is thus that it suffices for example, with dry wool (combed or piece), to pass from the top between two horizontal padding cylinders located one next to the other, the padding solution not being present only in the small cavity located above the line of contact of the two cylinders (this operating mode will be designated here by the expression "padding in the" corner "of a two-cylinder scarf).



   However, it is possible to envisage an immersion and a subsequent draining or a subsequent expression of the excess of the impregnation liquid.



   Most of the time, you enter the padding bath with the item dry. In special cases, for example when a batch of wool is to be impregnated directly after the last wash with the "Leviathan" wash, one can also enter with an impregnated and strongly expressed article. the temperature of the bath in the scarf can vary within wide limits, for example from room temperature up to 80. The fact that the quantitative proportion in the two-phase system does not depend very much on the temperature when using the system described in Example 1, is a particularly surprising phenomenon.

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 taking.

   Even at elevated temperature, the phase richer in auxiliary agent which contains the dye is not immediately fixed on the fiber, but it first adheres only mechanically and can then be completely removed from the surface of the fibers again. wool fibers by washing in cold water. A fairly high padding temperature is then particularly desirable when subsequently entering directly into the vaporization chamber in a continuous procedure. Preheating the impregnated material to be dyed, for example by an infrared apparatus, as in the so-called "Pad" roller system, or by using steam, can also be advantageous.



   Instead of bringing the impregnation liquid to the scarf on the fibrous material, it is also possible to pass the latter over transfer cylinders coated with felt and rotating in the liquid. The liquid is absorbed by the felt and is spread over the fibrous material in an amount which can be easily dosed.



   In addition, the fibrous material can be passed through a fine rain or fine mist of the impregnating liquid and thus charged with the necessary amount of the dye preparation. All the devices and methods known in the textile industry for the conditioning or wetness of yarns can be used for this purpose. Advantageously, the

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 fibrous material at most the quantity of liquid that it is capable of absorbing in a uniform distribution, because here, contrary to the treatment with a scarf, it is practically not envisaged to subsequently express an excess of liquid.



   After the fibers are removed with the two-phase system, heat fixing takes place which can generally be carried out with heat, in exceptional cases with dry heat. In general, the wet article is entered into the vaporization chamber or the fixing chamber. Occasionally, however, it is also possible that intermediate drying is recommended.

   For the heat treatment, the following treatment conditions are considered: a) Saturated steam at atmospheric pressure, for 2 to 20 minutes, for example, in a Mather-Plat, in other devices of vaporization working continuously, in Fleissner vaporizers, or for a fairly long time in a boiler vaporizer, in a J-Box or on a roller machine called "Pad". b) Saturated steam at elevated temperature, for example for 2 minutes at 120 on a vaporizer under pressure from Péter, or

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 for one minute at 160 in a MOntfort reactor.

   c) Saturated steam below 100, for example at 60, by winding airtightly in a rubber canvas the article impregnated with the scarf and rolled up on itself and closing, then leaving it to rest for 12 hours in an enclosure at 60.



     In addition, the following possibilities for heat treatment should be mentioned further: f) Shock-like drying of the impregnated article in a stream of air or steam superheated to 180 for one to two hours. About 5 minutes, or contact heat, as described in various known methods, for example by passing the padded article through a heated liquid metal alloy, with glass beads, sand, sand. oil or the like, or finally by heating in a high-frequency electric field (micrometer wave field), while giving the coupling electrodes a suitable size and shape,

   heating of the impregnated article is obtained

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 at the temperature required for the time required for fixing.



   Following the steam treatment or the heat treatment, preferably in the case of the latter, it is occasionally advantageous, especially in the case of wool, to cause fixing of the previously set dye. on the fiber by carrying out a brief "shock" type treatment in an aqueous acid bath which is heated to a temperature which may be between 60 and the boiling point, said bath containing, for example, from 2 to 4 char per liter of concentrated formic acid, said treatment lasting on the order of 10 to 120 seconds. The duration of the treatment, the temperature of the bath, the nature and the concentration of the acid may vary.



   This acidic bath is usually only insignificantly tinted by the remains of non-fixed dye. In many cases this treatment can also be omitted, or it can be combined with the subsequent cleaning operation.



   Then it is essential to carry out a cleaning in order to remove the excess colorant, the thickeners and the remainder of the auxiliary agent. This cleaning takes place, in general, by a heat treatment in a bath containing a detergent with surface activity, where appropriate in the presence of ammonia or

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 however acidic (combination with the acid shock mentioned above). When it is possible to work without prior shock with the acid, it may then be superfluous to add a detergent with surface activity when, as is the case, for example, when the auxiliary agent described in Example 1 is used the auxiliary agent which remains on the fiber is capable of developing a clean and sufficient detersive and emulsifying effect in a neutral or weakly alkaline bath.

   During this cleaning treatment, more dye generally reaches the bath than during the possible prior shock with the acid. In a continuous process, special attention should be paid to the continuous renewal of this bath. It is then rinsed and dried in the usual manner.



   Of particular interest is the dyeing of combed wool according to the process according to the invention, since these wet treatments can advantageously be carried out on the smoothing machine.



   When deo chromium dyes are used, the dyes which are then obtained without adding a chroming agent are then to be treated in a known manner in a hot acid bath with dichromate in order to obtain a complex of dye. If, however, it is desired, during the subsequent formation of the chromium complex on the fiber, also to work continuously, it

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 It is then necessary to treat the previously dyed article, in a continuous manner, advantageously again with a scarf, with a chromate solution, to spray again, to wash thoroughly and, if necessary, acidify. The dyes obtained with sulfuric esters of leuco-vat dyes must, as usual, be subjected to an oxidation treatment.



   For direct dyeing on a piece of wool, it was until now necessarily necessary to chlorinate the wool, otherwise only absolutely unsatisfactory printing results were obtained. By using the process according to the invention, it is possible in particular, with reactive dyes, to obtain very good impressions on non-chlorinated wool. A printing color is used, the composition of which fully corresponds to the padding baths described above, while the consistency of the printing color can optionally be adjusted as desired by adding simply more or less large amounts of thickeners.

   The other operational phase of printing is the dyeing process. Since prints generally need to be dried before spraying, care should be taken to provide particularly humid steam during the spraying operation, and as a first wet treatment

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 Acid shock at a temperature of around 60 should be recommended.



   The use in "vigorous" printing of the two-phase process according to the invention provides a higher flexibility of the dyes and makes it possible, in general, to shorten the duration of the vaporization. With the aid of the printing machine according to the "vigorous" process, it is also possible, according to the present process, to dye evenly, in a continuous procedure, very advantageously a combed, by replacing the raised cylinders by cylinders. full.



   All the methods known until now for fixing wool dyes by a spraying operation or by a dry heat treatment, which is dyed continuously or discontinuously or which is printed directly on an article non-chlorinated in wool, have hardly acquired any importance in the technique, because until now it has not been successful, especially in the case of medium shades and sustained shades, to prevent the stitching of the dye or the prints, and to ensure the dyeing of the wool pile surface.



  The phase richer in auxiliary agent of the system according to the invention causes a uniform distribution of the dye over the entire surface of the wool pile, and the subsequent heat treatment ensures uniform fixing of the wool.

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 dye, even when mixtures of dyes belonging to different classes are used for dyeing.



   Finally, the present process is also very advantageous for cleaning and simultaneous dyeing of wool containing fatty substances.



  This wool, which contains, for example, natural lanolin, spinning oils or spinning sizing masses, can be present in any stage of treatment. According to the present process, it is now possible, at any suitable stage of processing, to combine with the dye the removal of fatty substances. Thus, for example, one can dye, so to speak, at the same time as the first cleaning of the raw wool (surge wool), or else one can dye wool in a skein or in part, while removing the spinning oil. However, it is also possible, in the manner indicated, to rid the wool of the fatty substances which it contains, without cleaning it.



   Wool containing fatty substances, such as natural lanolin, spinning oils or sizing agents for spinning, can be present in any stage of treatment. It goes without saying that the method is mainly envisaged for cleaning wool in the usual way, in the first place to clean wool.

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 raw wool (fatty wool or surge), in which case one must further remove, besides lanolin, also other impurities, for example, water-soluble impurities, and in addition to remove spinning oils of which the wool can be discarded following the present process at any stage of treatment, after having completed
 EMI22.1
 {"'....." f ..t' .. .... ".." 'z- \ .. 7 "": .-- "" ",".,., -.f' <- #. ': i: ...' j ... rl. ,; or its purpose.

   The present cleaning method can also be used when there is a mixture of wool with other natural fibers or with synthetic fibers.



   The invention is described in more detail in the non-limiting examples which follow. In these examples, and unless otherwise indicated, the parts and percentages are by weight and the temperatures are, as in the above, indicated in degrees centigrade.

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     EXAMPLE 1
A combed wool is impregnated by passing through the cavity made between the two rollers of a horizontal scarf (or on a similar device serving to soak and remove excess bath), with the cold preparation. prepared as follows:
With 40 parts of the auxiliary agent which is described later, 10 parts of one of the complex metal dyes indicated below are put into a paste, and covered with 650 parts of cold water; 300 parts are then introduced. a 25: 1000 alginate thickener.



   The squeezed wet comb then passes directly into a continuously or discontinuously operating vaporizing chamber which is filled with saturated steam. It stays there for about 10 minutes and then immediately enters a bath at 60 which contains one cubic centimeter of 25% ammonia per liter. Then rinsed in hot water and dry. Wet treatment after spraying, as well as drying, can advantageously take place on a so-called trowel. The dyes obtained hardly differ, with regard to shade and fastness, from dyes produced in the usual manner with the same amount of dye.



   The auxiliary agent mentioned above is

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   prepared as follows: 1
In a round flask with a capacity of one liter which is provided with a descending condenser and an extension, 330 g of coconut fatty acid (1.5 mol), 345 g of diethanolamine ( 3.55 moles) and 1.5 g of p-toluenesulfonic acid. The air in the flask is removed with nitrogen, and heated to an internal temperature of 160 to 1650. Maintain at this temperature until it has collected in the flask. the ice-cooled extension of 27 to 28 g of water (1.5 moles), which is the case after about four hours.



   After cooling, 644 to 645 g of a pale brown liquid is obtained which is completely soluble in water to give a clear solution.



   600 8 'of the product is then mixed with an amount (to be determined in a preliminary test) of approximately 12 g of glacial acetic acid and one to two grams of a silicone-based anti-foaming agent. the amount of glacial acetic acid may vary somewhat from test to test and is determined as follows:
In a cylinder provided with a ground-glass stopper, 4 g of the product is dissolved in 100 cm3 of distilled water, resulting in a highly viscous solution formed which is completely clear. From a burette, we run 10% acetic acid drop by drop,

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 by adding; first 0.5 cm3.

   At the drop point
 EMI25.1
 .. $. ,, "-" "....> - ...!: i" i "'") .....: ... ".-' -t" "tes, it is: pro4td.t, a ;, ladle that disappears completely i ±; ..- 1 '(\ <"' '}, 7ti" t ......, t'; when shaken, the, cylinder. 0 .continued to add when it, '), #, route the acid A06tÎ quē in portions of 0.1 char and shake after - ;;, -. f, ..y ", .ß.: Ï : y, ..1 '' "-; each add1t1on 'utà: oe" that the solution remains strong-' '' '<f :: -;' .-: '. ... 1.0. , -1;: '. Lt..r. ,, i aent "'" '! -.,., ..., ......., .....-, <, .., , 'this efret ment troubled. In - general; approximately 0.300 of 1. ,, 0., ..... ": ;; 'acetic acid is required for this purpose. which provides C, ô .... "- 1-" ': "'" \ j .... .'l ... t "1-,. ¯ ....... "'> .........."' .... "" "$,." \ ......... 0llTflit the above indicated amount of 12 g of glacial acetic acid.



   The preparation obtained is then checked by dissolving 4 g again in 100 cm3 of distilled water.



  The resulting solution should be opaque. Upon rest, it should slowly separate into two layers.



   After standing for about 24 hours an oily layer forms constituting about 40 to 60% of the total liquid.



   If the 4% solution should only be slightly cloudy, then 1.6 g of glacial acetic acid are added to the preparation again and a further check is carried out.



   Examples of suitable dyes include the following

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1) The complex cobalt-rich compound (complex 1; 2) of the dye of formula
 EMI26.1
 JOH HO Cl. \ # N. N (red-bordeaux) so 01
2) The 1: 2 cobalt complex of the dye of formula
 EMI26.2
 OH m R a N - 0- -! * ¯ * (yellow) l # '(= 11 01 H30-802 H 0
3) The chromiferous complex 1: 2 of the cclorant of formula
 EMI26.3
 OH HO <Z> # H s H 8 (brown-purple) H5C-SO2
4) The chromiferous complex 1; 2 of the dye of formula
 EMI26.4
 COOE HO I C- H # <> (yellow) "" "" 0 ::

     H7j C

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5) The 1: 2 cobalt complex of the dye of formula
 EMI27.1
 CE hot 00 an- (green-blue) h3c4o2
6) The 1: 2 cobalt complex of the dye of formula
 EMI27.2
 OR --- 3 or¯- <3-, H h # <3 (grim)
7) The 1: 2 cobalt complex of the dye of formula
 EMI27.3
 0 OR H2 '! J-l¯-w = '11 L (olive-green) lcio2 (olive-green)
Instead of the dyestuffs mentioned which are free of sulfonic groups, it is also possible to use the chromium or cobalt compounds 1: 2 complexes of azo dyes having in the molecule of the metal complex only one aquasolubilizing acid group, or those containing more than an acidic water-solubilizing group.

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   As examples, we will mention the chromiferous complex 1: 2 (green) containing, in complex bond with a chromium atom, one molecule of each of the two azo dyes of the formulas
 EMI28.1
 and
 EMI28.2
 the chromium complex 1; 2 of the dye of formula
 EMI28.3
 we have HO HQ 3 'a 1I-b (blue-gray) and the cobalt complex 1:

  2 of the dye of formula
 EMI28.4
 OgN OH Hff PU * = 11 --b (olive) 02N 803

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   A woolen ribbon 10 cm wide with the following preparation constituting a two-phase system
With 50 parts of the auxiliary agent described in Example 1, 40 parts of the complex chromium compound containing, in complex bond with a chromium atom, one molecule of each of the two dyes are put into a paste in the cold state. azcic formulas
 EMI29.1
 cover with 870 parts hot water, and stir in 50 parts of a 25: 1000 alginate thickener.



   The impregnated tape passes directly into a high-pressure vaporizer working continuously (Firm PETER, Liestal), and it is treated there for 2 minutes at 120 with saturated steam. The ribbon which comes out is washed in a bath at 60 which contains per liter 2 cm of ammonia and 2 g of the sodium salt of 2-hepta- acid.
 EMI29.2
 decYl-N-benzyl-benmlmidazole-dieulfonique. A black dye is obtained, identical at the ends, which has good solidity properties.

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   EXAMPLE 3
A ski gabardine must be dyed, forming a mixed fabric consisting of 50 parts of wool and 50 parts of a polyamide loop yarn. We work advantageously on the known piece dyeing machine, roller, called "Pad", which is manufactured by the firm.
 EMI30.1
 Svetema in Qoteborg. The pulping bath contains 5 parts of the 1: 1 chromium complex of the azo dye of formula
 EMI30.2
 
40 parts of the auxiliary agent described in Example 1,
750 parts of water,
200 parts of 25: 1000 alginate thickener.



   After padding and expression, the article passes through an infrared irradiation chamber and, from there, still in the spread state, into the vaporization chamber where it is rolled up. After a treatment time of one hour after entry of the end of the article into the vaporization chamber, it is treated for 30 seconds in a 90 ° aqueous tin which contains

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 liter 4 car of concentrated fornic acid. Then, in order to remove the remaining thickener and excess non-fixed dye, it is washed at 50% with a nonionogenic detergent. An orange dye is obtained, the shade of which is identical on both categories of fibers and on both sides of the fabric.



   EXAMPLE 4
To dye an article made from a fiber mixture made up of equal parts of wool and cotton in a blue shade, the following padding bath is used:
7 parts of the dye of formula
 EMI31.1
 

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 EMI32.1
 and * # 1> - i 10 parts of the dye of formula
 EMI32.2
 dough with
30 parts of the agent! auxiliary described in Example 1, covered with
630 parts of cold water with the addition of
300 parts of alginate thickener
25: 1000.



   After impregnation and drying, the wet article enters a continuous vaporizer (Mather-Plat) containing saturated vapor and remains there for 10 minutes. It is then rinsed thoroughly, as is usual for semi-wool dyes.



    EXAMPLE
A non-chloro wool article is printed with a printing paste of the following composition

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 30 parts of the dye of formula
 EMI33.1
 
200 parts of urea,
40 parts of the auxiliary agent described in Example 1,
320 parts of water,
400 parts of alginate thickener
25: 1000,
10 parts of sodium m-nitrobenzenesulphonate
1000 games
After printing and drying, it is sprayed for 15 minutes in a "Stern" vaporizer or in a "Mather-Plat", then rinsed thoroughly, first cold, then at a temperature of 60 to 80, and then again. once cold, then dry. A uniform blue dye is obtained.

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   EXAMPLE 6
For carrying out the process according to the invention according to the preceding examples, it is also possible to use the auxiliary agents, the preparation of which is described below: a) The procedure is as described at the end of the example. - ple 1, but only heats up to the elimination of 21 g of water. b) The procedure is as described at the end of example 1, but heats up to the elimination of
31 g of water.

   c) In a 500 cm3 flask which is provided with a stirrer, a thermometer and a descending cooler, keep for
9 hours, at a temperature of 160 to 165,
110 g of coconut fatty acid (0.5 mole), 165 g of triethanolamine (1.1 mole) and 0.5 g of acid
 EMI34.1
 p-toluenesulphonic.



   The preparation obtained is soluble in water giving a slight ladle, but it is soluble in it completely homogeneously.



    200 g of the preparation are mixed with
12.5 g of glacial acetic acid. In a 4% solution, for example, it forms in

 <Desc / Clms Page number 35>

 bit of temple two layers.



   The indicated quantity of acetic acid is preferably again determined by preliminary tests carried out in a manner analogous to that described in Example 1 ..



   The formation of a two-phase system can also be recognized by the fact that when the solution is shaken, it becomes cloudy. d) In a round flask with a capacity of one liter which is provided with a stirrer, a thermometer and a descending condenser, maintain
420 g of technical oleic acid (1.5 mol),
345 g of diethanolamine (3.35 moles) and
 EMI35.1
 1.5 g of p-toluenesulphonic acid, 160-165, under nitrogen atmosphere, until 27-28 cm3 of water have separated in the cooled extension. ice.



   740 g of the reaction product are obtained,
Aqueous solutions of this product are slightly cloudy. e) Products which can also be used are obtained by condensing one mole of acid

 <Desc / Clms Page number 36>

 stearic with 2 moles of diethanolamine; one mole of capxylic acid with 2 moles of diethanolamine: one mole of coconut fatty acid with 2 moles of dihydroxy-ethyl-ethylenediamine, or one mole of coconut fatty acid with one mole of triethanolamine and one mole of diethanolamine.



    EMMELE 7
In a "Leviathan", a batch of raw wool is normally subjected to leaching. After the last rinsing bath, squeezing is carried out continuously, with as strong a pressure as possible between the expression rollers until a moisture content of about 60% is obtained.

   The cast of wool falls between the two rubber rollers of a scarf. The cavity between the rollers contains the following two-phase preparation
10 parts of one of the colorants ... mentioned in Example 1,
50 parts of the auxiliary agent described under d) in example 6,
838 parts of water,
100 parts of an alinate 25 thickener:

  1000,
2 parts of 40% acetic acid
1000 games

 <Desc / Clms Page number 37>

   The expression is calculated in such a way that there remains in the wool approximately 90% of humidity. This batch of wool arrives in a vaporizer where it is subjected to a brief and intensive treatment by steam, during a temperature. from one to two minutes approximately.

   Then. the batch of wool falls into another stainless steel "Leviathan" vat which contains the following washing and fixing preparation:
2 grams per liter of 85% fornic acid
0.5 gram per liter of the condensation product obtained from octadecyl alcohol and 25 to 30 moles of ethylene oxide.



  The temperature is 90 and the passage time is about one and a half minutes. The bath. must be constantly renewed by a continuous supply, because it enriches with the unbound dye and because the formic acid is consumed by the wool in the order of magnitude of one percent of the wool weight. In a vat of "Leviathan" which follows, rinse until the water which flows is clear, then dry.

 <Desc / Clms Page number 38>

 



   EXAMPLE 8 In an aqueous bath closing per liter 40 g of the auxiliary agent described in Example 1, 10 to 50 g of the copper compound of. formula dye
 EMI38.1
 and
100 to 200 g of an alginate thickener
25: 1000, we dive until complete imbibition of a suede leather of calfskin, kid, leather for gloves or split leather (which takes about 2 to 15 minutes), then we exhale with a scarf until to have an increase in weight of 90 to 100%, then, after having wound in plastic sheets, it is treated for one to four hours at 60-80 in an oven.

   To complete the fixing, and to wash out the unbound dye, the leather is then pressed for about 30 minutes, in a bath ratio of 1: 6 to 1; 10, in an aqueous solution containing, relative to the weight of dry leather , from 2.5 to 5% formic acid and one percent of a product resulting from the addition of about 35 moles of ethylene oxide to one mole of octadecyl alcohol.

 <Desc / Clms Page number 39>

   lique. The leather is well dyed in a uniform brown shade.



   On the categories of leather indicated above and according to the indications given, it is also possible to obtain uniform dyes, unitary in the core dyeing, with combinations of two or more dyes providing, according to the usual methods, uneven results in the distribution of the dye and non-unit in the shade.



   Dried cow, calf or kid leather which has been tanned with vegetable tanning agents can also be advantageously dyed as described above. In order to avoid damage to the leather, in this case one works with treatment temperatures which are advantageously not higher than 50.



   Finally, it is also possible to dye, according to the indications of this example, chrome leathers of cow, calf or buckshot which are surface tanned with synthetic tanning agents.



   EXAMPLE 9
Drayed chrome calfskin or drayed buckskin are, after neutralization, dehydrated, with a scarf for example. The leathers thus prepared are impregnated,

 <Desc / Clms Page number 40>

   lying down with the plush giving a /, or according to the indications of example 8 by immersion and expression, with an aqueous preparation of dye reinforcing per liter
40 g of the auxiliary agent described in example 1,
5 to 50 g of the copper dye of the composition indicated in Example 8, and
100-200 g of a 25: 1000 alginate thickener.



  The operating phases which follow are carried out completely in Example 8, and uniform dyes are thus obtained.



   EXAMPLE 1Q
Sheepskin well tanned with chrome or other skins capable of withstanding an extended treatment at 60, are impregnated with a scarf with an aqueous bath containing per liter
40 g of the auxiliary agent described in example 1,
5 to 50 g of one of the coloring agents of the composition indicated below, and
100 g of a 25: 1000 alginate thickener, then they are placed in plastic bags and stored for two to 8 hours at 60 in an oven.

   The skins are then washed at 50-60, for 15 minutes, in

 <Desc / Clms Page number 41>

 
 EMI41.1
 ce'2 cm of acetic acid fü 17r, !! ¯i, J ,, xrte4 ('rt r. f% iF'iaG .:' 40 6 é ^ '; Ô,'; â! ün 3du.xatl. so much of the addition of
 EMI41.2
 a = the alcohol
 EMI41.3
 octad 0 de, MI te # n16re get, '\' Q! plexes' on cobal- tlfèéé. '7hi'.> A1Î 'pr6able. with and leu ü11V1iV se oaraotéri-! com.p '! "lf ... 1'" and te1S # ractér: l- sent; '. 1: ë Qri4t6'm8me' when using. not cOl re: D; Vàt'tè {): '8aià' mixed.



  '.:;,' 90lora1'1t: ¯ one uses for example the complex / .hl: dú <éoÍOrant 'II1Onoazo! That of the formula
 EMI41.4
 CE Hl 0- <I> - '' - <'(green) 80 H
 EMI41.5
 or the cobalt-rich complex 182 obtained from the two
 EMI41.6
 colorants in formulas
 EMI41.7
 OH HO on HO 1 #C "> '# -: 4 r 0-, c 400 - = il OC-0-C8 3 02 113 (brown)

 <Desc / Clms Page number 42>

 or the reactive dye of formula
 EMI42.1
   EXAMPLE 11
In a known printing machine following; the "vigorous" process, the cylinder in relief is replaced by a full cylinder. When printing a combed, a result corresponding to the padding is obtained in this way.

   The aqueous impregnation liquid contains per liter
30 g of the formula coloring agent
 EMI42.2
 

 <Desc / Clms Page number 43>

 
40 g of the auxiliary agent described in example 1, covered with
624 g of water,
6 g of 40% acetic acid and
300 g of a 25: 1000 alginate thickener.



   After passing through the "Vigoureux" printing machine, the wet combed wool is placed in baskets and brought without drying to the vaporizer.



  Spray for one hour with saturated wet steam and then wash on the trowel. The baths are 60 on average, and the first bath contains per liter 0.5 g of the auxiliary agent according to Example 1, the second bath consists of water and the third bath contains one cubic centimeter. fornic acid. This gives a combed color in a deep red. A parallel run carried out without the auxiliary agent provides a weak, pitted dye which is unusable.



   If the usual embossed cylinder is kept in the printing machine by the "Vigorous" process and, for the rest, the combed sheet is printed as indicated and subjected to the finishing treatment, then a "Vigorous" effect is obtained. of a coloring intensity which, according to the usual known procedure, can only be obtained with a markedly higher amount of dye.

 <Desc / Clms Page number 44>

 



   EXAMPLE 12
On a suitable scarf, we impregnate at 70 a combed wool with the preparation which is obtained as follows: In
40 parts of the auxiliary agent described in Example 1, introduced slowly ent
40 parts of formula dye
 EMI44.1
 then add
620 parts hot water, and then
300 parts of alginate thickener
25: 1000.



   After impregnation, the combed piece enters a continuously working vaporizer and remains for 10 minutes in steam saturated at 100. Without rinsing, we then express strongly between rubber cylinders and pass again through a scarf containing the following solution brought to 60:

 <Desc / Clms Page number 45>

 
20 g per liter of potassium chromate or sodium chromate,
680 g per liter of water,
300 g per liter of alginate thickener
25: 1000.



   Again squeeze between rubber rolls and spray again for 10 minutes as described above. The combed material is then washed on the trowel as described in Example 11. Dark-black dyes are obtained which, during alkaline treatments, do not rub off yellow, a drawback that this dye exhibits during traditional processing methods. tinting with subsequent chrome plating.



   Likewise, natural silk can also be dyed with the above foraul's dye, and after chrome plating, the shade is dark gray.



   EXAMPLE 13 ######
A pure wool fabric for ladies' clothing is impregnated with a scarf with the following preparation increased to 60:

 <Desc / Clms Page number 46>

 15 parts of formula dye
 EMI46.1
 5 parts of the 1: 1 chromium complex of the dye of the formula
 EMI46.2
 1 part of the cobalt complex 1: 2 of the dye of formula
 EMI46.3
 
40 parts of the auxiliary agent described in Example 1, 709 parts of water, 250 parts of an alginate thickener
25: 1000.



  1000 parts.

 <Desc / Clms Page number 47>

 



   After expression, one rolls up uniformly on a stick, encloses in an airtight manner in plastic titillas or rubberized cloths, and drops to stand overnight at 600. Then rinsed thoroughly with water brought to 60, then dry. Despite ±% mixture of dyes of different classes, we obtain @@ unit dye. '
EXAMPLE 14
A so-called opicalized article consisting of 55 parts of polyester fibers (eg "Terylene") and 45 parts of loine should be dyed. Dyeing should be carried out on the bare part dyeing machine using the "Pad" roll process which is manufactured by Svetema Finish in eborg.



   The scarf bath, brought to 60, contains s
20 g per kg of the coloring agent of the formula
 EMI47.1
 

 <Desc / Clms Page number 48>

 7.5 g per kg of the 1: 2 chromium complex of the dye of formula
 EMI48.1
 
40 g per kg of the auxiliary agent described in Example 1, 741 g per kg of water,
200 g per kg of an alginate thickener
25; 1000,
4 g per kg of 40% acetic acid.



   The addition of acetic acid is necessary here to obtain the two-phase aqueous system. After padding and expression, the article passes through an infrared radiation chamber and from there it arrives, still in the spread state, in the vaporization chamber where it is wound up. The temperature of the vaporizer chamber thermometer should be kept as high as possible and should be above 90. After entering the end of the article, it is left for 5 hours in the steam chamber. It is then necessary to carry out a thorough cleaning to remove the dispersive dye tourniquet from the wool.

   This has. place on a boat at @

 <Desc / Clms Page number 49>

 adding one fat per liter release auxiliary described in 1 * Example 1 and treating for 30 minutes
 EMI49.1
 90 "approximately. Rinse \ enauij <? E to eh dry.



  A uniform yellow dye is obtained. r yk 'r e r ..7m EXEMPLK15.':! - \ '
Prepare a padding bath as follows
20 parts of the blue basic dye of formula are put into a paste.
 EMI49.2
 and 20 parts of the red reactive dye of formula
 EMI49.3
 with
40 parts of the auxiliary agent described in Example 1.

   We then add

 <Desc / Clms Page number 50>

   620 parts, boiling water and finally
 EMI50.1
 -; #> $ '# &&& * & * r-Vs ..--- #., 300 parts of an alginate thickener With this bath, -we scarf at 50 a fabric, mixed whose chain is made up of wool and weft
 EMI50.2
 with 3¯.béâ '4âN polyaCxloni trile (or vice versa), then' spray the fabric without intermediate drying for 10 minutes at 100.

   It is then treated for one minute in a boiling aqueous bath containing per liter 2 car of 85% formic acid and 0.5 g of a product resulting from the addition of 35 moles of ethylene oxide to one mole. octadecyl alcohol. Finally, it is washed at 60 for about 15 minutes, with a bath containing par. liter one gram of the product resulting from the addition of 9 moles of ethylene oxide to one mole of nonylphenol.



   In the fabric thus treated, the wool fraction is dyed red and the polyacrylonitrile fraction blue. When the auxiliary agent is not used together, the wool fraction is dyed significantly weaker.



   Instead of the red reactive dye, you can

 <Desc / Clms Page number 51>

 also use the chromium complex 1; 1 of the dye of formula
 EMI51.1
 the fraction of wool then being dyed orange.



     TRIPLE 16
A padding bath is prepared by pulping 20 parts of the dye of formula
 EMI51.2
 with 200 parts of the auxiliary agent described in Example 1 and adding 780 parts of boiling water.



  With this padding bath, a fabric made of polyamide fibers is padded at 50, then the fabric is dried at 80-100 and then subjected for 30 seconds to a treatment with hot air at 180-210. The tissue is then treated for about one minute in a boiling aqueous bath which contains per liter 2 parts of 85% formic acid.

 <Desc / Clms Page number 52>

 and 0.5 part of the product resulting from the addition of 35% ethylene oxide to one mole of octadecyl alcohol. Finally, we rinse hot and cold.

   The blue dye thus obtained is appreciably more intense than a corresponding dye for the production of which one of the auxiliary agents customary for this dyeing method is used instead of the auxiliary agent indicated.



   Instead of the anthraquinone dye indicated above, it is also possible to use the chronifer complex 1; 2 (dyeing gray) of the dye of formula
 EMI52.1
 
According to the indications of this example, it is equally possible to dye polyamide fibers obtained from ¼-caprolactam as those obtained from
 EMI52.2
 adipic acid and hexamethylenediamine.

 <Desc / Clms Page number 53>

 



   EXAMPLE 17
For carrying out the present process according to Examples 1 to 5 and 7 to 16, it is also possible to use the auxiliary agents in the table below. Column I indicates how the auxiliary agent is prepared; in column II the products are characterized by their behavior during the formation of coaservates in water using sodium chloride or acetate acid. - than at 20.
 EMI53.1
 
<tb>



  I. <SEP> Preparation <SEP> of <SEP> agent <SEP> II. <SEP> A <SEP> coaservat <SEP> is <SEP> formed
<tb>
<tb>
<tb>
<tb>
<tb> auxiliary <SEP> by <SEP> dissolution <SEP> of
<tb>
<tb>
<tb>
<tb>
<tb> 4 <SEP> g <SEP> of the <SEP> product <SEP> in
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> Product <SEP> resulting <SEP> from <SEP> the <SEP> 50 <SEP> cm3 <SEP> water <SEP> + <SEP> 50 <SEP> cm3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> reaction <SEP> of a <SEP> mole <SEP> of a- <SEP> of a <SEP> saturated <SEP> solution
<tb>
<tb>
<tb>
<tb>
<tb> cide <SEP> bold <SEP> technical <SEP> of <SEP> of <SEP> sodium <SEP> <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> coco <SEP> on <SEP> 1.05 <SEP> mole <SEP> of
<tb>
<tb>
<tb>
<tb>
<tb> diethanolamine,

   <SEP> in <SEP> pre-
<tb>
<tb>
<tb>
<tb>
<tb> sence <SEP> of a <SEP> gram <SEP> of acid
<tb>
<tb>
<tb>
<tb>
<tb> p-toluene-sulfonic acid,
<tb>
<tb>
<tb>
<tb>
<tb> with <SEP> expulsion <SEP> of a <SEP> mole
<tb>
<tb>
<tb>
<tb>
<tb> of water, <SEP> to <SEP> 160-165
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 2 <SEP> Product <SEP> resulting <SEP> from <SEP> 60 <SEP> cm3 <SEP> of water <SEP> + <SEP> 35 <SEP> to <SEP> 40 <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> the addition <SEP> of <SEP> 4 <SEP> moles <SEP> cm3 <SEP> of a <SEP> solution <SEP> satu-
<tb>
<tb>
<tb>
<tb>
<tb> of ethylene oxide <SEP> <SEP> to <SEP> a <SEP> role <SEP> of <SEP> chloride <SEP> of
<tb>
<tb>
<tb>
<tb>
<tb> mole <SEP> of <SEP> diethanolamide <SEP> sodium
<tb>
<tb>
<tb>
<tb>
<tb> of <SEP> the <SEP> fatty acid <SEP> of the <SEP> coconut
<tb>
<tb>
<tb>
<tb>
<tb>

  (product <SEP> N <SEP> 1)
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> The <SEP> produces <SEP> resulting <SEP> of <SEP> 100 <SEP> cm3 <SEP> of water <SEP> + <SEP> 2 <SEP> cm3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> a <SEP> said <SEP> ion <SEP> .de <SEP> 2 <SEP> moles <SEP> of acetic acid <SEP> <SEP> at <SEP> 10%
<tb>
<tb>
<tb>
<tb>
Ethylene oxide <SEP> <SEP> to <SEP> a
<tb>
<tb>
<tb>
<tb>
<tb> mole <SEP> of <SEP> diethanolamide
<tb>
<tb>
<tb>
<tb>
<tb> (product <SEP> N <SEP> 1) * <SEP> is <SEP> main-
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> held <SEP> for <SEP> one <SEP> hour <SEP> at
<tb>
<tb>
<tb>
<tb>
<tb> 140-1500 <SEP> with <SEP> 1.1 <SEP> mole
<tb>
<tb>
<tb>
<tb>
<tb> from <SEP> diethanolamine
<tb>
 

 <Desc / Clms Page number 54>

 
 EMI54.1
 
<tb> 4 <SEP> Like <SEP> 3,

   <SEP> but <SEP> with <SEP> 4 <SEP> 100 <SEP> cm3 <SEP> of water <SEP> and <SEP> 2 <SEP> cm3
<tb>
 
 EMI54.2
 moles of ethyl chloride in a 10% solution of the chloride; 1 ;; sodium dEr 5 C01IDe 'w' but 'with 6' fVA01 !? moles of e'id'étb7- solution "at 10 s:; of chlorine .. \> 1 <" ":" .. ride '' of "'' sodium ,. ' 6 As 3. put with 9 75 3- water + 22 to | 5 ca5 moles of Myde;

  .d'6thy- of a, '9301ution to 10 of
 EMI54.3
 
<tb> lene <SEP> sodium <SEP> chloride
<tb>
<tb> 7 <SEP> Like <SEP> 3, <SEP> but <SEP> with <SEP> 12 <SEP> 60 <SEP> as <SEP> of water <SEP> + <SEP> 40 <SEP> cm
<tb>
 
 EMI54.4
 moles dWde dl ethy- dtuùe saturated solution of
 EMI54.5
 
<tb> lene <SEP> sodium <SEP> <SEP> chloride <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 8 <SEP> A <SEP> a <SEP> mole <SEP> (429 <SEP> g) of <SEP> 100 <SEP> on? <SEP> of a <SEP> solution <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> product <SEP> obtained <SEP> following <SEP> saturated <SEP> of <SEP> chloride <SEP> of
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> example <SEP> 1 <SEP> (without <SEP> addi- <SEP> sodium
<tb>
<tb>
<tb>
<tb>
<tb> acetic acid <SEP> <SEP>),

  
<tb>
<tb>
<tb>
<tb>
<tb> on <SEP> addition <SEP> 8 <SEP> moles
<tb>
<tb>
<tb>
<tb>
ethylene oxide <tb> <SEP>
<tb>
 
 EMI54.6
 Product resulting from 100 cm3 of a solution
 EMI54.7
 
<tb> the addition <SEP> of <SEP> 8 <SEP> moles <SEP> saturated <SEP> of <SEP> chloride <SEP> of
<tb>
<tb>
<tb>
Ethylene oxide <SEP> <SEP> to sodium <SEP>
<tb>
<tb>
<tb>
<tb> a <SEP> molede <SEP> diethano-
<tb>
<tb>
<tb> <SEP> acid <SEP> olei- lamide <SEP>
<tb>
<tb>
<tb> than <SEP> technical <SEP> (prepared
<tb>
<tb>
<tb> in a <SEP> analogous <SEP> way
<tb>
<tb>
<tb> to <SEP> N <SEP> 1 <SEP> to <SEP> from <SEP> from aci-
<tb>
<tb>
<tb> of <SEP> civic <SEP> and <SEP> of <SEP> di- <SEP>
<tb>
<tb>
<tb> thanolamine)
<tb>
 

 <Desc / Clms Page number 55>

 
 EMI55.1
 
<tb> 10 <SEP> The <SEP> produces <SEP> resulting <SEP> from <SEP>.

   <SEP> With <SEP> the <SEP> N <SEP> 10 <SEP> and <SEP> 11, <SEP> on
<tb>
<tb> addition <SEP> of <SEP> 8. <SEP> moles <SEP> can <SEP> get <SEP> as <SEP> follows,
<tb>
 
 EMI55.2
 of oxide of extracted from one of the #caserN ¯ s *! <% # 'mole of diethanolamide' D8.ns65fC of water, we de 1 = acid:: ole1q \ té, tecli-. d1ss ("t; ff¯'tg. du 'du1 t aj.Qtie $;", e8 conj1D.t-emen.tTéo' -: anperidant uneâàewr ,, gra3HQô²dtun &C0Bmle33é; v'tf heurëéd 140-ï, SGiavea: "" "" '-4Iun <C1exe:':,!:. F \, lïeade didtiéw.ô- :; - 'f de {.sc1de8'; 'aqu lamine ", .r -,: r' s < uM3Santa) cb- # -: *, lorântpolq 8 | 'refe / aâoar | T. x' t. 1 ¯: r - # -fc, - J} "'1' - \ - tr" "'' '' ' "" 1.11 30lut-i6n .; o 5 11 The pr04u11r 'resulting from the addition of. 10 moles g1nat8 & '5% #: For the oxide of -. &. Fol' '1t.' ':' 'J, 1i8'lO- i'it .......,. - "::::" '. t;

   au% -ds-dxY-é CJ.LL8 Q, .. m: 1e '- .. jon.-O.r.u.KU. at "t ,.



  . mo1e;: d'ester; -d1bydrox; .r- aicroscopétle ooaserfat 'étby! àÎdnoétbyUque of which the dye rei8e
 EMI55.3
 
<tb> the <SEP> fatty acid <SEP> of the <SEP> coconut <SEP> (a <SEP> to <SEP> the state.dissolved, <SEP> and <SEP> can
<tb>
 
 EMI55.4
 mole of fatty acid of coconut the N * M1, one must still be reduced with one mole add 0 5 to one cm3
 EMI55.5
 
<tb> of <SEP> triethanolamine) <SEP> is <SEP> of acetic acid <SEP> <SEP> to <SEP> 40 <SEP>% <SEP>
<tb>
<tb> maintained <SEP> for <SEP> one <SEP> hour
<tb>
<tb> to <SEP> 140-150 * <SEP> with <SEP> 1.1 <SEP> mole
<tb>
<tb> from <SEP> diethanolamine
<tb>
 
 EMI55.6
 "" '1 -'- ">. I! I <' '' ';' .: ,,, -> of; ", '" ...,
 EMI55.7
 
<tb> 12 <SEP> Product <SEP> resulting <SEP> from <SEP> 10 <SEP> as <SEP> from <SEP> water <SEP> + <SEP> 85 <SEP> to <SEP> # 90
<tb>
 
 EMI55.8
 the addition of 6 * ca3 drowns of oued solut1on "satu - = ..:

   
 EMI55.9
 
<tb> of ethylene oxide <SEP> <SEP> to <SEP> a <SEP> rée <SEP> of <SEP> chloride <SEP> of <SEP> sodium
<tb>
<tb>
<tb>
<tb> mole <SEP> of ester <SEP> mologlycéri-
<tb>
<tb>
<tb>
<tb> that <SEP> of <SEP> fatty acid <SEP> <SEP> of
<tb>
<tb>
<tb> coco
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 13 <SEP> Product <SEP> resulting <SEP> from <SEP> 45 <SEP> cm3 <SEP> of water <SEP> + <SEP> 45 <SEP> to <SEP> 50
<tb>
<tb>
<tb>
<tb> the addition <SEP> of <SEP> 6 <SEP> moles <SEP> cm3 <SEP> of a <SEP> solution <SEP> satu-
<tb>
<tb>
<tb>
<tb> of ethylene oxide <SEP> <SEP> to <SEP> a <SEP> rée <SEP> of <SEP> chloride <SEP> of <SEP> sodium
<tb>
<tb>
<tb>
<tb> mole <SEP> of <SEP> 3.5,

  5-trimethyl-
<tb>
<tb>
<tb> hexanol
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 14 <SEP> The <SEP> produces <SEP> resulting <SEP> of <SEP> 60 <SEP> cm3 <SEP> of water <SEP> + <SEP> 35 <SEP> cm3
<tb>
<tb>
<tb>
<tb>
<tb> addition <SEP> of <SEP> 6 <SEP> moles <SEP> of a <SEP> solution <SEP> saturated
<tb>
<tb>
Ethylene oxide <SEP> <SEP> to <SEP> a <SEP> of <SEP> sodium <SEP> chloride <SEP>
<tb>
<tb>
<tb>
<tb> mole <SEP> of lauryl alcohol <SEP>
<tb>
<tb>
<tb> is <SEP> maintained <SEP> for <SEP> a
<tb>
<tb>
<tb> hour <SEP> to <SEP> 140-150 <SEP> with <SEP> 1.1
<tb>
<tb>
<tb>
<tb> mole <SEP> of <SEP> diethanolamine
<tb>
 

 <Desc / Clms Page number 56>

 
 EMI56.1
 l, pidiù ;. .r, f # 'kuy <f e,. ,,., 51: + nw>: i>.' .'H, .¯3,; rra - '' ".. '.., 5 ..> ^'. T: ,,. '. Hs.' ',' Rr ^. ¯ ':. S'" .t '' '. : .. "';: ..l j'.,. '. r. 1': .. t '" 4iu:,., L. \\ -...



  1 * audit iiL '..: 3:. ',: ya.J: ^' yrty..u "" 1- '. ,not . e ..



  16 Produ1't ': "..' t \ .y, '; i: ;; - d' ': 5;,. Ú., 80': '\" ;; l:,. Ti; {:, i'20 ",:, '. i the dBbleB additions of a' saturated with Odè ': d.'tJQ-Íe'A" Üiiê' dê "ch1ci .." de "sodiua d'Oed '& eunë dècorad me e. e uu. 18 ne '.!.'., ',' ,,>, "" '.' <'# .. ##' .. - t'i S r'I 3 wHi 'iv e' '.' t .. 'M3i: iE''M ".' '17 Product. réisu7.taiât, wde. '; r '6: cae | u + 35.0 the addition of 8 to 10; d. taië'isl, molar saturated ùtion of sodium chloride sodium at a lG <deJi1odéCY.l,: ..:; .,. ,,,:; :, ';. î;: x; i #erca tan: tertiiài3C * tf & -' #### :: - # # l ##:. - the additive of 9.1ea'a'pi oarydë. of ethiria ":

   'a 70' {4: èaÛ '+' "! JO mole of 'diethanolamide of a saturated solution of the fatty acid of coconut sodium chlorides is mixed to fltoid aveo -, 1.1 mole of diothano-
 EMI56.2
 
<tb> wool
<tb>
 

 <Desc / Clms Page number 57>

 
EXAMPLE 18
According to the indications given in Example 1, wool is dyed with the dyes, the constitution of which is indicated in column I of the table below. The shades indicated in column II of said table are obtained.
 EMI57.1
 
<tb>



  I. <SEP> 11.
<tb>
<tb> Constitution <SEP> of the <SEP> colorant <SEP> Shade
<tb>
 
 EMI57.2
 1 h. "0 - K # <'" "% # S0 * H <¯> # T H * H-CT Ç l 803H yellow
 EMI57.3
 
<tb> O <SEP> H3C-C <SEP> blade
<tb>
 
 EMI57.4
 HOHM - 80 # <(. # On, 0 H03S ::: ccJ- SO; H ruby <# C1 HOS 30-0 0-M SO, H fj'c: - <, => - CIIz -caza rouge> - <L- = = N ----- $ red
 EMI57.5
 
<tb> OH <SEP> HO
<tb>
 

 <Desc / Clms Page number 58>

 
 EMI58.1
 Colorant constitution- Shade --l ---- ooloocan * so 3Ï3 C-o-ç:> - CH '' 8os 803R3 1 2 l3uo3B
 EMI58.2
 
<tb> 4 <SEP> # OH-N = N <SEP> N = N # HO <SEP> red
<tb>
 
 EMI58.3
 H3C-O-o- - <=> - o-cH} So3H "03" sin 3 red 8- H03B
 EMI58.4
 
<tb> N-N2 # <SEP> red
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> HO
<tb>
<tb> complex <SEP> chromiferous <SEP> asymmetric <SEP> 1:

  2 <SEP> of the <SEP> two
<tb>
<tb>
<tb> <SEP> colorants of <SEP> formulas
<tb>
<tb>
<tb>
<tb> HO3SOH <SEP> HO-C-N- # <SEP> O2N-OH <SEP> HO-C-N- #
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 6 <SEP> and; <SEP> red
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> H3C <SEP> H3C
<tb>
<tb>
<tb>
<tb> Chromiferous <SEP> complex <SEP> asymmetric <SEP> 1; 2 <SEP> of the <SEP> two
<tb>
<tb>
<tb> <SEP> colorants of <SEP> formulas
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 7 <SEP> HO3S- # OHN = N-HO <SEP> and <SEP> OH # -O2N-N = N-HO # <SEP> b @ un
<tb>
 
 EMI58.5
 ¯¯¯¯¯¯H¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯. ###### L #####

 <Desc / Clms Page number 59>

 
 EMI59.1
 
<tb> I. <SEP> II.
<tb>



  Constitution <SEP> of <SEP> colorants <SEP> Shade
<tb>
<tb>
<tb> Complex <SEP> cobaltiferous <SEP> 1: 2 <SEP> of the <SEP> dye
<tb> from <SEP> formula
<tb>
<tb> OH <SEP> H?
<tb>
 
 EMI59.2
 HO, S * G - H I # <# s brown- H03 1 - C! 8. "yellow-brown ¯¯¯¯¯ o ¯¯¯¯¯ ,, ¯¯¯ ¯¯¯¯¯¯¯¯¯ ¯¯¯ ¯¯ ¯¯> ¯¯¯ .¯¯¯ ¯¯
 EMI59.3
 
<tb> Complex <SEP> cobaltiferous <SEP> 1: 2 <SEP> of the <SEP> dye
<tb>
<tb> deformula
<tb>
<tb>
<tb>
<tb> OH <SEP> HO <SEP> brown-
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> brown-
<tb>
<tb>
<tb> #N <SEP> = N- # <SEP> red
<tb>
<tb>
<tb>
<tb>
<tb> O2 <SEP> N
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> SO, H
<tb>
<tb>
<tb>
<tb> Complex <SEP> chromiferous <SEP> 1:

  2 <SEP> of the <SEP> colorant
<tb>
<tb>
<tb> from <SEP> formula
<tb>
<tb>
<tb>
<tb> OH <SEP> HO
<tb>
<tb>
<tb>
<tb>
<tb> 10 <SEP> HO38 - # - N = N- # <SEP> blue
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> HO3S- # N = N- # SO3H
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Cobaltiferous <SEP> Complex <SEP> 1:

  2 <SEP> of the <SEP> colorant
<tb>
<tb> from <SEP> formula
<tb>
<tb>
<tb> OH <SEP> HO
<tb>
 
 EMI59.4
 11 .C -CH-, SO, H yellow N = N-cr c3 so3H zain
 EMI59.5
 
<tb> O2N <SEP> C = O = HN- #
<tb>
 

 <Desc / Clms Page number 60>

 
 EMI60.1
 
<tb> I <SEP> II.
<tb> Constitution <SEP> of <SEP> colorants <SEP> Shade
<tb>
<tb>
<tb>
<tb> CI-C
<tb>
 
 EMI60.2
 12 02K - <> - CH * CH - <r> -N - <3Hr-0 B> yellow soe ROI # 3 bi c \ X h HO EN - 0 13 --N N = 9/61 red
 EMI60.3
 
<tb> HO3S - # - SO3H
<tb>
 
 EMI60.4
 3 - Hv Cl
 EMI60.5
 
<tb> 14 <SEP> Cl-C-C-N-C <SEP> -HN - # - SO3H3H-HO3S <SEP> orange
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
 
 EMI60.6
 SO 3 II HO NE-00 N s03n no lIH-OC c11 .PI - c .... J.



  B03S H03S 0 H = 0/1 red HOS'S30H (jl HO 0 - <; ::> - N .0 - S02-NE Young ï * yellow
 EMI60.7
 
<tb> 16 <SEP> SO2-NH-CH2-CH2-O-SO3H <SEP> H3C- <SEP> CH2-O-SO3H
<tb>
 

 <Desc / Clms Page number 61>

 
 EMI61.1
 
<tb> I. <SEP> II.
<tb>
<tb>



  Constitution <SEP> of <SEP> colorants <SEP> Shade
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> HO
<tb>
<tb>
<tb>
<tb> 17 <SEP> # -N = N - # - NH-CO-CH3 <SEP> orange
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 17 <SEP> HO3S-O-CH2-CH2-SO2 <SEP> HO3S- # <SEP> -m-OE3 <SEP> orange
<tb>
 
 EMI61.2
 0 HHg so3H
 EMI61.3
 
<tb> 18 <SEP> O <SEP> blue
<tb>
<tb> HN- # SO2-C2H-CH2-O-SO3H
<tb>
 
 EMI61.4
 19 Cuprophthalocyanin-trisulfonic acid, blue
 EMI61.5
 
<tb> turquoise
<tb>
 

 <Desc / Clms Page number 62>

 
EXE PLE 19
With a preparation obtained according to the indications of example 1, but reinforcing, instead of the complex metalliferous dyes indicated in the said example, the cobalt complex 1: 2 (brought to the state of fine dispersion) of the dye. formula
 EMI62.1
 we impregnate with the scarf a fabric of:

  polyacid based
 EMI62.2
 ammonium-undecane-carboxylic acid and, as described in Example 1, subject to spraying and finishing treatment. A dark gray dye is obtained.



   EXAMPLE 20
With 40 parts of the auxiliary agent described in Example 1, 40 parts of the leuco-sulfuric ester (sodium salt) of 5-nonobromo-indigo of formula are put into a paste.
 EMI62.3
 then dissolve the whole in 600 parts of hot water. We

 <Desc / Clms Page number 63>

 add together 300 parts of 25: 1000 alginate thickener and 20 parts of sodium nitrite. To obtain the coaservate system, acetic acid is slowly added. With this preparation, a woolen fabric is impregnated with a scarf, then sprayed for 10 minutes and finally developed at 80 for 10 minutes in a bath containing per liter 20 parts of 98% sulfuric acid. It is then rinsed thoroughly, hot and cold, then dried.

   The wool is well dyed through to a uniform blue shade.



   If, instead of the leuco-sulfuric ester of the blue dye of the above formula, that of the red-pink dye of the formula is used
 EMI63.1
 had that of the green dye of formula
 EMI63.2
 uniform dyes are then also obtained.

 <Desc / Clms Page number 64>

 



   EXAMPLE 21
Cape surge wool. 60's unwashed, is impregnated on a horizontal two-roller scarf with a coaservate preparation consisting of 645 parts of water, 40 parts of the auxiliary agent described at the end of Example 1, 300 parts of 'a thickener containing 25: 1000 alginate and 15 parts of the chromium complex 1; 2 of the dye of formula
 EMI64.1
 After squeezing until there is an increase in weight of 100%, the wool is wrapped in gauze fabrics and treated for 15 minutes with saturated steam.



  Then, it is washed, advantageously in the known washing machine called "Leviathan"; in the first bath which contains, per 100 parts of water, 0.5 part of the auxiliary agent of the composition indicated and the temperature of which is 60, the wool remains for one to two minutes, while in the second and third baths it stays each time for one to two minutes at 50, and in the fourth washing bath, consisting of water at 40 to which has advantageously been added, for 1000 parts, 2 parts of 85% formic acid, it stays from one to

 <Desc / Clms Page number 65>

 two minutes. We obtain a wool dyed in a uniform scarlet red and containing only a small amount of Fat.



     EXAMPLE 22
An unwashed woolen fabric, made from carded woolen yarn, is impregnated with a scarf with a preparation consisting of 640 parts water, 40 parts of the auxiliary agent described at the end of this article. Example 1, 300 parts of an alginate thickener and 20 parts of the dye of formula
 EMI65.1
 then expresses until having a weight increase of 65%. The fabric is then wound up and the roller rotated for two hours at 92 in the vaporization chamber of a so-called "pad" roller machine. It is then cooled in the spread state and then washed for 30 minutes in the washing machine at 60 with a bath containing, per 1000 parts, 0.5 part of the auxiliary agent described. in example 1.

   After rinsing with cold water, it is possible to further acidify in a bath containing,

 <Desc / Clms Page number 66>

 per 1000 parts of water, 2 parts of 85% formic acid. The fabric is dyed in a pure shade of a uniform red. Its fat content is only about 0.4%.



   EXAMPLE 23
With 40 parts of the auxiliary agent described in Example 1 and 8 parts of sodium alginate, 25 parts of the dye of formula are put into a paste.
 EMI66.1
 add 500 parts of boiling water to the whole and leave to stand for a while to swell the thickener. If after standing no coaservate had formed, then another 5 to 10 parts of 40% acetic acid would be added. While stirring, 25 parts of the finely dispersed dye of the formula are dissolved in 400 parts of water.
 EMI66.2
 

 <Desc / Clms Page number 67>

 The dispersion of the anthraquinone dye is introduced into the preparation of the aazolque dye.



   A mixed comb consisting of equal parts of wool and of a polyester is printed with the printing color thus obtained, on the printing machine according to the "vigorous" process, with overlapping bands of 50% , then it is then vaporized for 45 minutes under a pressure of an effective half-atmosphere and subjected to the usual finishing treatment. The "vigorous" impression of pink color which is thus obtained is of a more vivid shade and distinctly more sustained than a "vigorous" impression obtained as to the rest in the same way, but without the addition of l auxiliary agent.



   EXAMPLE 24
A 60's unwashed Cape surge wool is impregnated with a scarf with a coaservate preparation containing, per 1000 parts by volume of water, 40 parts of the auxiliary agent described in Example 1, then it is expressed until there is an increase in weight of 100%. The wool is then vaporized for 15 to 30 minutes in 1000 saturated steam.

   Then it is washed, advantageously in the washing machine known under the name of "Leviathan"; in the first bath which contains, per 1000 parts of water, 0.5 part of the auxiliary agent

 <Desc / Clms Page number 68>

 according to example 1 and whose temperature is 60, the wool stays from one to 2 minutes, in the second and in the third bath% it stays from one to 2 minutes at 50, and in the fourth bath, consisting of water at 40 to which has advantageously been added, for 1000 parts, 2 parts of 85% formic acid, the wool stays for one to two minutes.



   A wool surge having a fat content of 20.8% no longer contains, after the treatment described above, only 0.3% fat.



   EXAMPLE 25
A batt of wool combed according to the Bradford system and containing about 3% vegetable spun oil is impregnated with a scarf as described in Example 24, expressed until it shows a 90% increase in weight. , then it is vaporized for 20 minutes with 100% saturated steam. Then washed with a smoothing machine in a known manner without adding other detergents. The combed only contains, after this treatment, only 0.4% oil.

 <Desc / Clms Page number 69>

 



   EXMPLE 26
An unwashed Australian fluff wool is scarf impregnated as described in Example 1 and then squeezed. The wool is then packaged in an airtight manner as possible / in a polyethylene sheet and stored for 6 hours at 800 in an oven. After this heat treatment, the wool is washed as indicated in Example 1.



   The fat content of such wool falls, during this treatment, from 14.6% to 0.4%.



   EXAMPLE 27
A woolen fabric made from a carcô wool yarn and containing a content of 4% of an olein-based sizing agent is impregnated with a scarf
 EMI69.1
 ..o:;) r and expressed, then it is wound and processed in the "Pad" roller machine for one hour at 93, spinning slowly. then washing in the machine with an aqueous washing bath containing, per 1000 parts by volume, 0.5 part of the auxiliary agent described at the end of Example 1. The fat content falls, during this treatment to About 0.5%.

 <Desc / Clms Page number 70>

 



   When washing wool according to Examples 1 to 4 above, it may be advantageous to increase the fouling resistance power ;. impregnation solutions, to add a further thickener thereto, for example a solution of 25 g of sodium alginate in one liter of water.


    

Claims (1)

Claims I. A process for dyeing or printing nitrogenous fibers, characterized in that said fibers are provided with an aqueous preparation containing a wool dye and an auxiliary agent capable of forming with water and, where appropriate, adjuvants, a system. of two liquid phases having a mixing interval, the quantitative proportion between the water possibly containing adjuvants and the auxiliary agent being in the mixing interval or in its vicinity, and the mixing interval already being present for a relatively low content of the auxiliary agent and the phase richest in the auxiliary agent constituting a large fraction over a large range of the mixing interval, and then the fibrous material provided with the fiber is subsequently subjected to a heat treatment. aqueous preparation. The present process can be further characterized by the following points: 1) Wool is dyed in the manner indicated, optionally as a mixture with other fibers such as polyamide fibers or cellulose fibers. 2) The dye preparation is brought to the fibrous material in a continuous procedure. <Desc / Clms Page number 72> 3) The quantitative proportion between the water and the auxiliary agent and where appropriate the adjuvants is chosen so that the preparation forms a two-phase system which can be homogenized and lies in the vicinity of the proportion quantitative for which a saturated solution of the auxiliary agent in water is also obtained, optionally containing adjuvants. 4) A coaserv6 system of a hydrophilic colloid is used. 5) The dye preparation further contains a thickener, preferably an alginate. 6) As auxiliary agents are used products resulting from the reaction of fatty acids of high molecular weight and hydroxyalkyllamines, as well as, where appropriate, ethylene oxide. 7) As auxiliary agents are used products obtained by reacting fatty acids of high molecular weight with hydroxyalkyllamines in a quantitative proportion of 1: 2 8) Auxiliary agents are used for reaction products of coconut fatty acid . <Desc / Clms Page number 73> 9) Reaction products obtained from triethanolamine or, preferably, diethanolamine, are used as auxiliary acents. 10) After supplying the aqueous preparation, the dye is fixed by a spraying operation. 11) As aqueous preparations, printing pastes of the composition indicated are used and impregnated with them in a comb according to the "Vigoureux" printing process or in the "Vigoureux" printing machine provided with a full cylinder. 12) Wool containing fatty substances is dyed in the manner indicated and washed after the heat treatment in order to remove said fatty substances. <Desc / Clms Page number 74> II.- As new industrial products, the dyes and prints obtained by carrying out the process defined under I.) and 1) to 12).