DE889737C - Process for dyeing polyamide fibers and acetate silk with ice colors - Google Patents

Description

Process for dyeing polyamide fibers and acetate silk with ice colors The invention relates to an improvement in the dyeing of polyamide fibers and acetate silk, by the fibers with an ice color coupling component and an amine base in the presence a guanidine compound are impregnated and the azo dye then on the fiber is formed.

To dye polyamide and acetate silk fibers has already been proposed the fiber with an alkali metal salt, for example the sodium salt to impregnate an ice color coupling component and an amine base, then the To diazotize base and then to couple this with the ice color coupling component. However, the colorations obtained in this way are economically insignificant Worth because they are weak and have poor fastness properties. That after no useful colorations are obtained with the above process is on the one hand the very low affinity of the fibers towards the salt of the ice color coupling component, on the other hand, the essentials that take place prior to the formation of the dye in the fiber Decomposition of the diazonium compound and finally the incomplete coupling of the salt of the ice color coupling component with the diazonium compound.

In order to remedy these disadvantages, swelling agents such as alcohol, ethylene glycol monoethyl ether, thiocyanates and thiourea have already been used for the purpose of increasing the absorption capacity of the fiber materials for the dye components. The improvement thus achieved is small at best and is more than offset by the increased cost resulting from the use of the expensive reactants in question used. The actual current situation regarding the dyeing of polyamide fibers by means of an ice dye coupling component and an amine base is very accurately reproduced in the following excerpt from p. 748 of the magazine "American Dyestuff Reporter" of October 17, 1949, where it says: "The naphthol dyes can with the Wate and the base are applied in one bath and then diazotized and developed in one operation in a second bath. However, we have not been able to achieve the same vivid tones on polyamide fibers that are obtained on cotton, nor have we obtained the required lightfastness and rub resistance. Work continues to obtain the desired properties of the naphthol inks on polyamide fibers. «It has now been found that the above-mentioned process can be used with polyamide or acetate silk fibers and dyeings are obtained which have a good depth of color and vividness and excellent fastness properties if the impregnation of the fibers is carried out in the presence of a guanidine compound. The guanidine compound has multiple functions in producing excellent colorations. It increases the affinity of the fiber materials for the coupling component by converting the ice color coupling component into a salt that is bound more firmly by the fiber materials than the coupling component itself or its sodium salt. The coupling component, the guanidine salt, also gives the diazonium compound greater resistance than the corresponding sodium salt. Finally, it also has a buffering effect, through which more even and livelier colors are obtained.

The dyeing of polyamide and acetate silk fibers with an ice color by impregnating the fibers with an ice color coupling component and a Amine base with the use of a guanidine compound during the impregnation as well as the salts of guanidine compounds and ice color coupling components and the Impregnation mixtures comprising a guanidine compound and one or both of the foregoing Containing dye components thus form the purpose and object of the present invention Invention.

Any aromatic primary amine such as used in the manufacture of azo dyes. Examples such amines are: 4-nitro-o-anisidine, 2,5-dichloro-aniline, 4-benzoylamino-2, 5-diethoxy-aniline, 2-amino-4, 4'-dichloro-diphenyl oxide, amino-azotoluene, 5-methyl-o-anisidine, m-chloro-aniline, o-chloroaniline, 4-nitro-o-toluidine, 4-amino-6-benzoylaminom-xylene, Tolidine, 3-amino-carbazole, amino-azo-benzene, 4-chloro-o-tohiidine, a-naphthylamine, 4-amino-4'-diOxyäthylaminoazobenzol, 4-chloro-2-nitroaniline, 4, 4'-diamino-diphenylamine, r-Amino-anthraquinone, N- (p-aminobenzoyl) -p-toluidine and the like. These compounds are as known, typical ice color bases. To form the azo dye can be used as Coupling component the well-known ice color coupling components can be used. Examples of such compounds are: ß-oxy-naphthoic acid, ß-oxy-naphthoyl-p-chloroanilide, ß-Oxy-anthroyl-o-toluidid, ß-Oxy-naphthoyl-z-naphthylamide, Benzoylacetaxnino-2, 5-dimethoxy-benzanilide, ß-oxynaphthoyl-2-naphthylamide, 2-oxy-zr-benzo- (a) -carbazole-3-carboxyl-p-anisidide, ß-O2ty-naphthoyl-m-nitroanilide, 5-chloro-2, 4-dimethoxy-acetoacetanilide, ß-oxynaphthoyl-anilide, ß-oxy-naphthoic acid dianisidide, ß-oxy-naphthoic acid-o-phenetidide, 4-oxy-diphenyl-3-carboxyl-anilide, 6-chloro-2, 3-oxy-naphthoic anilide, ß-oxy-anthroyl-anilide, ß-oxy-anthroyl-o-anisidide, ß-Oxy-anthroyl-m-nitroanihd, 3-oxydiphenylene oxide-2-carboxyl anilide, 3-oxydiphenylene oxide-2-carboxylic acid anisidide, 9-methyl-2-oxycarbazole-3-carboxylic acid anilide, 9-methyl-2-oxycarbazole-3-carboxylic acid anisidide, 9-methyl-2-oxycarbazole-3-carboxylic acid toluidide, 3-oxyfluoren-2-carboxylic acid-o-toluidide and the like

Guanidine compounds which can be used for the present purposes have the following composition in which R, and RZ are hydrogen or an alkyl group such as methyl, ethyl, propyl, butyl, octyl, decyl and the like, or an aryl group such as phenyl, naphthyl; Tolyl, ethylphenyl and the like, or an aralkyl group such as benzyl, menaphthyl and the like, or a cycloaliphatic group such as cyclopentyl, cyclohexyl and the like, and the salts of these compounds such as carbonate, hydrochloride, nitrate ; Sulfate, phosphate or acetate.

Examples of such compounds are: guanidine, guanidine carbonate, Guanidine hydrochloride, guanidine sulfate, guanidine nitrate, guanidine acetate, guanidine phosphate, Aminoguanidine, aminoguanidine bicarbonate, aminoguanidine hydrochloride, aminoguanidine sulfate, ß-Diphenylbiguanid, ß-Diphenylbiguanidhydrochlorid, Methylguanid, Ethylguanid, Propylguanid, Phenylguanid, N, N-diphenylguanid, benzylguanid, ß-dibenzylbiguanid, biguanide hydrochloride, Phenyl biguanide hydrochloride, methyl biguanide, ethyl biguanide hydrochloride and the like.

The effect sought by the use of the guanidine compound can be achieved in several ways. For example, the amine base and the guanidine compound dissolved, the ice color coupling component the Solution added and the solution applied to the fibrous material, or it the ice color coupling component and the guanidine compound can be mechanically mixed, the mixture is dissolved together with the amine base and the solution is then applied to the fibrous materials can be applied, or the ice color coupling component, the amine base and the guanidine compound mechanically mixed, the mixture dissolved and applied to the fibrous materials be applied. Furthermore, the guanidine compound and the ice color coupling component reacted with each other and converted to a salt, the salt and the Amine base can be dissolved and applied to the fibrous materials. Regardless of which one special mechanical processes the components are brought onto the fiber, so the result is always the same, namely that colorations are obtained, which have the special advantages mentioned above.

For the impregnation of the fibers, the components are shaped an aqueous solution used. If necessary, a small amount of one can also be used water-miscible organic solvents such as ethanol, butanol, ethylene glycol monoethyl ether, Benzyl alcohol, ethylene glycol, etc., can be added to, if necessary, to support the dissolution of the components. Preferably the impregnation bath also added a small amount of a wetting agent, and for. this purpose can for example oleylmethyltaurine, the addition product of diisobutylphenol and 8 up to 10 molecules of ethylene oxide, the sulfonated condensation product of benzene and Keryl chloride (chlorinated kerosene), the diisobutylnaphthalene sulfonate and the condensation product of 2-naphthalenesulfonic acid and formaldehyde and the like can be used.

The amounts of the various dye components and those used Guanidine compounds can be very different. Usually equivalent amounts can be used the amine base and the coupling component are used; in practice. themselves however, it has been shown that better results are obtained when from the coupling component a slight excess is used.

The influence of the guanidine compound is already noticeable, even if only small amounts of this are added. However, it is best to use the Guanidine compound in amounts of 1 to 1 weight percent calculated on the to be colored Material to use.

If the guanidine compound is used in the form of a salt, so it is advisable to add an alkali to the impregnation bath. For this purpose will it is best to use a small amount of a strong inorganic or organic base, such as caustic soda, potassium hydroxide, caustic potash, ethylene diamine, tetraethylene pentamine and the like

After impregnating the fibers with the guanidine compound and the dye components are placed in a diazotizing bath, the sodium nitrite and an acid such as sulfuric acid, hydrochloric acid, acetic acid, formic acid and the like, contains. The bath temperature can range from room temperature to boiling from about i to Change 45 minutes to allow dye to form. The fabric is then rinsed and finished in the usual way.

It has already been stated that one of the effects of the guanidine compound is that the ice color coupling component depends on the amounts used the ice color coupling component and the guanidine compound in whole or in part is converted into its salt, and it has already been pointed out that the salt formation can be carried out before the components on the fibrous materials be applied. If the salt is not prepared, it is to be assumed that the salt formation safe during the dyeing of the fibers with the guanidine compound containing mixtures takes place.

To determine that when the various ice color coupling components treated with guanidine compounds actually results in salt formation a number of experiments have been carried out. Thus, 2.97 g of β-oxynaphthoic acid-p-chloroanilide were obtained and 2.73 g, B-diphenyl biguanide mixed with enough alcohol until uniform yellow colored paste was obtained. The paste was made at 50 ° under reduced pressure dried and then grated to a fine powder. The light yellow-brown powder, d. H. the ß-diphenyl biguanide salt of ß-oxynaphthoic acid p-chloroanilide had one Melting point from 137 to 1q.3 ° and is soluble with the formation of greenish-yellow solutions in alcohol and ethylene glycol monoethyl ether.

The corresponding ß-oxynaphthoic acid-p-chloroanilide is in these solvents practically insoluble and has a much higher melting point, namely 262.5 up to 263 °.

The corresponding sodium salt is in the solvents mentioned Although it is highly soluble, it does not have a precise melting point because it has a Decomposition begins.

In no case was caustic soda present, such as the sodium salt cannot be responsible for the melting point determination carried out.

3.37 g of 2-oxy-3-carbazolecarboxylic acid p-chloroanilide, 0.955 g of guanidine hydrochloride and 0.4 g of dry caustic soda were mixed with an amount of alcohol sufficient to form a paste, the mixture was dried at 50 ° under reduced pressure and then added grated a fine powder. The light yellow-brown powder had a melting point of 29 to 224 ° and was highly soluble in alcohol and ethylene glycol monoethyl ether.

The corresponding 2-oxy-3-carbazolecarboxylic acid p-chloroanilide is in practically insoluble in the above solvents and has a melting point of 258.5 up to 259.5 ° #. In this case too, salt formation thus took place.

3.13 g β-oxynaphthoic acid a-naphthanilide, 2.14 g phenyl biguanide hydrochloride and 0.4 g of dry caustic soda were mixed in alcohol and the mixture was dried and was powdered. The greenish yellow powder was in alcohol and ethylene glycol monoethyl ether highly soluble and had a melting point of 165 to 168 °. The corresponding On the other hand, oxynaphthoic acid a-naphthanilide is practical in the above solvents insoluble and has a melting point of 22o to 22I °.

The sodium salts of 2-oxy-3-carbazolecarboxylic acid p-chloroanilide and of β-oxynaphthoic acid-a-naphthanilide melt with decomposition. It is known that this is a peculiarity of the sodium salts of the compounds in question.

0.6575 g of β-oxynaphthoic anilide were dissolved in zoo cc of methyl alcohol. To this solution was added 0.46 g of guanidine carbonate, which had been dissolved in about 10 cc of distilled water. This solution was added to 0.6575 g of the above β-oxynaphthoic anilide, which had been completely dissolved in 600 cc of methyl alcohol. The methyl alcohol was then distilled off.

The X-ray diffraction pattern of the crystalline product thus obtained was obtained with the X-ray diffraction pattern of a sample of β-oxynaphthoic anilide on the one hand and of guanidine carbonate on the other hand.

The diffraction patterns were obtained by using a narrow bundle of rays was passed through a thin sample of each of the compounds examined. The X-ray beam itself was hidden in a small lead capsule. The diffraction effects, obtained from the samples were then imaged on a curved film, which was enclosed in black paper.

It has been known for many years that these X-ray diffraction patterns of crystalline substances are very characteristic and for identification such substances can be used.

The X-ray diffraction patterns obtained from the three compounds are shown in the drawing. This drawing shows that the experiment 3, carried out with the salt from the guanidine carbonate and the ß-oxynaphthoic anilide provides a diffraction pattern that of the images of guanidine carbonate on the one hand and the oxynaphthoic anilide on the other hand is completely different. Thus the images of the latter compounds in Experiment No. 3 are perfect disappeared. This sample therefore corresponds to a new crystalline state of the Substance that results from the formation of a compound that is so persistent that it can be isolated.

The foregoing attempts made with various ice color coupling components and guanidine compounds have been carried out suggest that the Guanidine compound forms a salt with the ice color coupling component, from which is explained by the fact that the guanidine compound produces strong, even colors the process of making ice colors by coupling an amine base with a Coupling component supplies.

The invention is described in more detail with reference to the following examples.

Example i 0.1 g of 4-benzoylamino-2, 5-diethoxyaniline, o, iio g ß-oxynaphthoyl-p-chloroanilide, o, oi g of oleylmethyltaurine and o, 3 g of guanidine carbonate were in 1 cc of ethylene glycol monoethyl ether, 1.5 ccm of hot water and 0.25 ccm of caustic soda solution at 40 ° B6 dissolved. The mixture was then slowly heated and diluted in the desired manner (e.g. zoo cc warm water was added). A sample of polyamide fibers from io g was then treated in the above bath at 60 to 65 ° for 45 minutes and then rinsed. The material was then placed in a bath containing 5% sodium nitrite (calculated on the material weight) and 10 ° / a acetic acid (calculated on the material weight) and was left in the bath at 60 to 65 ° for 20 minutes. It then became rinsed and finished in the usual way.

A strong greenish-blue coloration of the polyamide fibers was obtained, which was much stronger and more vivid than in the case of a sample which had been dyed in the same way but without the addition of the guanidine carbonate. Example 2 The procedure of Example i was repeated using acetate silk instead of polyamide fibers. The colorations obtained on the acetate silk corresponded approximately to those obtained on the polyamide fibers. Example 3 There were dissolvedo, 194-Benzoylanüno-2, 5-diethoxyaniline, o, i-, og ß-oxyanthroyl-o-toluid, o, oi g oleylmethyltaurine and 0.3 g of guanidine carbonate and as in Example i for dyeing polyamide fiber and acetate silk samples used.

A vivid green turned on the polyamide fibers and the acetate silk Color obtained which was much stronger and more vivid than if the guanidine carbonate was omitted.

Example 4 o, ig 2-amino-4,4'-dichlorodiphenyloxide, 0.13 g of β-oxynaphthoyl-i-naphthylamide, o, oi g of oleylmethyltaurine and 0.3 g of guanidine carbonate were dissolved as in Example i. A sample of a fabric made of polyamide fibers weighing 10 g, which was impregnated as in Example i, was in a developing bath containing 50 % sodium nitrite (calculated on the weight of the material) and 5 °; o Contains sulfuric acid (calculated on the weight of the material), leave it for 20 minutes at 60 to 65 °. After rinsing and finishing, a very strong and vivid blue-tinged red tone was obtained on the fiber, which was much more vivid and vivid than if the guanidine carbonate was omitted. The result is the same with acetate silk. Example 5 o, ig 2-amino-4,4'-dichlorodiphenyloxide, 0.175 g of 4 'benzoylacetan-iino-2', 5'-dimethoxybenzanilide, o, oi g of oleylmethyltaurine and 0.3 g of guanidine carbonate were dissolved and as in Example 4 used for dyeing polyamide fibers. A very strong, golden yellow tone was obtained on the polyamide fibers, which is considerably more vivid than is obtained if guanidine carbonate is excluded. Similar results were obtained with acetate silk.

Example 6 o, rg aminoazotoluene, o, = 5 g of β-oxynaphthoyl-2-naphthylamide, o, oi g of oleylmethyltaurine and 0.3 g of guanidine carbonate were dissolved and used as in Example 4 for dyeing polyamide fibers and acetate silk. In both cases a very lively, chestnut-brown shade was obtained which, when the guanidine carbonate was used, was much stronger and livelier than when the same dyeing was carried out with the exclusion of the guanidine carbonate.

Example 7 o, 1 g of aminoazotoluene, o, 185 g of 2-oxy-ii-benzo- (a) -carbazole-3-carboxylic acid-p-aniside, o, oi g of oleylmethyltaurine and o, 3 g of guanidine carbonate were dissolved and as in the example 4 used for dyeing polyamide fibers and acetate silk. When using guanidine carbonate strong deep black tones were obtained, while with the exclusion of guanidine carbonate only dull, grayish black tones were obtained.

Example 8 0.05 g of 5-methyl-o-anisidine, 0.11 g of β-oxynaphthoylm-nitroanilide, 0.1 g of oleylmethyltaurine and 0.3 g of aminoguanidine bicarbonate were dissolved as in Example i. A pattern of polyamide fibers of 10 g was impregnated in this solution as in Example i and then developed in a bath (10 minutes at 60 to 65 °) which contained 5% sodium nitrite and 5% sulfuric acid. The bath was neutralized with 7% ammonia (calculated on the weight of the material), whereupon the color was allowed to develop for a further 0 minutes. The swatch was then rinsed and finished as usual. A lively, strong burgundy red tone was obtained on both polyamide fibers and acetate silk, which is very different from the same colorations with the exclusion of the guanidine compound.

Example g The procedure was the same as in Example i, except that 0.3 g of aminoguanidine bicarbonate was substituted for the guanidine carbonate. The colorations obtained corresponded approximately to those of example i. Example = oo, ig 5-methyl-o-anisidine, 0.22 g of 5-chloro-2,4-dimethoxyacetoacetanilide, ooi g of oleylmethyltaurine and 0.3 g of guanidine carbonate were dissolved and colored as in Example i. A vivid greenish yellow coloration was obtained both on polyamide fibers and on acetate fibers. Without the addition of guanidine carbonate, the tone was reddish, dull and weak.

Example = io, ig 2-amino-4, 4'-dichlorodiphenyloxyd, o, o8 g of phenylmethylpyrazolone, o, oi g of oleylmethyltaurine and 0.3 g of guanidine carbonate were dissolved and used as in Example 4 for dyeing polyamide and acetate fibers. A yellow tone was obtained which was considerably stronger than in the case of the same colorations carried out without guanidine carbonate.

Example 12 The procedure was the same as Example i, but the guanidine carbonate was replaced by 0.3 g of guanidine hydrochloride. The results were practically the same.

Example 13 The procedure was the same as Example i, but became replaced the guanidine carbonate with guanidine sulfate. The colorations obtained were excellent.

Example 14 0.06 g of 4-benzoylamino-2,5-diethoxyaniline, 0.05 g of β-oxynaphthoic anilide and 0.3 g of β-diphenyl biguanide were dissolved in 2 cc of ethylene glycol monoethyl ether. This solution was poured into zoo cc warm water containing 0.025 g oleyl methyl taurine.

In this solution a pattern of polyamide fibers with a weight of 45 minutes was dyed at 65 °, then rinsed and developed in a fresh bath containing 5 % sodium nitrite and 0% acetic acid for 20 minutes at 6o to 65 °. The colorations were rinsed and finished in the usual way. Deep blue colorations were obtained on the polyamide fibers and also on the acetate silk if they were treated as above, on the other hand the colorations were dull and weak without the use of the β-diphenyl diguanide.

Example 15 The procedure was the same as Example 14 but was the ß-diphenyl biguanide replaced by guanidine. The results obtained corresponded practically those of example 14.

Example 16 The procedure was the same as Example 8 except that 0.3 g of guanidine acetate was substituted for the aminoguanidine bicarbonate. The colors were roughly the same as in Example B.

Example 17 The procedure was the same as Example i, but became replaced the guanidine carbonate with guanidine nitrate. In this case, too, were excellent Preserved discoloration.

Example 18 0.06 g of 4-benzoylamino-2,5-diethoxyaniline, 0.05 g of β-oxynaphthoic anilide and 0.3 9 β-diphenyl biguanide were dissolved in 2 cc of ethylene glycol monoethyl ether and 0.25 cc of sodium hydroxide solution at 40 ° B6. This solution was poured into zoo cc warm water containing 0.25 g of oleynethyltaurine. As in Example 14, vivid dark blue colorations were obtained on the polyamide fibers and the acetate silk. Example 1 0.1 g of 2-amino-4,4'-dichlorodiphenyloxide, 0.13 g of β-oxynaphthoic acid-i-naphthylamide, 0.1 g of oleylmethyltaurine and 0.3 g of phenyl biguanide were dissolved as in Example i. That. Coloring was carried out as in Example 4 and the same results were obtained.

Example 2o 0.1 g of 2-amino-4,4'-dichlorodiphenyloxide, 0.13 g of β-oxynaphthoyl-2-naphthylamide, 0.1 g of olymnethyltaurine and 0.3 g of phenyl biguanide hydrochloride were dissolved, colored and developed as in Example . Strong, vivid red colorations were obtained on acetate silk and polyamide fibers.

Example 21 o, 1 g of the compound of the following formula: o, ii g ß-oxynaphthoyl-p-chloroanilide, o, oi g oleylmethyltaurine and 0.3 g guanidine carbonate were dissolved as in example i. When dyeing polyamide fibers and acetate silk, a deep black tone was obtained on both fibers during development as in Example 4.

Example 22 0.1 g of 2-amino-4, 4'-dichlorodiphenyloxide, 0.13 g of β-oxynaphthoyl-i-naphthylamide, 0.1 g of oleylmethyltaurine and 0.3 g of biguanide were dissolved as in Example. The results obtained correspond to those of example ig.

Example 23 0.1 g of 2-amino-4, 4'-dichlorodiphenyloxide, 0.13 g of β-oxynaphthoyl-i-naphthylamide, o, oi g of oleylmethyltaurine and o, 3 g of biguanide hydrochloride were as in the example ig solved. The results corresponded to the example ig.

Example 24 2.97 g of β-oxynaphthoic acid p-chloroanilide and 2.73 g of p-diphenyl biguanide were mixed well with a sufficient amount of alcohol until a yellow colored uniform paste was obtained. The paste was stirred at 5o ° under reduced - dried then ground to a fine powder and pressure. The slightly amber-yellow powder is the ß-diphenyl biguanide salt of ß-oxynaphthoic acid-p-chloranilide. Its melting point is 137 to 143 °, and it is soluble in alcohol and ethylene glycol monoethyl ether with the formation of greenish yellow solutions.

0.220 g of this product and 0.075 g of 2-amino-4, 4'-dichlorodiphenyloxide were dissolved in 1 cc of ethylene glycol monoethyl ether and 0.25 cc of sodium hydroxide solution at 40 ° B6. This mixture was mixed with zoo cc of warm water which contained 0.1 g of the reaction product of a naphthalene sulfonate with formaldehyde. A sample of polyamide fibers weighing 10 g was impregnated with this solution at a temperature of 60 ° for 45 minutes and then developed for 20 to 30 minutes at 60 ° with 5% sodium nitrite and 5% sulfuric acid. The dyeings were rinsed and dried in the usual manner, whereby a bright red tone was obtained. When dyeing acetate silk, the sulfuric acid in the developing bath is expediently replaced by 100% acetic acid. Example 25 3.27 g of β-oxyanthronic acid-o-toluidide, 1.35 g of aminoguanidine bicarbonate and 0.40 g of dry caustic soda were combined with enough alcohol to make one The paste was mixed well, dried at 50 ° under reduced pressure and ground to a fine brick-red powder which is soluble in alcohol and ethylene glycol monoethyl ether and has a melting point of about 360 °.

.0.16o g of the above product and 0.08o g of 4-amino-2,5-diethoxybenzanilide were in 1 ccm of ethylene glycol monoethyl ether and 0.25 ccm of sodium hydroxide solution at 40 ° B6 solved. This solution was poured into zoo cc warm water containing o, ioo g des Contained reaction product of a naphthalene sulfonate with formaldehyde.

A sample of acetate silk of 10 g for 45 minutes was impregnated with this solution at 60 °, then rinsed and finally developed for 20 to 30 minutes at 60 ° with 50% sodium nitrite and 30% acetic acid (28 ° B6). The coloring was rinsed and finished as usual; it was a strong green tone.

Similar results were obtained when polyamide fibers were dyed instead of acetate silk. EXAMPLE 26 3.37 g of 2-oxy-3-carbazolecarboxylic acid p-chloroanilide, 0.955 g of guanidine hydrochloride and 0.40 g of dry caustic soda were mixed well with enough alcohol to form a paste, whereupon the paste was dried at 50 ° under reduced pressure and then added a fine powder. The light brown-yellow powder had a melting point of Zig to 224 ° and was soluble in alcohol and ethylene glycol monoethyl ether.

0.140 g of the above powder, 0.065 g of the reaction product of a naphthane sulfonate with formaldehyde and 2-amino-4,4'-dichlorodiphenyl oxide were dissolved as in Example 24. The polyamide fibers dyed as in Example 24 had a deep brown tone. Example 27 3.13 g of β-oxynaphthoic acid-a-naphthanilide, 2.4 g of phenylbiguanide hydrochloride and 0.409 of dry caustic soda were mixed in alcohol, dried and powdered. The greenish yellow powder obtained was soluble in alcohol and ethylene glycol monoethyl ether and had a melting point of 165 to 168 °.

0.180 g of the above powder and 0.075 g of 2-amino-4,4'-dichlorodiphenyloxide were dissolved as in Example 24. The dyeings obtained on polyamide fibers and acetate silk were as in Example 24, specifically in a lively bluish-tinted red shade.

Example 28 3 g of β-oxynaphthoic acid-2-naphthylamide, 2 g of guanidine carbonate, 2 g of the reaction product of a naphthalene sulfonate with formaldehyde and 0.44 g Caustic soda were mixed and placed in a mixer at about go ° with water processed into a paste. The latter was dried under reduced pressure at go °. The greenish yellow product is soluble in alcohol and ethylene glycol monoethyl ether.

0.25 g of the above product and 0.1 g of 4-amino-2, 5-diethoxybenzanilide were dissolved as in Example 25 and the colorations produced as in Example 25. A dark greenish blue tone was obtained on polyamide fibers and acetate silk.

Example 29 19 4-Amino-2,5-diethoxybenzanilide, ig ß-oxynaphthoic acid-p-chloroanilide and ig guanidine carbonate were mixed and made into a fine powder.

0.31 g of this mixture were dissolved in 0.5o ccm of ethylene glycol monoethyl ether and 0.25 cc of sodium hydroxide solution at 40 ° B6 dissolved. This solution was made with zoo ccm warm Water containing oleyl taurine, diluted. With this solution a polyamide or acetate silk swatch impregnated with io g and as in example i with the same results developed. Example 30 1.30 g of β-oxynaphthoic acid-i-naphthylamide and i g of β-diphenyl biguanide were mixed and ground to a fine even powder.

0.23 g of the above mixture, 0.1 g of 2-amino-4, 4'-dichlorodiphenyloxide and 0.1 g of oleylmethyltaurine were dissolved as in Example 4. When dyed as in Example 4, vivid blue-tinged red tones were obtained on polyamide fibers and acetate silk.

Example 31 i g of aminoazotoluene and i g of guanidine carbonate were mixed and ground into a fine uniform powder. 0.2o g of the above powder, ö, 1 @ g ß-oxynaphthoic acid-2-naphthylamide and o, oi g oleylmethyltaurine were dissolved and developed as in Example 3. It became very strong, lively chestnut browns Get tones.

Example 32 0.075 g of 2-amino-4,4'-dichlorodiphenyloxide, 0.1 g of β-oxynaphthoic acid-p-chloroanilide and 0.40 g of guanidine carbonate were admixed with 1 cc of ethylene glycol monoethyl ether. The mixture was heated slowly and the resulting yellow-colored solution was poured into 200 cc of warm water containing 0.03 g of oleylmethyltaurine. The solution had a milky appearance.

In this bath, a sample of polyamide fibers of 10 g was used for 45 minutes Impregnated at 60 °. During the impregnation, the polyamide yarn turned dark, greenish yellow, and the bath was complete with the ß-oxynaphthoic acid-p-chloroanilide exhausted. The greenish yellow color of the polyamide fibers results from the formation of the guanidine salt of ß-oxynaphthoic acid-p-cbloranilids on the fiber.

The pattern was then developed by treating it with 5% sodium nitrite and 5% sulfuric acid at 60 ° for 30 minutes, after which it was rinsed and finished in the usual manner. A strong, vivid red color was obtained. Example 33 0.08 g of 4-amino-2,5-diethoxybenzanilide, 0.075 g of β-oxynaphthoic anilide and 0.300 g of guanidine carbonate were dissolved with 1 cc of ethylene glycol monoethyl ether. The mixture was heated slowly and then poured into zoo cc of warm water containing 0.02 g of oleylmethyltaurine. A greenish yellow solution was obtained.

A sample of polyamide fibers from io g was greenish with this Solution impregnated at 60 ° for 45 minutes and then rinsed. The polyamide fibers stained turned deep yellow, and the coupling component was practically completely exhausted.

The color was then developed by treating it with 5% sodium nitrite and 10% acetic acid at 60 ° for 30 minutes. The swatch was rinsed and finished in the usual way. A very strong blue color was obtained. EXAMPLE 34 0.1 g of 4-amino-2,5-diethoxybenzanilide and 0.1 g of β-oxynaphthoic anilide were dissolved with 1 cc of ethylene glycol monoethyl ether and 0.25 cc of sodium hydroxide solution (40 ° B6). This solution was poured into a prepared solution which consisted of 0. oi g of oleylmethyltaurine and 0.2o g of guanidine carbonate in zoo cc of water.

10 g of polyamide fibers were impregnated in this solution at 60 ° for 45 minutes, then rinsed and finally 30 minutes at 60 ° with 5% sodium nitrite and 30% Acetic acid (28 ° B6) developed. The stain was then rinsed and used in the usual manner completed, a strong blue hue was obtained. With one in the same way, but the specimen treated without the addition of the guanidine salt was the color obtained very weak.

Example 35 5 g of β-oxynaphthoic anilide and 50 g of guanidine carbonate were made into a paste with alcohol on a steam bath. The alcohol evaporated in the process, and a yellow product remained as a residue, which was soluble in cold water.

This product is made from a mechanical blend of ß-oxynaphthoic anilide and guanidine carbonate, which has no yellow color and is in water dissolves to a yellow solution only with the application of heat.

In both cases, when developing with a diazonium compound any of the preceding examples obtained strong colors.

Example 36 50 g of β-oxynaphthoic acid p-chloroanilide and 50 g of guanidine carbonate were treated as in Example 35.

A mechanical mixture of the same coupling component and guanidine carbonate produced colorations that were just as strong as those produced with the above compound. Example 37 50 g of β-oxynaphthoic acid-2-naphthylwnide and 50 g of guanidine carbonate were mixed under the same conditions as in Example 35. A yellow powdery product was obtained, with which colorations were obtained, the properties of which were equivalent to those of a mechanical mixture of the coupling component and the guanidine carbonate Alcohol in a paste. As the mixture was heated, the yellow color of the toluidide gradually turned reddish brown, indicating a chemical reaction. When colored, the product had approximately the same coloring properties as a mechanical mixture of the above-mentioned toluidide and guanidine carbonate. Example 39 50 g of β-oxynaphthoic anilide and 50 g of guanidine carbonate were mechanically mixed with one another by grinding. An almost colorless mixture with coloring properties which were equivalent to those of the compound of Example 25 was obtained.

The following examples illustrate the manner in which the guanidine compounds Affect the attachment of the ice color coupling components to polyamide fibers.

Example 40 10 g of β-oxynaphthoic acid m-nitroanilide were mixed with 1 cc Ethylene glycol monoethyl ether and 1/4 ccm sodium hydroxide solution (40 ° B6) dissolved. This solution was with 150 cc of warm water, the o.10 g of the reaction product of a naphthalene sulfonate with formaldehyde, diluted.

To g of polyamide yarn were immersed in this bath at 60 ° for 45 minutes and then rinsed. After this time, a test of the impregnation bath with a Spectrophotometer that 6o, 60 /, of ß-oxynaphthoic acid-m-nitroanilide on the fiber raised and 39W04 remained in the bath.

o, iog ß-oxynaphthoic acid-m-nitroanilide and o, 2og guanidine carbonate were dissolved with 1 ccm of ethylene glycol monoethyl ether and 1 / $ ccm of sodium hydroxide solution (40 ° B6). This solution was diluted with 150 cc of warm water, the o.10 g of the reaction product of a naphthalene sulfonate with formaldehyde.

Ten grams of polyamide yarn was immersed in this bath as above. When the impregnation bath was tested with a spectrophotometer, it was found that 92.7% of the β-oxynaphthoic acid-m-nitroanilide was taken up by the fiber and only 7.3% remained in the bath, in contrast to the same experiment without guanidine carbonate , in which the values 6o, 6 and 39.4 0/0 were obtained. EXAMPLE 41 0.975 g of ß-oxynaphthoic anilide and 0.08 g of 4-benzamino-2, 5-diethoxyaniline were dissolved in 1 cc of Äthylenglyko'.monoäthyläther and 1/4 cc of sodium hydroxide solution (40 ° Be), and this solution was then with 150 ccm warm water containing o, IO g of the reaction product of a naphthalene sulfonate with formaldehyde, diluted.

10 g of polyamide yarn were dyed for 45 minutes at 60 °, rinsed and then with 511%, sodium nitrite (calculated on the weight of the polyamide) and 10% acetic acid Developed in 150 cc of water for 30 minutes at 60 °.

The dyebath was tested spectrometrically as in Example 40, and it was found that 43.7% of the β-oxynaphthoic anilide was taken up by the fiber and 56.3% remained in the bath.

0.075 g ß-oxynaphthoic anilide, o, o8o g 4-benzamino-2, 5-diethoxyaniline and 0.2oo g of guanidine carbonate were dissolved in 1 cc of ethylene glycol monoethyl ether and% cc Caustic soda (20 ° B6) dissolved. This solution was diluted with 150 cc of warm water, which contained 0.1 g of the reaction product of a naphthalene sulfonate with formaldehyde.

Ten grams of polyamide yarn were dyed and developed as above. When testing with the spectro = photometer it was found that 71.8% of the ß-oxynaphthoic anilide had been absorbed by the fiber and only 28.2 % was left in the bath, in contrast to the above values of 43.7 or 56.3%. In addition, the yarn dyed using guanidine carbonate was much more vivid and darker in tone than when no guanidine carbonate was used.

About 60% of the β-oxynaphthoic acid m-nitroanilide was consumed without and 93 % with guanidine carbonate. As a result, 64 parts of this amide plus guanidine carbonate should be at least zoo parts of the amide without guanidine carbonate. The following baths were set up accordingly. (Unless otherwise stated, the quantities are grams.) control I II III IV ß-Oxynaphthoic acid-m-nitroanilide ................ o, ioo o, ioo 0, o64 0.032 Guanidine carbonate ............................... - 0.200 o, 2co 0.200 Caustic soda (40 ° B6). . . . . . . . . . . . . . . . . . . . . . . . . . . . 1, '1 ccm 1 / $ ccm 1 / $ ccm 1; s ccm Ethylene glycol monoethyl ether ...................... 1. 2 cc 1, '2 cc 1/2 cc 1,' 2 cc Warm water .. . .... ... .... .... . ... . . ... ... 150 ccm 150 ccm 150 ccm 150 ccm Reaction product of a naphthalene sulfonate with Formaldehyde. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . o, ioo 0.100 o, ioo o, ioo 10 g polyamide yarn in strand form were impregnated in the baths mentioned for 45 minutes at 6p °, then rinsed in fresh water and finally developed for 45 minutes at 35 ° in a bath containing 3 g of 2-methoxy-4-anilinoanilinediazonium sulfate, 0.3 ccm des The reaction product of oleyl alcohol with ethylentene and 300 ccm of water contained. The yarn was soaped at the boil for 5 minutes, rinsed and dried.

The coloration from the bath II (control bath) is extremely strong and lively. The color from bath III is much stronger than that from bath I. According to the calculations, the same amounts of ß-oxynaphthoic acid-m-nitroanilide should be used be taken from baths I and III. Half the amount of anilide was in bath IV as used in Bad III, but Bad IV still provided a stronger and livelier one Colored as bath I. This proves that guanidine carbonate is a very advantageous one Has an effect.

Example 42 The following two baths were made: I II 5-chloro-2,4-dimethoxy acetoacetanilide. . . . . . . . . . o, 250 g 0.2509 Guanidine carbonate. . . . . . . . . . - 0.3009 Ethylene glycol monoethyl ether 1/4 ccm 1/4 ccm Caustic soda 40 ° Be. . . . . . . . . 1/4 cc - warm water . . . . . . . . . . . . 150 cc 150 cc 5-methyl-o-anisidine. . . . . . . . o, iio go, iio g Oleyl methyl tauride. . . . . . . . o, oio go, oio g Ethylene glycol monoethyl ether 1/4 ccm 1/1 ccm The 5-chloro-2,4-dimethoxyacetoacetanilide, ethylene glycol monoethyl ether and caustic soda on the one hand and guanidine carbonate on the other hand were diluted with the water, and the mixture of 5-methyl-o-anisidine, oleyl methyl tauride and ethylene glycol monoethyl ether was then added . Polyamide yarn weighing 10 g was then impregnated for 45 minutes at 60 °, rinsed and developed with 5 ° / p sodium nitrite (calculated on the weight of the material) and 10% acetic acid in 300 ccm of water for 30 minutes at 60 °. The colorations were then completed in the usual way.

The coloring from the bath I, which did not contain any guanidine carbonate, was dull orange-yellow, while the one made with the use of guanidine carbonate Coloring had a very lively, strong greenish yellow tone.

Claims (5)

PATENT CLAIMS; i. Process for dyeing polyamide fibers and acetate silk with ice dyes by impregnating the fibers with an amine base and an ice color coupling component, then diazotizing the base and coupling the diazo compound with the coupling component, characterized in that the impregnation of the fibers with at least one of the components mentioned, preferably with the Ice color coupling component, in the presence of a guanidine compound of the following compositions in which R1 and R2 are hydrogen or an alkyl, aryl, aralkyl or cycloalkyl group, or the salts of these compounds and the guanidine compound is used in amounts of not more than 5 percent by weight of the material to be colored. 2. The method according to claim i and 2, characterized in that that the fibrous materials in the presence of the guanidine compound with an aqueous solution the amine base and the ice dye coupling component are impregnated. 3. Procedure according to claim i and 2, characterized in that the fibrous materials with an aqueous Solution of a reaction product from the ice color coupling component and the guanidine compound and the amine base are impregnated. 4. The method according to claim i to 4, characterized characterized in that guanidine carbonate is used as the guanidine compound. 5. Procedure according to claims i to 4, characterized in that guanidine carbonate is used as the guanidine compound and a ß-oxynaphthoic acid arylide is used as the coupling component.