US2649353A

US2649353A - Dyeing of nylon and acetate silk in

Info

Publication number: US2649353A
Authority: US
Publication date: 1953-08-18
Anticipated expiration: 1970-08-18

Description

Patented Aug. 18, 1953 DYEING F NYLON AND ACETATE SILK IN SITU WITH ICE COLORS Clemens Streak, Loudonville, N. Y., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application February 23, 1950, Serial No. 145,715

8 Claims. 1

The present invention relates to an improvement in the dyeing of nylon and acetate rayon by impregnating the fibers with an ice-color coupling component and an amine base in the presence of a guanidine compound, and subsequently forming azo dyes therefrom on the fiber.

It has been proposed to dye nylon or acetate rayon fibers by impregnating the fibers with an alkali metal salt, 1. e., sodium salt of an ice-color coupling component and an amine base and subsequently diazotizing the base and coupling the same with the ice-color coupling component. The dyeings obtained in this way, however, are of little commercial value, being weak, off-shade dyeings of poor fastness properties.

The inability of the art to obtain satisfactory dyeings by the above procedure is attributable (l) to the very low affinity of the fibers for the salt of the ice-color coupling component, (2) to the considerable decomposition ofthe diazonium compound which occurs before formation of the color in the fiber takes place, and (3) to incomplete coupling of the salt of the ice-color coupling component and the diazom'um compound.

Attempts had been made to eliminate these objections by employing swelling agents, such as alcohol, Cellosolve, thiocyanates and thiourea in an effort to increase the afiinity of the fibers for the dye components. The improvement attained in this way is at best minor and is more than oifset by the increase in cost resulting from the use of the rather expensive agents involved. As a matter of fact, the status at the present time of nylon dyeing by means of an ice-color coupling component and an amine base is rather precisely stated by the following extract from page 748 of the issue of October 17, 1949, of American Dyestufi Reporter: The Naphthol dyes can be applied with the prepare and base in one bath and subsequently be diazotized and developed in one operation in a second bath. However, we have not succeeded in obtaining on nylon the bright shades obtained on cotton, nor have we obtained the light and crocking fastness that is required. Work is being continued to obtain the desirable properties of the Naphthol dyes on nylon.

It has now been discovered that the aforementioned method may be utilized in connection with nylon or acetate rayon fibers while obtaining dyeings having a satisfactory depth of shade and brightness and excellent fastness properties by effecting the impregnation of the fibers in the presence of a guanidine compound. The

guanidine compound operates in a poly functional manner in insuring the formation of excellent dyeings. Thus, it increases the affinity of the fibers for the coupling component by converting the ice color coupling component into a salt which is more strongly attracted by the fibers than the coupling component per se or its sodium salt. The coupling componentguanidine salt imparts greater stability to the diazom'um compound than the corresponding sodium salt. Finally, it effects a buffer efiect leading to more even and brilliant dyeings.

The dyeing of nylon and acetate rayon fibers with an ice color by impregnating the fibers with an ice color coupling component and an amine base while insuring the presence of a guanidine compound during such impregnation, salts of guanidine compounds with ice color coupling components, and impregnating compositions containing a guanidine compound and one or both of the aforesaid dye components constitute the purposes and objects of the present invention.

The amine base employed may be any aromatic primary amine useful in the preparation of azo dyes. Examples of such amines are:

4-nitro-o-anisidine 2,5-dichloro aniline i-benzoylamido-2,5-diethoxy aniline 2-amino-4,4-dichlor-diphenyl oxide Amino azo toluene 5-methyl-o-anisidine m-Chlor aniline o-Chlor aniline 4-nitro-o-toluidine 4-amino-S-benzoylamino-m-xylene Tolidine 1 3-amino carbazole Amino azo benzene 4-chloro-o-toluidine a-Naphthylamine 4-amino-4-dihydroxyethylaminoazobenzene 4-chloro-2-m'tro aniline 4,4'-diamino diphenylamine l-amino-anthraquinone N- (p-aminobenzoyl) -p-toluidine, and the like.

Such compounds, as is well known, are typical ice-color bases.

The coupling component to be utilized in forming the azo dye is any of the well knownicecolor coupling components. Examples of such compounds are the following Naphthol AS type compounds:

,8Hydroxy naphthoic-p-chloranilide cally mixed and the mixture dissolved and ap plied to the fibers. Finally, the guanidine compound and the ice color coupling component may be reacted to form a salt and the salt and the amine base may be dissolved and appliedto the fibers. Irrespective of the particular mechanical method utilized in bringing the components on the fiber, the net result is invariably the same, to wit, dyeings are obtained 3-hydroxydiphenyleneoxide2 carboxylic amine 3-hydroxydiphenyleneoxide 2 carboxylic acid anisidide 9-methyl-2-hydroxycarb'azole 3- carboxylic acid anilid'e 9-methyl-2-hydroxycarbazole-3-carboxylic acid anisidi'de 9-methyl-2hydroxycarbazole-3-carboxylic acid toluidide 3-hydroxy fluorene-Z-carboxylic acid o-toluidide,

and .the like.

Guanidine' compounds which I have found to be effective for my purpose are those of the following formulae:

wherein R1 and R2 are hydrogen, alkyl such as methyl, ethyl, propyl, butyl, octyl, decyl and the like, aryl such as phenyl, naphthyl, tolyl, ethylphenyl and the like, aralkyl such as b'enzyl, 'menaphthyl and the like, cycloaliphatic such as cyclopentyl, cyclohexyl and the like, and. the salts of such compounds, .suc'h, as carbonate, hydrochloride, nitrate, sulfate, phosphate and acetate. Illustrative examples of such compounds are guanidine, guanidine carbonate, guanidine hydrochloride, guanidine sulfate, guanidine nitrate, guanidine acetate, guanidine, phosphate, amino guanidine, amino guanidine bicarbonate, amino guanidine'. hydrochloride, amino guanidine sulfate, B-diphenyl biguanide, B-diphenylbiguane ide hydrochloride, methyl guanide, ethyl guan ide, propyl guanide, phenyl guanide, N,N-diphenyl guanide, benzyl guanide, B-dibenzylbiguanide, biguanide hydrochloride, phenyl biguanide hydrochloride, methyl biguanide, ethyl biguanide hydrochloridaand the like.

The effect desired .byutilization of th e guanidine compound may be realized in a numberof ways. For instancathe amine base andthe guanidine compound may be dissolved, the ice color coupling component added to the solution and th solution applied to the fibers; or the ice color coupling component and the 'guanidine compound may be mech'ar'iically mixed and the mixture dissolved along with the amine base whereupon the. solution is applied to the fibers;

or the ice color coupling component, amine whilerealizing the particular advantages previ'ou'sly discussed.

For impregnation of the fibers, the components are applied thereto in the form of an aqueous solution. A smallamount of a water miscible organic solvent suchas ethanol, butanol, Cellosolve,- benzyl alcohol, ethylene glycol, and the like,

added t'o assist dissolution of the components if desired. Preferably a small amount of aZ-W-etting agent is included in the impregnation bath and for this purpose there may be employed, inter alia, oleyl methyl taurine, the addition product of diisobutyl phenol with '8 to 10 mole cules of ethylene oxide, th sulfonated' condensation product of benzene with keryl chloride (i. 'e.-, chlorinated kerosene), di-isobutyl naphthalene sulfonate, the product sold under the trademark Tamol NNO (a product produced by condensing, Z-naphthalene-sulfo-nic acid with formaldehyde), and the like.

The quantities of various dye components and guanidine compound employed may vary to a considerable extent. Usually, equivalent quantities of amine base and coupling component may be used but in practice it has been found that better results ensue when employing a slight excess of the coupling component.

The in'fiuence of the guanidine compound is-felt even when traces are added to the impregnation bath. It is recommended, however, that the quantity of the guanidine compound range from 1% to 5% by weight ofthe material to 'be dyed.

When the guanidi-ne compound is used in the form of a salt, it is desirable to include an alkali in the impregnation bath. For this purpose, there is preferably used a small'amount of a stron-g'inorganicor organic'base, such as caustic soda,-potassium, hydroxide, caustic potash, ethylene diamine, tetraethylene pentamine, or the'like.

After the impregnation of the fibers with the guanidine compound and the dye components, the fabric is subjected to the action of a 'diazotization bath containing sodiumnitrite and an acid such as sulfuric, hydrochloric, acetic, formic, or the like. The temperature of the bathmay vary from room temperature tothe boil'for about i to 45 minutes to permit dyeformationto take place. The materialis then rinsed and finished in the usual manner.

It has been s'tatedabove' that one of thee-ffects 0f the guanidine compound is-the'conversion of the ice color coupling component into'the'salt thereof, either in whole ;or impart, depending upon the quantities of the ice color coupling component and guani'dine compound employed; It has also been stated that salt formation may be effectedprior to the application of the components to the fibers. Where the saltis not preformed, it is consideredthatsalt formation inevitably takes place during dyeing of the fibers With the compositions containing-theguanidine compound.

7 Various tests have ibeen made forthe purpose of establishing that'salt formation actually results when treating various ice color coupling com ne s. wi eua idine com-pounds. 'Thus,

2.97 g. of c-hydroxynaphtholic acid p-chloroanilide and 2.73 g. of B-diphenylbiguanide were mixed with sufficient alcohol until a yellow colored uniform paste resulted. The paste is dried at 50 C. under vacuum and then milled to a fine powder. The light tan powder, i. e., the p-diphenylbiguanide salt of p-hydroxy-naphthoic acid p-chloroanilide, has a melting point of 137- 143 C. and is soluble in alcohol and Cellosolve forming greenish yellow solutions.

The corresponding c-hydroxynaphthoic acid p-chloroanilide is practically insoluble in these solvents and has a much higher melting point, to Wit, 262.5-263C.

The corresponding sodium salt has a high degree of solubility in the aforementioned solvents but does not have an exact melting point, decomposition setting in before melting occurs.

No caustic soda is present in any case, so that the sodium salt could not possibly have been responsible for the melting point determination which was made.

3.37 g. of 2-hydroxy-3-carbazoleca1 boxylic acid p-chloroanilide, .955 g. of guanidine hydrochloide and .4 g. of dry caustic soda are mixed well with sufficient alcohol to form a paste, dried at 50 C. under a vacuum and then milled to a fine powder. The light tan powder has a melting point of 219-224 C. and is soluble in alcohol and Cellosolve to a high degree.

The corresponding 2-hydroxy-3-carbazolecarboxylic acid p-chloroanilide is practically insoluble in the above solvents and has a melting point of 258.5-259.5 C. Salt formation accordingly occurred also in this instance.

3.13 g. of ,B-hydroxynaphthoic acid a-naphthanilide, 2.14 g. of phenylbiguanide hydrochloride and .4 g. of dry caustic soda are mixed in a1- cohol, dried and pulverized. The greenish yellow powder is soluble to a high degree in alcohol and Cellosolve and has a melting point of 165- 168 C.

The corresponding p-hydroxynaphthoic acid a-naphthanilide, on the other hand, is practically insoluble in the above solvents and has a melting point of 220-221 C.

The sodium salts of 2-hydroxy-3--carbazolecarboxylic acid p-chloroanilide and of fi-hydroxynaphthoic acid a-naphthanilide melt with decomposition. It is known that this is a pecularity of sodium salts of the type of compounds under discussion.

.6575 g. of ,B-hydroxynaphthoic acid anilide were dissolved in 200 ml. of methyl alcohol C. P. To the solution there were added .46 g. of guanidine carbonate dissolved in about ml. of distilled water. This solution in turn was added to .6575 g. of the above B-hydroxynaphthoic acid anilide which was dissolved completely in 600 ml. of methyl alcohol. The methyl alcohol was then distilled oil.

The X-ray diffraction pattern of the crystalline product thus obtained was compared with the X-ray diffraction pattern of a sample of ,3- hydroxynaphthoic acid anilide, on the one hand, and of guanidine carbonate on the other hand.

The diffraction patterns were obtained by permitting a narrow pencil radiation to penetrate a thin sample of each of the compounds under investigation. The X-ray beam itself is trapped in a small lead cup. The diffraction effects which arise from the sample are then recorded on a curved film wrapped in black paper.

It has been found over a period of many years 6 that these X-ray difiracti'on effects from crystalline materials are very characteristic and can be used as "finger prints for the identification of such materials.

The result of the X-ray diffraction pattern performed on the salt of guanidine carbonate and the beta-hydroxynaphthoic acid anilide shows a diffraction pattern differing entirely from the pattern obtained from guanidine carbonate on the one hand and of the beta-hydroxynaphthoic acid anilide on the other hand. The: patterns of the latter two compounds are completely absent in the pattern obtained from the salt of guanidine carbonate and the beta-hy droxy-naphthoic acid anilide, clearly indicating. therefore that the latter mentioned compound corresponds to a new crystalline state of matter resulting from the formation of a compound suificiently stable to be isolated.

The afcrestated tests, performed with different ice color coupling components and guanidine compounds, are considered to establish the conclusion that the guanidine compound forms a salt with the ice color coupling component, thus providing an explanation as to why the guanidine compound operates as it does to yield intense even dyeings by the amine base-ice color coupling component method.

The invention is further illustrated by the following examples, although it is to be understood that these examples are not limitative.

Example I .1 gram of 4-benzoylamido2,5-diethoxyaniline, .110 gram of p-hydroxy-naphthoic-p-ch1oroanilide, .01 gram of oleyl methyl-taurine and .3 gram of guanidine carbonate are dissolved in 1 cc. of Cellosolve, 1.5 cc. of hot water and .25 cc. of 40 B caustic soda. The mixture is heated gently and diluted to the desired dilution (as an example, 200 cc. of warm water are added). A sample of nylon weighing 10 grams is treated in the above bath for 45 minutes at 6065 C. followed by rinsing. The material is then transferfed to a bath containing 5% sodium nitrite (based on the weight of material) and 10% acetic acid (based on the weight of material) and maintained in the bath for 20 minutes at 60-65 C. The material is rinsed and finished in the usual manner.

A bright greenish blue coloration is obtained on the nylon, much stronger and brighter than in a sample dyed in similar manner without the addition of the guanidine carbonate.

Example II The procedure of Example I Was repeated While utilizing acetate rayon in lieu of nylon. The dyeings obtained on the acttate rayon were comparable to those obtained on the nylon.

Example III Example IV .1 gram of 2 amino-4,4-dichlorodiphenyloxide, .13 gram of p hydroxy-napthoic-1-naph-- .1. grain of 2-aniinoeAf-dichlorodiphenyloxide, .175 gramof: -benzoyla:ce.tamido -2: ,5 -di'- methoxybenzanilide,,.0l gram of oleylmethyltanrine and..3 gram of gnanidineg-carbonate are dissolved and employed. todya nylonasinExample IV. A very strong golden. yellow shade is obtained on the nylonwhichzis remarkablybrighterthan thatobtained ii the. guanidine carbonate. is excluded. A sample oiacetate rayon gives similar results.

Example VI .1 gram of aminoazotoluene. .15 gram-of fl-hydroxy-naphthoic-Znaphthylamide, .01 gram of oleylmethyltaurine and .3 gram ofguanidine carbonate are disolved' and dyed on nylon and acetate rayon as in Example IV. A very bright.

maroon shade is obtained inboth casesand the shade is much strongerandbrighter in the presence of the guanidine carbonate than in a similar; dyeing which excludes the guanidine carbonate;

Example VII' .1 gram. of: aminoazotoluene, .185 gram of 2- hydroxy ll benzo; (a) carbazole 3 carboxylic-p-aniside. .01: grant of oleyl-methyltaurine. and .3 era-moi guani'dine carbonate are dissolved; and-:- employed to. dye nylon and ace- 'tate. rayon asin Example IV. Strong, deep black shades are; obtained when guanidine carbonate is present Which contrast greatly to the dull grayish blaclc shades obtained when guanidine carbonate is excluded.

Example VIII .05 gram of 5-methyl-o-anisidine, .11 gram of ,c-hydroxy-naphthcic-m-nitroanalide, .01 gram of oleylmethyltaurine and .3; gram of" amidoguanidine bicarbonate are dissolved as in Example I. A gram sampl of, nylon is impregnated as in Example I and then developed in a bath containing 5% sodium nitrite and 5% sulfuric acid for 10 minutes at 60-65 C. The. bathis neutralized with 7% ammonia. (based on the weight of material) and the color is allowed to develop for another 10. minutes. The sample is rinsed and finished as usual. A bright, strong bordeaux shade is obtained on both nylon and acetate rayon which contrasts greatly to similar dyeings excluding the guanid-ine compound.

Example IX The procedure is the same as in Example I excepting that the guanidine carbonate is replaced by .3 gram of amido guanidine bicarbonate. The dyeings obtained. were quite similar to those of Example I.

Eaiample X ..1 gram of. 5-methyl-o-anisidine, .22 gram of 5 chloro 2 ,4 dimethoxy acetoacetanilide, .01

gram. 1 of oleylmethyltaurine and? .3 gram of guanidine carbonate are dissolved and dyed as-in Example I. A bright greenish yellow dyeing resuits. on bothnylon and acetate fibers. Without the addition of guanidine carbonate, the shade is reddish, dull and weak.

Example XI .l' gram of 2'-amino-4,l-dichlorodiphenyl oxide, .08 gram of phenyl methyl pyrazolone, .01 gram of oleylrnethyltaurine and .3 gram of guanidine carbonate are dissolved and employed to dye nylon and acetate fibers as in Example IV. A yellowish shade is obtained which is noticeably stronger than. similar dyeings made without guanidine carbonate.

Example XII The procedure is the same as in Example I excepting that the guanidine carbonate is re placed by .3 gram of guanidine hydrochloride. The results are substantially the same.

Example XIII The procedure is the same as in Example I excepting. that the guanidine carbonate is replaced by guanidine sulfate. The dyeings resulting' are excellent.

Example XIV .66 gram of 4-benzoylamido-2,5-diethoxyaniline, .05 gram of fi-hydroxy-naphthoic anilide and .3 gram of p-diphenylbiguanide are dissolved in 2 cc. of Cellosolve. This solution is poured into 200' cc. of warm water containing .025 grain of oleylmethyltaurine.

A 10 gram sample of nylon is dyed in this solution at 65 -C. for 45 minutes, then rinsed and developedin a fresh bath of 5% sodium nitrite and. 10% acetic acid for 20 minutes at Gil-65 G. The dyeings are rinsed and finished as usual. Deep blue. dyeings are obtained on the nylon also on acetate rayon when treated as above. Dyeings without the p diphenylbiguanide are dull and weak.

Example XV The procedure is the same as. in Example XIV excepting that the ,B-diphenyl biguanide is replaced by guanidine. The results are substantially the same as those of Example XIV.

Example XVI Eaample XV'I I I .06 gram of l-benzoylamido-lEa-diethoxyaniline; .05 gram of ,B-hydroxy-naphthoic anilide and .3 gram of B-ciiphenylbigUanide are dissolved in 2 cc.of'Cell'osolve and .25 cc. of caustic 49 B. This solution'is poured into 200cc. of warm water containing- .25 gram of oleyl methyl taurine.

Bright deep blue; dyeings. are obtained on nylon and'acetate rayon as in Example Example XIX' ..1 gram 0f. -zeamino lA -dichlor.odiphenyl oxide, .13 gram of fl-hydroxy-naphthoic-lnaphthylamide, .01 gram of oleyl methyl taurine and .3 gram of phenyl biguanide are dissolved as in Example I. Dyeing is as in Example IV and results are similar.

Example XX Example XXI .1 gram of the compound of the formula:

C2HiOH .11 gram of S-hydroxy-naphthoic-p-chloroanilide, .01 gram of oleyl methyl taurine and .3 gram of guanidine carbonate are dissolved as in Example 1. Nylon and acetate rayon are dyed and developed as in Example IV. A deep black shade is obtained on either fiber.

Example XXII .1 gram of oxide, .13 gram of ,B-hydroxy-naphthoic-l-naphthylamide, .01 gram of oleyl methyl taurine and .3 gram of biguanide are dissolved as in Example XIX. Results are similar to Example XIX.

Example XXIII .1 gram of 2-amino-4,4'-dichlorodiphenyl oxide, .13 gram of ,B-hydroxy-naphthoic-l-naphthylamide, .01 gram of oleyl methyl taurine and .3 gram of biguanide hydrochloride are dissolved as in Example XIX. Results are similar to Example XIX.

Example XXIV 2.97 g. of ,B-hydroxynaphthoic acidp-chloroanilide and 2.73 g. of fl-diphenylbiguanide are mixed well with sufficient alcohol until a yellow colored uniform paste is obtained. The paste is dried at 50 C. under vacuum and then milled to a fine powder. The light tan powder is the fi-diphenylbiguanide salt .of p-hydroxynaphthoic :acid p-chloroanilide. It has a M. P. of 137-143" C. and is soluble in alcohol and Cellosolve forming greenish yellow solutions.

.220 g. of this product and .075 g. of 2-amino- 4,4-dichlorodiphenyl oxide are dissolved in 1 cc. of Cellosolve and .25 cc. of caustic soda 40 Be. This is combined with 200 cc. of warm water containing .1 g. of "Tamol NNO. A 10 g. sample of nylon is impregnated with this solution for 45 min. at a temperature of 60 C. and developed with 5% sodium nitrite and 5% sulfuric acid for 20-30 min. at a temperatuer of 60 C. The dyeings are rinsed and dried as usual, giving a strong red shade. In dyeing acetate rayon, it is preferred to replace the sulfuric acid of the developing bath by acetic acid.

Example XXV 3.27 g. of fi-hydroxyanthroic acid o-toluidide, 1.35 g. of aminoguanidine bicarbonate and .40 g. of dry caustic soda are mixed well with sufficient alcohol to form a paste. The paste is dried at 50 C. under vacuum and milled to a fine brick red powder which is soluble in alcohol and Cellosolve and ha .3 M- B Somewhat a ove 360 C.

2-amino-4,4-dichlorodiphenyl 10 .160 g. of the above product and .080 g. of 4-amino-2,5-diethoxy-benzanilide are dissolved in 1 cc. of Cellosolve and .25 cc. of caustic soda 40 B. This solution is poured into 200 cc. of warm water containing .100 g. of Tamol NNO. A10 g. sample of acetate rayon is impregnated with this solution for 45 min. at 60 C., rinsed and developed with 5% sodium nitrite and 30% acetic acid (28 B.) for 20 to 30 min. at 60 C. The dyeing is rinsed and finished as usual, giving a strong green shade.

Similar results are obtained when dyeing nylon in place of acetate rayon.

Example XXVI 3.13 g. of B-hydroxynaphthoic acid-a-naphthanilide, 2.14.- g. of phenylbiguanide hydrochloride and .40 g. of dry caustic soda are mixed in alcohol, dried and pulverized. The greenish yellow powder is soluble in alcohol and Cellosolve and has a M. P. of 165 to 168 C.

.180 g. of the above powder and .075 g. of '2-amino-4,4'-dichloro-diphenyl oxide are dissolved as in Example XXIV. Dyeings on nylon and acetate are obtained as in Example XXIV, the coloration being a bright bluish red shade.

Example XX VIII 3.0 g. of s-hydroxynaphthoic acid-2-naphthy1- amide, 2 g. of guanidine carbonate, 2 g. of Tamcl NNO and .44 g. of caustic soda are mixed and pasted well with water in a mixer at about C. It was dried at 90 C. in a vacuum. The greenish yellow material is soluble in alcohol and Cellosolve.

.25 g. of the above product and. .10 g. of 4-amino-2,5-diethoxy-benzanilide are dissolved as in'Example XXV and dyeings made as in Example XXV. A deep greenish blue shade is obtained on nylon and acetate rayon.

Example XXIX 1 g. of 4-amino-2,5-diethoxybenzanilide, 1.1 g. of fl-hydroXy-naphthoic acid p-chloroanilide and 1.0 g. of guanidine carbonate are mixed together and pulverized into a fine powder.

.31 g. of this mixture are dissolved in .50 cc. of Cellosolve and .25 cc. of caustic soda 40 B. This is diluted with 200 cc. of warm water containing oleyl methyltaurine. A 10 g. sample of nylon or acetate rayon is impregnated with this solution and developed as in Example I with similar results.

Example XXX 1.30 g. of ,c-hydroxynaphthoic acid l-naphthylamide and 1.00 g. of ,B-diphenylbiguanide are mixed and ground to a fine uniform powder.

.23 g. of the above mixture, .1 g. of 2-amino- 4,4-dichloro-diphenyl oxide and .01 g. of oleyl methyltaurine are dissolved as in Example IV. V

11 Bright bluish red shades are obtained on nylon and acetate rayon when dyed as in Example IV.

Example XXXI 1.0g. of aminoazotoluene and 1.0 g. of guanidine carbonate are mixed and ground to a fine, uniform powder.

.20 gram of the above powder, .15 g. of ,B-hydroxynaphthoic acid-Z-naphthylamide and .01 g. of oleyl methyltaurine are dissolved and developed as in Example III. Very strong, bright maroon shades are obtained.

Example XXXII .075 g. of 2-amino-4,4'-dichlorodiphenyl oxide, .10 g. of B-hydroxy-naphthoic acid p-chloroanilide and. .40 g. of guanidine carbonate are combined with 1- cc. of Cellosolve. The mixture is gently heated and the yellowish colored solution is poured into 200 cc. of warm water containing. .03 g. of oleyl methyltaurine. The solution hasa milky appearance.

A 10 g. sample of nylon is impregnated in this bath for 45 min. at 60 C. During impregnation the nylon yarn takes on a deep greenish yellow coloration and the fi-hydroxynaphthoic acid-p-chloranilide is completely exhausted from the bath. The greenish yellow colorationof the nylon fiber is due to the formation on the fiber of the guanidine salt of the B-hydroxynaphthoic acid-p-chloranilide.

The sample is then developed by treatn'ient with sodium nitrite and 5% sulfuric acid for 30 min. at 60 C., rinsed and finished as usual. A strong, bright red coloration results.

Example XXXIIL .08 g. of 4-amino-2,5-diethoxybenzanilide, .075" g. of S-hydro'xyhaphthoic acid anilideand .300 g. of guanidine carbonate are dissolved with 1 cc. of Cellosolve. The mixture is heated gentl and then poured into- 20000. ofwarm water containing .020 g. of oleyl methyltaurine. A greenish y'ellovv solution is formed.

A g. nylon sample is impregnated with'thi's' greenish-solution for 45 min. at 60 C. and thenrinsed; The nylon takes ona deep yellow coloration and the coupling component is practically completely exhausted.

The dyeing is developed by treatment with 5% sodium nitrite and 10% acetic acid for min. at 60 C. The sample is rinsed and finished asusual. A very strong blue dyeing is obtained.

Example XXXI V .10 g. of 4-amino-2,5-diethoxybenzanilide and .09 g. of p-hydroxy-naphthoic acid anilide are dissolved with 1 cc. of Cellosolve and .25 cc. of caustic soda- This solution" is poured intoan already prepared solution containing-200 cc. of water, .01 g. of oleyl m'ethyltaurid'e' and" .20'-g. of guanidine carbonate.

10 g. ofnylo'n are impregnated in thisfsolution for min. at 60 C., then rinsed andldeveloped" with 5% sodium nitrite and 30% acetic. acid' (28 Bi) for 30min. at 60 C. The dyeing is rinsed: and finished as usual, yielding a strong blueshade. A sample treated in similar manner without the addition of the guanidine salt is very weak in color.

Example XXXV g; of B-hydroxynaphthoic acid. anilideand 50 g. of guanidine carbonate are pasted. up with alcohol on a steam bath. During this operation the alcohol evaporates off, leaving as residue a yellow stubstance which is solubleiii-col a e caustic soda (40 Be).

This product differs from a mechanical mixture of s-hydr'oxy naphthoic acid anilide and guanidinecarbonate which is not yellow in color and which dissolves in water only when heat is applied to form a yellow solution.

In both cases equally strong dyeings are obtained on developing with a diazonium compound of any of the preceding examples.

Example XXXVI 50 g'. of B hydroxynaphthoic-p-ch1oranilide and 50 g. of guanidinecarbonate are treated as in Example A mechanical mixture ofthe same coupling compound and guanidine carbonate give dyeings which are as strong as those produced with the above compound.

Example XXXVII 50 g. of fi -hydrox-yn'aphthoic-2-naphthylamide and 50 g". of guanidine carbonate are mixed to gether under the same conditions as in Example XXXV. A yellow" pulverulent substance results which exhibits dyeing properties equivalent to those of a mechanical mixture of the coupling component and-guanidine carbonate.

ExampleXXXl HI 50 g. of B-hydroxy'anthroic-o-toluidide are pasted up with alcohol on' a steam bath as in Example While heating the mixture, the yellowish color of the toluidide gradually changes to a' reddish brown, thus indicating a chemical reaction. The product exhibits about equal dyeing properties when dyed against a mechanical mixture of the aforesaidtol uidide and guanidine carbonate. a

50 g; of ,e-hy'droxy'nap'hthoi'c acid anilide and 50" g. of guanidine carbonate are mechanically m'ixedby grinding't'ogether'. An almost colorless mixture results which exhibits dyeing properties that are on a par'witli the' compound of Example The following indicate how guanidine compounds affect the exhau'stof ice color coupling components on nylon.

.10 g. or B-hydroxynaplithoic acid-m-nitroanili'd'e were dissolved with 1 cc. of Cellosolve and. A1. cc. of caustic soda (40 Bel). This solution was diluted with 150 cc. of warm water containing. .10 g. of Tamol NNO'.

10 g". of nylon ya'rn' were steeped-in this bath at C. for 45 mina-n'd then-rinsed. At this point the impregnating bath, on testing with a spectrophotometer, indicated that 60.6% of the c-hydroxynaphthoi'c acid m nitroanilide was taken up by the fiber and" 30.4% remained in the bath.

.10 g; of B hydroxynaphtho'i'c acid-m-nitroanilide and .20 g. of' guanidine carbonate were dissol'vedwith 1 cc. of Cellosolve and A; cc. of

with cc; orwa'rmwa'ter containing .10 g. of Tamol NNO.

10 g. of nylon yarn were steeped in this bath as above. The impregnating; bath, on testing with a spectrophotometer indicated that 92.7%

This solution was diluted Example X LI .075 g. of p-hydroxynaphthoic anilide and .08 g. of 4-benzamido-2,5-diethoxy-aniline were dissolved in 1 cc. of Cellosolve and 4 cc. of caustic soda (40 B.). This was diluted with 150 cc. of warm water containing .10 g. of Tamol NNO.

10 g. of nylon yarn were dyed for 45 min. at 60 C. and then rinsed and developed with 5% sodium nitrite (based on the weight of the nylon) and acetic acid in 150 cc. of water for 30 min. at 60 C.

The dyebath was tested by spectrophotometer as in Example XL, which test indicated that 43.7% of the B-hydroxynaphthoic acid anilide had been taken up by the fiber and 56.3% remained in the dyebath.

.075 g. of fl-hydroxynaphthoic anilide, .080 g. of 4-benzamido-2,5-diethoxy-aniline and .200 g. of guanidine carbonate were dissolved in 1 cc. of Cellosolve and cc. of caustic soda (40 B.). This was diluted with 150 cc. of warm water containing .10 g. of Talmol NNO.

10 g. of nylon yarn were dyed and developed as above. On spectrophotometric test, 71.8% of the B-hydroxy-naphthoic acid anilide was taken up by the fiber and only 28.2% remained in the dyebath in contrast to the above figures of 43.7% and 56.3% respectively.

Also the yarn dyed in the presence of the guanidine carbonate was much brighter and darker than in the case where the guanidine carbonate was missing.

The p-hydroxynaphthoic acid-m-nitroanilide exhausted to about 60% without and 93% with guanidine carbonate. Accordingly 64 parts of such amide plus guanidine carbonate should at least equal 100 parts of the amide without guanidine carbonate.

Accordingly the following baths were prepared (amounts are in grams, unless otherwise specified):

10 g. skeins of nylon yarn were impregnated in the respective baths for 45 min. at 60 C., then rinsed in fresh water and developed in a bath for 45 min. at 35 C. containing 3 g. of 2-methoxy-4- anilinoaniline diazonium sulfate, .3 cc. of Diazopon A (commercial surface active agent) and 300 cc. of water. The yarn was soaped at the boil for 5 min., rinsed and dried.

Dyeing from bath II (the control) is extremely strong and bright. Dyeing from bath III is considerably stronger than that from bath I. According to calculations, the same amounts of B- hydroxynaphthoic acid-m-nitroanilide should be absorbed from baths I and III. In bath IV, half the amount of such anilide was used as in bath III but IV still exhibits a stronger and brighter dyeing than I. This means that the guanidine carbonate exerts an extremely beneficial action.

Example XLII The following two baths were prepared (quantities in grams unless otherwise specified) I II 5-chlore-2,4-dimethoxyacetoacetanilide 250 250 guanidine carbonate 300 Oellosolve c. V4 caustic soda, 40 BL 34 warm Water cc 150 150 fi-rnethyl-o-anisidine... 110 oleyl methyl tauride 010 010 Cellosolve I .cc. $4 ,-4

The 5-chloro-2,4-dimethoxyacetoacetanilide, uanidine carbonate, Cellosolve and caustic soda were combined and diluted with the Water. The mixture containing the 5-methyl-o-anisidine, oleyl methyl tauride and Cellosolve was added. 10 g. samples of nylon yarn were dyed at 60 C. for 45 min., rinsed and developed with 5% (based on the weight of material) of sodium nitrite and 10% acetic acid in 300 cc. of water for 30 min. at 60 C. The dyeings were then finished as usual.

The dyeing from bath I which contained no guanidine carbonate is a dull orange yellow whereas the dyeing made in the presence of guanidine carbonate is a very bright strong greenish-yellow shade.

I claim:

1. In the process of dyeing nylon on the fiber by impregnating the fibers with an amine base and a Naphthol AS coupling component simultaneously and subsequently diazotizing the base and coupling the diazo with the coupling component, the improvement which comprises effecting the impregnation of the fibers with said coupling component in the present of an amount of a uanidine compound at least molecularly equivalent to the Naphthol AS but within the limits of 1% to 5% by weight of the fibers to be dyed, said guanidine compound selected from the class consisting of those of the following formulae:

wherein R1 and R2 are selected from the class consisting of hydrogen, alkyl, aryl, aralkyl and cycloalkyl, and the salts of such compounds.

2. The process as defined in claim 1 wherein the fibers are impregnated in the presence of the guanidine compound with an aqueous solution of the amine base and the coupling component.

3. The process as defined in claim 1 wherein the fibers are impregnated with an aqueous solution of a salt of the ice color coupling component and guanidine compound and the amine base.

4. The process of dyeing nylon on the fiber with an ice color which comprises impregnating the fibers with an amine base and a Naphthol AS coupling component simultaneously present in an aqueous solution containing an amount of guanidine carbonate at least molecularly equivalent to the Naphthol AS but within the limits of 1% to 5% by weight of the fibers to be dyed, effecting the diazotization of the amine base and 15 coupling the diazo compound thereby resulting with the coupling component.

5.' In the process of dyeing acetate rayon on the fiber by impregnating the fibers with an amine base and a Naphthol AS coupling component simultaneously and subsequently diazotizing the base and 'couplingthe'diazo with the coupling component, the improvement which comprises efiecting the impregnation of the fibers with said coupling component in the presence of an amount of a guanidine compound at least molecularly equivalent to the Naphthol AS but within the limits of 1% to by weight of the fibers to be dyed, said guanidine compound selected from the class consisting of those of the following formulae:

wherein R1 and R2 are selected from the class consisting of hydrogen, alkyl, aryl, aralkyl and cycloalkyl, and the salts of' such compounds.

6. The process as defined in claim 5 wherein the fibers are impregnated in the presence of the guanidine compound with an aqueous solution of the amine base and the coupling component.

1 6 7. The process asrdefined in. claim 5 wherein the fibers are impregnatedwith an aqueous solution of a salt: of the" coupling component and guanidine compoundand' the amine base.

8. The processoft dyeingacetate rayon on the fiber with an ice color which comprises impregnating the fibers with an amine base and a Naphthol AS-coupling'component simultaneously present in an aqueous solution containing an amount of guanidine carbonate at least molecularly equivalent to the Naphthol AS but within the limits of 1% to 5% by weight of the fibers to be dyed, efi'ecting the diazotization of the amine base and coupling the diazo compound thereby resulting with coupling component.

CLEMENS STRECK.

References-Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,822,548 Ter. Horst- Sept. 8, 1931 1,963,974 Ellis June 26, 1934- 2,190,746 Von Glahn Feb. 20, 1940 2,304,821 Hansenet a1; Dec. 15, 1942 2,367,534 Smith et a1 Jan. 16, 1945 2,385,719 Migrdichian Sept. 25, 1945 FOREIGN PATENTS Number Country Date 502,861 Great Britain Mar. 22, 1939 486,696 Germany Nov. 23, 1929 348,269 Great Britain May 14, 1931 643,323 France-. l May 15, 1928

Claims

1. IN THE PROCESS OF DYEING NYLON ON THE FIBER BY IMPREGNATING THE FIBERS WITH AN AMINE BASE AND A NAPHTHOL AS COUPLING COMPONENT SIMULTANEOUSLY AND SUBSEQUENTLY DIAZOTIZING THE BASE AND COUPLING THE DIAZO WITH THE COUPLING COMPONENT, THE IMPROVEMENT WHICH COMPRISES EFFECTING THE IMPREGNATION OF THE FIBERS WITH SAID COUPLING COMPONENT IN THE PRESENT OF AN AMOUNT OF A GUANIDINE COMPOUND AT LEAST MOLECULARLY EQUIVALENT TO THE NAPHTHOL AS BUT WITHIN THE LIMITS OF 1% TO 5% BY WEIGHT OF THE FIBERS TO BE DYED, SAID GUANIDINE COMPOUND SELECTED FROM THE CLASS CONSISTING OF THOSE OF THE FOLLOWING FORMULAE: