US2263387A - Process of dyeing - Google Patents

Description

Patented Nov. 18, 1941 PROCESS OF DYEING Alva L. Honk and Louis H. Bock, Philadelphia,

Pa., assignors to 8; Haas Company,

Philadelphia, Pa.

No Drawing. Application July 7, 1939, Serial No. 283.140

7 Claims.

This invention relates to a process of dyeing in 1 which fixation of dyestufi on textile material is improved. It relates in particular to the fixation of certain dyestuifs by condensing them with formaldehyde and a non-aromatic, primary or secondary amine, impregnating textile material.

therewith, and subsequently heating the impregnated material to cause the dyestufi condensate to combine with the textile material.

The object of this invention is to improve the fastnessof certain dyestuffs, herein called methylol-forming, on textile materials. It is another object of this invention to provide a process for imparting to dyed fibers, yarns, and

fabrics a high degree of resistance to removal of dye from cleaning during laundering, and dry cleaning or from wear. It is also an object to provide a process for dyeing which does not require the use of a mordant. It is another object to provide dyestufis by which color may be imparted to different types of fibers by the same dye. A further object is to provide a universal one-bath dyeing process.

Fixation of certain dyestuffs may be accom-' plished by processing textile material with a dyestuif possessing the group in which Ar represents an aromatic nucleus carrying a nuclearly-bound oxygen or sulfur atom, A

represents a member of the group consisting of hydrogen, and aliphatic and alicyclic radicals, and B represents a member of the group consisting of aliphatic and alicyclio hydrocarbon groups. A and B may represent, when taken jointly, a divalent hydrocarbon radical or a divalent heteroradical which jointly with the nitrogen forms a heterocyclic ring, such as found in piperidine, piperazine, pyrrolidine, morpholinc, and other cyclic,'basic, secondary amines. This essential fixative group may be formed in any dyestuff which is capable of reacting with formaldehyde to form a methylol compound. Aromatic compounds which possess a phenolic hydroxyl or sulfhydryl group with positions available for substitution ortho or para to the hydroxyl or sulfhydryl group are known to react with formaldehyde and are commonly designated methylolforming phenols. The term methylol-forming dyestufi or dye is used in the same sense and is applied to those dyestuffs which have available for substitution ortho or para positions relati e to a nuclearly-bound phenolic hydroxyl or sulfh'ydryl triethylene tetramine, and the like.

pregnate fibers, yarn,

non-aromatic amines possessing at least one hy-' drogen held bythe nitrogen atom and are operable in this process.

Methylol-forming dyestuflfs are thus reacted with formaldehyde and amines and used to imbatting, or fabric by paddipping, spraying, or printing according to such well known methods as skein-dyeing, chaindyeing, raw stock dyeing, package dyeing, piece dyeing, roll printing, screen printing, and the like.

Excess dyeliquor may be removed by any suitable means. such as squeeze rolls, centrifugal extractor, or the like, when so desired; Then, with or without previous drying, the impregnated material is subjected to a temperature high enough to bringabout a reaction ofthe dyestuif and the textile material. The required temperatures are above C. The temperature used will depend upon the material being dyed, the

dyestuff, the process of treating, the presence completing the reaction. At temperatures of to C. a; few minutes usually sufllces to fix the dyestufi. At temperatures below 120 C. longer times are necessary, even times up to an hour being sometimes required. After the reaction of organic fiber and modified dye has been eifected,- it is usually desirable to washthe treatedmaterial to remove unreacted excess dye, soluble reaction products, etc.,' as in the usual soaping-ofi procedure.

The dyes which are amenable to fixation by this process are most conveniently classified according to chemical structure and include azo dyes, such as Tannin Orange R (basic) Resorcin Yellow (acid), Betanaphthol Orange (acid). Para Red (acid), Sudan III (a disazo dye) etc.; nitroso dyes, such as Resorcin Green; indophenol dyes, such as Indophenol Blue (basic); hydroxyketone dyes, such as Alizarine Yellow C, Flavopurpurin, alizarinirisol, etc.; indanthrene dyes, suchas Indanthrene Blue 5G; triphenyl methane dyes, such as fiuorescein, aurine, xanthene, etc.

The secondary amines which are effective in this process are aliphatic, heterocyclic'and alicyclic amines of a wide range of molecular size and structure. Examples of secondary amines which maybe used include dimethylamine, diethylamine, dibutylamine, diamylamine, methyl dodecylamine, dicyclohexylamine, morpholine, piperidine, piperazine, pyrrolidine, diethanolamine,

Primary amines are also eflective in-our process. Typical compounds include. monomethyh amine, monoethylamine, ,t-amy'lam'ine, caprylamine, cyclohexylamine, ethylenediamine, monoethanolamine, etc. It is possible with primary amines to use more than one equivalent of iormaldehyde for each equivalent-of amine to obtain various products of structures which-have not been determined.

In general the condensation of a .methylolforming dye with formaldehyde and a primary or a secondary amine is performed under conditions which do not greatly alter the dye or lessen its value as a dyestufl. Reacting proportions of the materials aremixed. It is often advantageous to 1 use an inert solvent, such as alcohol,-water, ether,

dioxane, or benzene. The mixture may the allowed to stand for twenty-four hours'or more at room temperature or the may be heated under reflux or :in a closed vessel. If desired, the formaldehyde and amine may be mixed first and the dye added in successive increments. In another procedure dye and amine may be mixed and formaldehyde solution gradually added. The product may be separated by .distilling of! the solvent. It may sometimes be separated .by crystallization. It is also possible to use the dye solution directly without .further treatment for purification.

It is necessary to use at least one "molecular equivalent of formaldehyde and at least one'molecular equivalent of an amine for .each molecule of dye. When more than one :reactive ortho or para position in a phenolic nucleus'is available for substitution, more than one equivalent each of formaldehyde and aminemay beused, if desired, to introduce two or more methylene amine groups.

The reacted dye may be .app'liedin the same way as any comparabledyestuif. It maypbe used in the presence of an acid, such as acetic acid, in which case a salt form is applied. It may, if desired, be used in the presence of :an alkaline material, such as soda ash, sodium bicarbonate,

In applying the modified dyestuffs 2 small I 55 amounts of an acid or an acidic salt seem to provide catalytic action in the reaction o1 the dye'and textile material, but they are not essential in the process.

methylene amine .group in the dye is the improved solubility or .dispersibility of many or the treated :dya. Furthermore, any of the dyes obtained by the herein described method may be reacted with practically any natural or artificial fiber which contains reactive groups, such as the hydroxyl groups in cellulosic materials. It does not follow that identical shades result on all types of fibers, but the treatment does allow the use of dyes on fibers which would otherwise not be receptive to a particular dye. Likewise, dyes which are not otherwise test may be applied.

The following examples illustrate the preparatiomof dyes used in this process:

"Pansiwrron A.-Dimethylaminomethyl fluorescein To 16.6 g. of fluorescein in 150 ml. of water was added a solution containing 20 g. of 30% formal- .dehyde and 36 :g. of 25% dimethylamine. This was stirred at 70 C. for 3 hours. The solution becamedark red when concentrated, and green- .ish yellow when very dilute. Acid changed it to green in any concentration. It was concentrated in vacuo at C. to a brittle, light red solid. It was more soluble in water than was fluorescein. Nitrogen analysis was 7.07%, showing it to contain slightly more than two dimethylaminomethyl groups.

PREPARATION B.Benzyl chloride quaternary salt of dimethylaminomethyl fluorescein To 5 g. of dimethyl aminomethyl fluorescein was added 4 g. of benzyl chloride with thorough mixing. This mixture was heated on the steam bath for 2 hours. It became gummy,- then brittle, and yielded a red powder which contained 4.08% nitrogen.-

Pasrans'rron C.-Morpholinomethyl 3-amino-4- methylbenzeneazo-a-naphthol To 9.2 g. of 3-amino-4-methylbenzeneazo-anaphthol was added a solution containing 7 g. of 15% formaldehyde and 3.4 g. of morpholine and 50 ml. of water. These were stirred together for 3 hours at 70 C. and concentrated in vacuo at 50 C. A red powder resulted, soluble in dilute acids.

"PREPARATION ,D.P1'oduct from quinizarin, formaldehyde and monomethylamine To 24 g. oi quinizarin suspended in- 150 ml. of

' water was added g. of 35% aqueous monomethylamine and.20 g. of 30% aqueous Iorma1dehyde. The mixture was stirred at C. for 3 hours. Concentration in vacuo at 50 C. gave a dark brown powder, containing 3.68% nitrogen. It; was soluble in amine solutions or other basic solutions and to a limited extent in dilute acids.

The dyestufls bearing a methylene amine group react with a wide variety of organic textile materials, such as -wool, silk, cotton, mercerized vcotton, rayon, cellulose acetate, paper, linen, kapok, jute, straw, etc. These materials may be in the form of fibers, or raw stock, yarn, ,woven or knitted cloth, felts, batting, etc. Any of the organic materials which are used in making fabrics, yarns, sheets, battings, and the like, and

which are not damaged by treatment in an equeous bath and by heating above 100 C. may be used in'the herein described process. The textile material and the modified dye react, it is believed, through the methylene group, which has been added to the dye, and yield a complex which resists removal of dye by any ordinary means. Another advantagev of the introduction of the Details or various typical applications are -givn herewith to illustrate the wide application oi the new dyeing procedure.

' 1 1 Example 1 pieces of cotton, silk, and wool were dipped in a 5% aqueous solution of bis-dimethyl- .aminomethyl' fluorescein, squeezed and dried.

They were then heated at'l30 C. for one-half hour and given a thorough washing. Colors were Wool and cotton fabrics were treated as in Example No. 1, except that the benzyl chloride aaeaser 3 quaternary salt of dimethylaminomethyl nunrescein was used in aqueous solution. I

After being heated at about 130 C. and washed, the cotton was permanently d'yed a bright yellow-orange, and the wool a pale peach shade.

Example 3 Cotton, silk, and wool fabrics were run through a bath of a 5% aqueous solution of bis-dimethylaminomethyl 3,6-dihydroxy-9-phenyl xanthene containing a trace of acetic acid. They were squeezed, dried, and heatedone-half hour at 130- C. After being washed, the cotton and silk were deep rose-red, and the wool was pale rose.

Example 4 Cotton, silk, and wool fabrics were run through a 1% alcoholic solutionof dimethylaminomethyl 3-amino-4-methyl benzene-azo-a-naphthol, and

subsequently treated as in Example 3. All retained arich chocolate brown color after thorough washing.

Example 5 Cotton, linen and wool samples were treated as in Example 3, except that the dye used was a -2% aqueous solution of dimethylaminomethyl quinizarin as the acetate. The colors produced were deep purple on cotton and linenand medium purple on the wool.

Example 7 A viscose rayon fabric was treated with a solumols of aqueous monomethylamine. It was dried, heated one-half hour at 130 C., andwashed. A deep purple color was retained.

7 process of this application may be substituted for the sulfonation. In this way the dye is obtained in a soluble form and atthefsame time the new method of fixing'thedye may be used. However, sulfonated dyes can '1 be used in the process 'By condensing a methylol' forming dye with formaldehyde and a non'l-aromatic amine having at least one hydrogen on each nitrogen atom, thereis obtained a dye'stu'if' which may be fixed to an organic textile matcrial'by the application of heat. Certain dyes not previously retained by fibres may thus be applied without the use of mordants or precipitating agents. -;Dyes which were heretoforeretained only by one type of fibre may be used with other'types as well. Only a single dye-bath is required in processing and the process of fixation of dyes herein described may be carried out with the equipment available in practically any finishing and dyeing plant.

vPhenolic dyestuffs which have been avoided betion of bisdimethylaminomethyl 3,6-dihydroxy- 9-pheny1 xanthene as in Example 3. ,It retained a rose-red color, fast to washing.

Example 8 A cellulose acetate fabric was run through a alcoholic solution of dimethylaminomethyl 3-amino-4-methyl benzeneazonaphthol, squeezed, dried, and heated one-half hour at 130 C. After washing, the color was cocoa-tan.

- Example 9 Pieces of linen fabric were dipped through an aqueous solution containing 2% of dimethylaminomethyl quinizarin and 2% of acetic acid.

They were treated as in Example 8. A'deep bluepurple color resulted.

Example 10 cause of sensitivity to alkaline soaps may be used in our new process of dyeing. This is particularly true of vat dyes containing phenolic hydroxyl groups. The treatment usually improves solubility and dispersion of dyes and thus increase their effectiveness in application.

We claim:

1. The process of fixing on organic textile material a phenolic dyestuff having available for substitution at least one hydrogen atom in the Po itions ortho and para to the aromaticallybound hydroxyl group, which comprises condensing said dyestuifwith formaldehyde and a non-aromatic amine, having at least one hydrogen atom held by the nitrogen atom, to form a methylene amine condensatewiththe dyestufi, applying said'condensate to textile material, and heating the treated textile material until the modified dy'estufl is fast thereto.

2. The process of fixing on organic textile material a phenolic dyestufi having available for substitution at least one hydrogen atom in the sol the dyestuif bearing a methylene amine group to stufi is fast'thereto.

3. The process of fixing on organic textile material a phenolic dye having available for substitution at least one hydrogen atom in the positions ortho and para to the aromatically-bound 3 hydroxyl group, which comprises condensing said -dye with at least one mol equivalent each of retained a deep rust shade and the mohair was a lightly colored, giving an attractive effect of differential dyeing.

Example 11 A cotton sheeting was dipped through a solution containing 10% of acetic acid and about of the product from the reaction of quiniformaldehyde and of a non-aromatic, strongly basic, secondary amine, applying the condensate thus formed to'textile material, and subsequently heating the textile material carrying the condensate above 100 C.

4. The process of fixing on organic textile material a dyestuff, possessing a hydrogen atom in a position ortho or para to a nucleariy-bound hydroxyl group, which comprises condensing said dyestuff with at least equivalent proportions each of formaldehyde and of a non-aromatic,

zarin with 2 mols of aqueous formaldehyde and 6 strongly basic, secondary amine,- to form a methmaterial a phenolic dye having available for substitution at least one hydrogen atom in the positions ortho and para to the aromatically-bound hydroxyl group, which comprises condensingsaid dye with at least one mol equivalent of formaldehyde and. at least one mol equivalent of di-] applying the condensate thus; formed to textile material and heating the treat-' methylamine,

ed textile material above 100 C.

6.,The process of fixing onjorganic textile material a phenolic dye having. available for substitution at least one'hydrogen atom in the positions ortho and para to .'the 'aromaticallybound hydroxyl group, which, comprises condensing said dye with at least one mol equivalent of formaldehyde and at least one mol equivalent or monomethylamine, applying the condensate thus formed to textile material and heating the i 5 treated textile material above 100 C.

7. The process of fixing on organic textile material a phenolic dye having available for substitutionat least one hydrogen atom-in the positions ortho and para. to the aromatically- 1 bound hydroxyl group, which comprises condensing said dye with formaldehyde and a nonaromatic, secondary amine to form a methylene amine condensate, allrylating said amine condensate to form a quaternary ammonium salt,

15 aPDh'ing said salt to'dye said textile material,

and heating the dyed textile material until the v modified dyestufl' is fast thereto.

ALVA L. HOUK.

LOUIS H. BOCK.