US2263616A - Composition comprising ice color coupling components - Google Patents

Description

inconvenience.

Patented Nov. 2 5, 1941 COMPOSITION COMPRISING ICE COLOR COUPLING COMPONENTS Miles A. Dahlen, Wilmington, Del., and Arthur L.

Fox, Woodstown, N. J., assignors to E. I.

du Pont de Nemours & Company, Wilmington,

DeL, a corporation of Delaware No Drawing. Application August 9, 1939,

' Serial No. 289,182

6 Claims.

This invention relates to dispersible solubilized compositions containing azo dye intermediates which are devoid of sulfonic acid and'carboxylic acid groups, such as the class of which the arylamides of 2:3-hydroxy-naphthoic acid are representative, and to new compositions of matter useful in printing which includes those dispersible solubilized intermediates.

These intermediates are generally knownas ice color coupling components and they are extensively used in the making of developed dyeings. One difficulty encountered'in the making of developed dyes with these coupling components is that the coupling components are largely insoluble in the ordinary dye bath and they must be first brought into solution in a bath containing an excess of caustic soda. The developed colors have been applied in various ways but they are usually applied by impregnating the entire fabric with one component of the dye, developing by printing onto the fabric in the selected design with a printing paste containing the other component, and then removing the an atmospheric drum drier in order to obtain a flaked or granular product and, when this is done, the sodiumsalt of Turkey red'B'il is preferred. This composition is readily soluble in aqueous sodium hydroxide solutions. An excess of alkali over'that required to form the sodium salt is commonly required in the composition to excess of the first intermediate by soaping and washing. The excess of caustic soda in the solution of the coupling component presented an When arylamides, such as an arylamide of 2,3-hydroxy-naphthoic acid were mixed with diazoimino compounds, they had to be wet out with an agent, such as alcohol, "Cellosolve or some other active solvent before they could be dissolved in caustic soda solution. The wetting out of the coupling component was an operation which was desirable to avoid.

According to the present invention the wetting out of the coupling component in the compounding of a printing paste is avoided. The presence of an undesirable excess of caustic soda in a paste which'contains both components of the dye is also avoided. In making a dyeing the 40 Turkey red oil, a dispersing agent such as the 5 condensation product of formaldehyde and naphthalene beta sulfonic acid, subjecting the mixture to milling so as to attain uniformity, drying, and subdividing to selected fineness. It

make the product instantly soluble. It is frequently desirable from the point of view of health to include only enough alkali to produce a turbid suspension. The turbidity of the suspension can then be removed by adding alkali to the bath. The preferred composition of matter of this invention, consequently, comprises a coupling component of the type described, or the alkali metal salt thereof, alkali, dextrin or the sodium salt of Turkey red oil, and a dispersing agent. The preferred process comprises mixing these components and subjecting them to plastic milling or drying on an atmospheric drum drier.

If a complete composition useful in printing is desired, an alkali stable diazoimino compound is included in the mixture.

Where the free acid form of certain favorable ice color coupling components is used, no alkali is added, and the products wet out and disperse in water rapidly to produce turbid suspensions. Addition of alkali to these suspensions produces clear solutions of the alkali salts of the ice color coupling components. Where the alkali metal salt of the ice color coupling component is used, the products exhibit similar behavior, producing turbid solutions containing both the ice color coupling components in the free state and alkali metal salts if little alkali is added. Clear solutions are produced at once if sufiicient alkali is included.

The class of ice color coupling components to which this. invention is particularly applicable ortho hydroxy-aryl-carboxylic acids, and to the is the arylamides of 2:3-hydroxy-naphthoic acid, which constitutes a preferred class. The invention is also applicable to the arylamides of other arylamides of beta-keto-carboxyiic acids. In the following examples only the preferred class of arylamides of 2-:3-hydroxy-naphthoic acid are used. However, the processes are equally applicable to the preparation of dispersibie and/or soluble compositions from all other ice color coupling components, examples of which are the arylamides of 2-hydroxy-carbafiole-3-carboxylicacid, 7 hydroxy alpha-naphtho-carbazole 6- carboxylic-acid, 2-hydroxy-anthracene-3-carboxylic-acid, and 2-hydroxy-diphenylene-oxide-3- is frequently preferred to dry the compound on carboxylic acid, arylamides of acyi-acetic-acids and tere-phthaloyl-bis-acetic-acids, amino-naphthols, and acylamino-naphthols. Examples of particular coupling components which give products quite as satisfactory as those listed in the examples are:

1- (2' :3-hydroxy naphthoylamino) 4 methylbenzene 1-(2':3-hydroxy-naphthoylamino) 2:4-dimethyl-benzene 1-(2' :3-hydroxy-naphthoylamino) -2 methoxybenzene l- (2' :3'-hydroxy-naphthoylamino) -4 methoxy benzene l- (2 :3-hydroxy-naphthoylamino) 2 :5-dimeth- Dl-4: '-(2":3"-hydroxy-naphthoylamino)1-3:3'-

dimethoxy-diphenyl. Y

If the composition is to be dried on a drum drier the sodium salt of Turkey redoil should be used, but if other methods of drying are to be used dextrin is preferred. Any of the dextrins can be used. 7 Certain assistants to dextrin, such.

as sugar, can also be employed.

The dispersing agents used are those custoaaeaeie marily employed in the art for the dispersing V of dyes. The condensation product of formaldehyde and naphthalene-beta-sulfonic acid is particularly satisfactory, but any such dispers- 7 'ing agent can be used.

The composition must be a uniform mixture such as a mixture producible by plastic milling.

By "plastic milling is meant the subjection of the mass, to disintegration by internal world However, any mixing'of the components which produces a uniform composition is satisfactory.

By drying the composition on an atmospheric drum drier flakes may be produced which have the advantage of eliminating dust and all its attending disadvantages from the dye house.

The following examples illustrate the invention but do not limit it. All quantities are stated in parts by weight.

Example I A mixture of 49 parts of dextrin and 2 parts of the condensation product of naphthalene-betasulfonic acid with formaldehyde was placed in -a Werner and Pfleiderer mixer and made into a smooth paste by mixing with 30 parts of water.

To this paste was added 49- parts of 2-(2':3'-hydroxy-naphthoyl-amino) -naphthalene and the resulting plastic mass was milled for one hour. Additional water (10 parts) was added during the milling to replace part of that lost by evaporation due to the heating up of the plastic mixture. The well-mixed product was removed from the mixer, dried in a vacuum oven, and coarsely ground. The virtually-dry product wet out and dispersed readily in water, forming a turbid suspension which dissolved completely when heated in the presence of caustic soda.

F 'ree arylamides of 2:3-hydroxy-naphthoic naphthoic acid protects them from decomposi- 4 5 tion over reasonable periods of time and the mix- I ous suspension.

acid described in the prior art do not wet out and disperse in water. In everyone they must first be made into a paste with a wetting out agent, such asan alcohol or a. sulfonated castor oil derivative, before an aqueous dispersion can beobtained.

Erample II 2' :3' -hydroxy-naphthoyl-amino benzene (40 parts) wasstirredtoasmoothpastewith20 parts of ethyl alcohol. This paste was diluted with 40 parts of water and transferred from the mixing vessel to a vacuum graining bowl. Dextrin (29 parts). p wdered cane sugar (28 parts).

and the condensation product from naphthalenebeta-sulfonic acid and formaldehyde (3 parts) were added and the mixture agitated until uniform. Water was removed by warming the mixture under vacuum until a viscous, plastic mass was obtained. Thismass was agitated under atmospheric pressure, for one hour, and then dried by warming and applying vacuum. The dried product was removed from the graining bowl and coarsely ground. 7

The product so obtained wet out and dispersed readily in water and dissolved .to' a clear solution on addition of caustic soda to the resulting aque- Erample III 2- (2' :3"-hydroxy-naphthoyl-amino) naphthalene (34 parts) wasstlrredtoasmoothpaste with 20 parts of ethyl alcohol and converted to its sodium salt by addition of 34 parts of 36 B. caustic soda solution. This mixture was transferred from the mixing vessel to a vacuum grain- "ing bowl. The alcohol was removed'by warming slightly and applying vacuum. The residue was diluted with 40 parts of water and then dextrin (2'! parts), powdered cane sugar (26 parts), and 9. agent (3 parts of the condensation product of formaldehyde and naphthalene-betasulfonic acid) were added. This mixture was agitated and the excess water removed'by warming under vacuum. The resulting rmous. plastic mass was groimd by plastic milling under atmospheric pressure for one hour and tuen dried by warming and applying vacuum. The dried product was removed from the graining bowl and coarsely ground. When added to water this product rapidly wet out and dispersed. Upon addition of a small amount of alkali complete solution was rapidly obtained.

In the making of a composition for application to and development on a fabric, a diazoimino compound, such as the compound made by reacting'piperidine-alpha-carboxylic acid with 4- chloro-2-amino-toluene, is added to the'mixture after it has been'well mixed with alkali and the plastic milling is continued. 'Theresulting dried product is made into a paste in the usual way with starch tragacanth thickener, applied to a roll and by a roll to the fabric. The printed fabric is subjected to hot acetic acid vapors which overcome the alkalinity of the composition and permit coupling on the fiber. Material prepared by this procedure wets out and dissolves completely in-hot dilute caustic soda solution.

2':3'-hydroxy-naphthoyl-amino-benzene processed by the above procedure yields a product which dissolves completely in water without the addition of more caustic soda solution.

The presence of dextrin in these mixtures of alkali metal salts of arylamides of 2:3-hydr'oxypattern of good brilliance and Products of the prior art neither exhibit the ease of solubility shown by these products nor involve the use of a protective agent.

Example IV 1- (2' :3 hydnoxy naphthoyl amino) -naph-' thalene (34 parts) was stirred to a smooth paste with 20 parts of ethyl alcohol and converted to a sodium salt by addition of 34 parts 01' 36 B.

1- (2 3' -hydroxy-naphthoyl-amino) -2-ethoxybenzene (40 parts) was Stirred to a smooth paste with 25 parts of ethyl alcohol and the paste was diluted by the addition of 135 parts of a 30% 2,263,616 'tures wet out and disperse rapidly in water.

solution of an assistant; such as the condensation product of beta-naphthalene-sulfonic acid with formaldehyde. This suspension was further diluted by the addition of a solution of 15 parts of dextrin and 8 parts of powdered cane sugar in 50 parts of water. The suspension was thoroughly mixed and then dried on a rotary drum drier. The product wet out rapidly in water and dissolved to a clear solution in dilute, aqueous caustic soda solution.

Example VI A water-soluble composition of matter suitable for the production of dyes on the fiber was prepared by mixing a dispersible ice color coupling component of this invention with a water-soluble diazoimino. or diazoamino compound in approximately equimolecular proportions. Such a composition consising of 100 parts'of the dispersible sodium salt of 1-(2':3'-hydroxy-naphthoylamino)-2-methyl-benzene of 40% strength and 40 parts of a diazoimino compound, obtained by reacting the diazo compound from 4-chloro-2- amino-toluene with piperidine-alpha carboxylic acid was completely soluble in hot water. An aqueous solution of the above mixture was added to neutral starch gum tragacanth' thickener and printed on cotton cloth. The printedmaterial was dried and then subjected to steam and acetic acid fumes for a short period. A red printed fastness was obtained.

Example VII Example VIII 2'z3' hydroxynaphthoylamino benzene (50 parts) was mixed with ethyl alcohol (25 parts) and water (50 parts) to form a smooth paste. To this paste was added Turkeyv red oil (10 parts) and isopropylated naphthalene-beta-sultonic acid (1.5 parts). This mixture was agitated and caustic soda solution (70 parts, 36 B.) was Example IX 2 3'-hydroxybenzoylamino-benzene (10 parts) was mixed with Turkey red oil (2.5 parts) and an aqueous solution of isopropylated beta-naphthalene-sulfonic-acid (0.8 part in 10 parts of water). This mixture was stirred to a smooth paste and caustic soda solution (17 parts, 36 B.) was added to convert the 2':3'-hydroxynaphthoylamino-benzene to its sodium salt. The resulting thick paste was thoroughly mixed and then diluted with an aqueous solution of sodium carbonate, (1.8 parts in 10 parts of water). The resulting mixture was further diluted with water (4 parts), agitated until uniform, and then dried on a rotary drum drier. The product was collected as non-dusting flakes which showed excellent wettability and solubility in cold water.

The usual diazoimino compounds can be employed,examp1es of which are the reaction products of diazo compounds from primary arylamines with sarcosine, proline, and methyl-glucamine. The diazo components are preferably free from sulfonic and carboxylic acid groups. Examples of these primary arylamines are Aniline m-Chloro-aniline 2:5-dichloro-aniline 5-chloro-2-amino-toluene 4-chloro-2-amino-anisole 2 5-dimethoxy-aniline 4-nitro-2-amino-toluene 5-nitro-2-amino-toluene 4-n'itro-2-amino-anisole 5-nitro-2-amino-anisole Dianisidine 4-benzo3 lamino-2 5-dieth'oxy-aniline -carbomethoxy-amino -2 5 -diethoxy-aniline The composition of the new compositions other than the ice color coupling components may vary widely. Dextrin may be supplemented by cane sugar or similar water-soluble carbohydrate material. The ratio of protective colloid and diluent to ice color coupling component also may vary widely, but the preferred-products contain from 20% to 70% of the ice color coupling component. As wetting out and dispersing agents,

' finished cry compositions.

' the drying process,

I superiorto-those of aration' of dye baths,

scribed in the present application are stances, the, wetting out agents remain in the The wet compositions may be converted to virtually products by evaporation in graining bowls containing heavy duty, agitators. During the materials are" subjected to plastic milling in such equipment. Alternatively the mixtures may be dried on rotary drum the alkali metal salts of the ice color coupling components, said coupling components being,

s from the group consisting of arylamides of orthoof a dispersing agent and Turkey red; oil alkali,

driers on vacuum tray driers,'or in other suitable equipment. The compositions are uniformly constituted and nolack of uniformity is noticeable in the subdivided products. In order to. ob: ,tain the best wetting out characteristics in the finished products. the dry materials should con,-

tain a small amount of residual moisture usual- 1y less than 2%. The products are virtually.

dry, somewhat porous and friable. They are There,

is no advantage in easily subdivided to a suitable degree of fineness; I I and uniformity, 'asby grinding. The subdivided material is granular. I extremely fine grinding. The grain sizes in the,

preferred products range from approximately 10 1 to 200*mesh' but largeror smaller grain sizes can be used. j

,j J The new compositions of the-present inven tion are especially useful for baths for padding textile fibers with'the ice color coupling components, such fibers subsequently to'b'e dyed or printed with diazo salts. The dry compositions also maybe mixed with drywater soluble diazoimino' compounds, with dry nitro'sthe preparation of I hydroxy-aryl-ca andcarboxyl 8 3 19 at least a suiilcient mount metal salt to make a dispersion when the com 1 position is added to water; and an excess of an alkali metal hydroxide over that necessary to form an alkali metal'salt of the coupling com- I ponent; said composition being characterized by its property to wet-out rapidly with water, by

being rapidly solublein water, by being nondusting and by stability upon storage.

I 2. A' virtually dry'flaked non-dusting article of a uniform porous friable composition which comprises a subdivided compound of a group consisting of the alkali metal salts, of the ice' color, coupling components, said coupling components being from the group consisting of arylamides' I of orthohydroxy arylcarboxylic acids and beta keto-carboxyllc acids which are devoid of sulfonic acid andcarboxyl groups; at least a sufficient amount of dispersing a ent and Turkey red oil alkali metal'salt to make a dis- I persion when the composition is added to water;

amines (antidiazotates) prepared from arylamines, or with dry 'diazo' sulfonates. to produce mixtures suitable for dyeing and printing. ,Such I mixtures show advantagesin wetting out and dispersing properties The products of and printing pastes. It is wellknown that the alkali metal salts of the arylamides of 2:3-hydroxy-naphthoic acid are quite unstable to storage.

sitions containing such alkali metal salts destable.

The dyeing value of the products of the presis observed with the new also solve another problem of the prior art. Dry

over similar mixtures; con- I taining the ice color coupling componentsin'the form of their free ac I I l the present invention are, I the prior art in ease of pre and at least a sumcicnt excess of an alkali metal hydroxide over that necessary to form an alkali 1 metal salt of the coupling component to make the composition soluble' in water: said cflmposl tion being characterized by being non-dusting. abyaits, property, to wet-out rapidly with water, by

being readily" soluble in water and by stability upon storage.

3. A virtually dry flaked article porous friable 'composition which comprises a subdivided alkali metal salt of an arylamide of an ortho' hydroxy --aryl carboxylic acid which is devoid of 'sulfonic' acid and carbonyl groups; I

. ,suiiicient dispersing agent and Turkey red all However. the compo- .80 tinctorial value and bril- This perhaps may be attributed color coupling components, the new products mixtures of the components are dusty and cause textile plants. The

a definite health hazard in and they subdinew compositionsare friable vide into grains without producing nets. 4

From the foregoing disclosure it will be recdusty prqdthat necessary to ognized that the invention is susceptible of modi- I flcation without departing from the spirit and scope thereof and it is to be understood that the invention is not restricted to the specific illustrations thereof herein set forth.

We claim:

1. A virtually dry granular article of a' uniform porous friable composition which comprises a subdivided compound or a group consisting of acterized by being acids and beta-keto-carboxylic acids devoid of 'sulfonic acid and carboxyl groups; at

alkali metal salt to'make a dispersion when the composition is added to water; and at least a suflicient excess of an alkali metalhydroxide over that necessary to form an alkali metal salt of the coupling component to make the composition soluble in water; said composition being characterized by being non-dusting, by its property to wet-out rapidlywith water, by being readily soluble in water and by stability upon storage.

4. A virtually dry flaked article of a uniform porous composition which comprises a subdivided sodium salt of a 2,3hydroxy-naphthoyl-arylamide of the benzene series which is devoid of sulfonic acid and carboxyl groups; sufllcient of a-dispersing agent and the'sodium salt of Turkey red oil to make a dispersion when the composition is added to water, said dispersion agent being the condensation product of naphthalenebeta-sulfonic acidwith formaldehyde; and at least a sufiicient excess of sodium hydroxide over form .the sodium salt of the coupling component to make the composition soluble in water; said composition being charnon-dusting, by its property to wet-out rapidlywith water and by stability upon storage.-

5. The process which comprises intermixing water; an arylamide of an acid from the group consistingof ortho hydroxy aryl carboxylic which are least sufllclent of an alkali metal hydroxideto boxylic acids and b'eta'keto-carboxylic acids which are devoid of sulfonic' acid of a uniform form an alkali metal salt of said coupling component; at least a sufiicient amount of a dispersing agent and the alkali metal salt 01' Turkey red oil to make a dispersion when the virtually dried composition is added to water; subjecting the mixture to plastic milling until a uniform composition is produced; and removing volatile liquid constituents until the composition is virtually dry and porous and subdividing the virtually dry porous composition;

6. The process which comprises intermixing water; a volatile liquid organic wetting agent; an arylamide of an ortho-hydroxy-naphthalenecarboxylic acid which is devoid of sulfonic acid and carboxyl groups; an excess of sodium hydroxide over that necessary to form the sodium salt of said arylamide; at least a suflicient amount of a dispersing agent and the alkali metal salt of Turkey r'ed oil to make a dispersion when the virtually dried composition is added to Water; subjecting the mixture to plastic milling until a uniform composition is produced; and removing volatile liquid constituents until the composition is virtually dry'and subdividing the virtually dry composition. v 4

. MJLES A. DAHLEN.

. ARTHUR L. FOX.