US3072611A

US3072611A - Dyeing assistants and process for producing same

Info

Publication number: US3072611A
Application number: US836327A
Authority: US
Inventors: Sellet Lucien
Original assignee: Jaques Wolf & Co
Current assignee: Jaques Wolf & Co
Priority date: 1959-08-27
Filing date: 1959-08-27
Publication date: 1963-01-08
Anticipated expiration: 1980-01-08

Description

UnitedStates Patent Ofitice 3,072,611 DYEING ASSISTANTS AND PROCESS FOR PRODUCING SAME Lucien Sellet, Saddle River, N. J., assiguor to Jaques Wolf & Co., Newark, N.J., a corporation of New Jersey No Drawing. Filed Aug. 27, 1959, Ser. No. 836,327 1 16 Claims. (Cl. 260.-70)

This invention relates, in general, to a class of novel compounds which are useful as assistants in the dyeing of textiles. More particularly, the invention relates to new and improved dye leveling and dye retardant agents which are especially well suited for use in the dyeing of nylon, wool, cotton, silk and rayon fibers and combinations of such fibers.

In the dyeing of wool, silk or nylon with acid dyes, dyeing assistants are generally employed. Moreover, in the dyeing of cotton and rayon with direct dyes, dyeing assistants have also proven to be most helpful. Acid dyes are characterized in that they contain, as the active principal thereof, an aromatic nucleus having both a chromop'noric group, that is, a color bearing group, and a Watersolubilizing group in their structure. In an acid dye, the water-solubilizing group is generally a sulfonic radical. on the other hand, practically'all direct dyes are of the are type. The azo group is the chromophor and this type of compound generally contains sulfonic radicals to impart water-solubility thereto. Direct dyes are characterized in that they are water-soluble and in that they exhaust onto thecellulosic fibers from a salt bath without mordanting of the fiber. Y

. In general, dyeing assistants may be described as materials which are added to a dye bath to promote or to con trol dyeing. These assistants aid in the achievement of uniform absorption of the dye by the fiber. The precise manner in which level dyeing is accomplished will depend, for the most part, first, upon the particular dyestufl in use and, second, upon the assistant which is employed therewith. As a general rule, however, a dyeing assistant will aid in promoting level deposition of the dye on the fiber or fabric in one of several ways. For example, certain dyeing assistants will promote level dyeing by increasing the solubility of the dye in the bath. Others, however, will accomplish the desired result by delaying the absorp tion of the dye by the fiber. Finally, other dyeing assistants will function as such by aiding the dye to penetrate more readily the material to be colored. The expressions dye leveling agents and dye retardant agents are frequently used when referring to dyeing assistants. Both of these expressions are employed to denote compounds which promote level dyeing. However, the expression dye-retardant agent is used most often in a more specific sense, namely, to designate compounds, which, when added to a dye bath, promote level dyeing by preventing rapid exhaustion of the bath. A dye retardant agent accomplishes this by decreasing the rate of absorption of the dye present in the dye bath.

It is the object of this invention to provide a class of compounds which are useful as dyeing assistants.

It is a further object of this invention to provide compositions which are useful as dye leveling agents and dye retardant agents in the dyeing of textile fibers.

A more particular object of the invention is to provide a class of substantially non-foaming dye leveling and dye retardant agents which are especially well suited for use as assistants in the dyeing of textile fibers, and combinations of these fibers, either with acid dyes or with direct dyes.

Other objects of the invention in part, appear hereinafter.

It has been discovered that the objects of the invention are accomplished by compounds prepared by the reacwill be obvious and will,

Patented Jan. 8,

tion of certain sulfonic acid derivatives with aqueous resinous condensates produced by the reaction of formaldehyde, ammonium sulfate and either urea or biuret.

The sulfonic acid derivatives which are employed in the preparation of the novel products of this invention are compounds produced by the reaction of 'a naphthalene sulfonic acid with certain saturated aliphatic monohyd'roxy alcohols. These derivatives, as well as processes for their production, are well known in the art. Derivatives which are completely suitable for use in the practice of the invention can be obtained by mixing, and heating at a temperature Within thera'nge of from about C. to 120 C. and, preferably at a temperature within the range of from about C. to about C., approximately equimolar quantities of a suitable alcohol and a naphthalene sulfonic acid. Slight excess quantities of the alcohol or slight excess quantities of the sulfonic acid compound can be used however, if desired. Th'e'duration of the heating step will depend to a great extent upon the temperature used in carrying out the reaction. At lower temperature, longer heating periods will be necessary to complete the reaction. For example, it has been found, that when a temperature of about C. is used, the reaction will be complete in at least about eight hours. However, when, for example, a temperature of about 80 C. is used in carrying out the reaction, the heating period will be extended to about twelve hours. It is to be noted, however, that the procedure used in the production of the naphthalene sulfonic acid derivative is not a part of the present invention. The foregoing description of a method for producing suitable derivatives is exemplary only. Modifications in the described process can be made without affectingthe natureor the utility of the product. Such modifications will be readily-apparent to those skilled in the art.

In producing the desired derivative of naphthalene sulfonic acid, beta-naphthalene sulfonic acid is preferably used. Alpha-naphthalene sulfonic acid can be used in its place, however. The alcohols which are used in the production of the desired derivatives are saturated, aliphatic monohydroxy alcohols containing from 1 to about 3 carbon atoms. Moreover, the alcohols employed are substantially anhydrous. As used herein, the expression substantially anhydrous should be construed as including alcohols containing not more than about 2.0% by weight of water. Thus, for example, derivatives of naphthalene sulfonic acids, which are well suited for use in the practice of this invention, are those prepared by heating the naphthalene sulfonic acid with a substantially anhydrous alcohol, such as, methanol, ethanol l-propanol, 2-propanol or mixtures thereof. In the preferred practice of the invention, a derivative produced by reacting betanaphthalene sulfonic acid with 2-propanol, or, as it is commonlycalled, isopropyl alcohol, is used.

As indicated heretofore, the aforementioned naphthalene sulfonic acid derivative is reacted with an aqueous resinous condensate to produce the improved dyeing assistants of this invention. These resinous condensates can be either preformed by the reaction of formaldehyde, ammonium sulfate and urea or biuret in the presence of water or, as Will be more fully shown hereinaftenthey can be formed in situ in the naphthalene sulfonic acid derivative. Pre-formed resinous condensates, completely suitable for use can be prepared, for example, as follows: aqueous formaldehyde is first charged into a suitable re.- action vessel. Formalin, which is an approximately 37% by weight aqueous solution of formaldehyde, is preferably employed. However, formaldehyde in any of its poly meric forms, as, for example, paraformaldehyde, trioxane, etc.', can be used. Therefore, whenever the term formaldehye is used in the present specification and claims, it shouldbe construedas encompassing not only formalin but also the various polymeric forms of formaldehyde as well. Thereafter, ammonium sulfate, preferably dissolved in water, is added to, and mixed with, the aqueous formaldehyde. The aqueous reaction mixture is then heated, with stirring. As a general rule, the reaction between these reactants will proceed at any elevated temperature. However, the rate at which the reaction proceeds will vary according to the temperatures employed with the reaction rate increasing as the reaction temperature is increased. In the preferred practice of the invention, the resinous condensate is prepared at a temperature within the range of from about 60 C. to 100 C; and preferably at a temperature within the range of from about 65 C. to 75 C. When the reaction temperature, that is, a temperature of from about 60 C. to about 100 C., is reached, urea or biuret is added to the reaction mixture. The step of adding the urea or biuret to the mixture is carried out slowly and gradually and the addition is accompanied by continuous stirring of the reaction mixture. The mixture is maintained at the elevated reaction temperature during the addition of urea or biuret and heating, at lower temperatures in the aforesaid range, and stirring are continued for a period of about two hours after the addition of the urea or biuret has been completed. Where high reaction temperatures are used in preparing the pre-formed condensate, that is, temperatures of about 90 C. to 100 C., it is preferred to use a shortened heating period. The aqueous reaction product, thus obtained, is used as is, that is, without any further processing, in producing the novel dyeing assistants of this invention. 1

It has been indicated previously that the preparation of the resinous condensate is carried out in an aqueous media. The most satisfactory results are obtained when water comprises from about 45.0% to about 80.0% of the total weight of the reaction mixture. In producing the condensates which are employed in the preferred embodiment of the invention, water comprises from about 55.0% to about 65.0% by weight, of the total weight of the mixture. Moreover, in the production of the resinous condensate, sufiicient quantities of reactants will be used to provide the reaction mixture with a ratio of from about 3.0 mols to about 4.5 mols of formaldehyde and from about 0.2 mol to about 0.5 mol of ammonium sulfate for each mol of urea or biuret employed.

The improved dye leveling and dye retardant agents of this invention are readily prepared from this pre-formed condensation product. For example, in the preferred practice of the invention, this is accomplished by adding the resinous condensate to the beta-naphthalene sulfonic acid derivative while heating the mixture at the temperatures, and for the periods of time, designated hereinafter. While the quantity, of each reactant employed can be varied somewhat, it has been found that products having superior properties will be obtained when the reaction system comprises a mixture of a ratio of from about 0.3 mol to about 0.45 mol of resinous condensate for each 2.0 mols of beta-naphthalene sulfonic acid derivative.

In an alternate embodiment of the invention, the resinous condensate is prepared in situ. In this method, the resinous condensate is prepared by adding, in the manner indicated hereinafter, water, urea, or biuret, ammonium hydroxide and formaldehyde to the beta-naphthalene sulfonic acid derivative and heating same therein. This particular procedure takes advantage of the fact that naphthalene sulfonic acids of commercial production generally contain an excess of sulfuric acid. The free sulfuric acid which is present in the reaction system reacts with the added ammonium hydroxide to form the ammonium sulfate ingredient in situ. This alternate procedure may be more particularly described as follows: The sulpho derivative prepared from the naphthalene sulfonic acid and the aliphatic alcohol is first produced by the method described heretofore. Thereafter, urea or biuret, ammonium hydroxide and water are slowly added to this heated derivative of naphthalene sulfonic acid. During the addition of these ingredients, the temperature of the mixture is maintained preferably within the range of from about 65 C. to about 75 C. However, in general, the addition of these ingredients can be carried out at any temperature between about 60 C. to 100 C. Subsequently, formaldehyde is introduced slowly, for example, over a period of from about 2 to 3 hours, into the mixture. The addition of formaldehyde to the mixture is preferably carried out with the mixture heated to a temperature of from about 100 C. to 110 C. However, if desired, the addition can be made at lower temperatures, for example, at a temperature of from about 60 C. to 100 C. The ammonium hydroxide which is added reacts with the free sulfuric acid present in the reaction mixture to form the required ammonium sulfate reactant. Subsequent heating of this mixture, in the manner described hereinafter, results in the production of a compound which, in its chemical structure and physical properties, is identical to a product prepared by heating the naphthalene sulfonic acid derivative with a pre-formed resin. As was the case in the method first described, that is, where the naphthalene sulfonic acid is reacted with the pro-formed condensate, when this alternate method is utilized in carrying out the invention sufiicient quantities of reactants should be used to provide the reaction mixture with from about 3.0 mols to about 4.5 mols of formaldehyde and from about 0.2 mol to about 0.5 mol of ammonium sulfate for each mol of urea or biuret to be employed. Moreover, sufficient quantities of reactants should be used to provide the reaction system with a mixture of from about 0.3 mol to about 0.45 mol of resinous condensate for each 2.0 mols of sulfo compound present therein.

In the actual preparationof the dye leveling and dye retarding compositions of this invention, the reactants, namely, the derivative of the naphthalene sulfonic acid and either the pre-formed resinous condensate or the ingredients used in its in situ production are heated, with continuous stirring, at an elevated temperature. In general, the reaction is accomplished by heating the reactants, under reflux, at a temperature within the range of from about C. to about 120 C. In the preferred embodiment of the invention, the reaction is carried out at a temperature within the range of from about C. to C., however. The duration of the heating step will be determined, to a large extent, by the reaction temperature employed. For example, at lower temperatures a longer period of heating will be required to drive the reaction to substantial completion. However, other factors, such as, the chemical structure of the particular naphthalene sulfonic acid derivative in use and the quantity of water and acid present in the reaction mixture, also bear on the question of how long the reaction mixture should be heated at a particular temperature in order to insure the production of a completely satisfactory product. It has been established, however, that when the isopropyl alcohol derivative of beta-naphthalene sulfonic acid is in use and it is to be reacted with an aqueous resinous product containing from about 55% to about 65% of water under. the preferred reaction conditions, namely, a reaction temperature of from about 100 C. to about 110 C., a heating period of from about 7 to about 9 hours will generally sufiice.

After the heating step is completed, the aqueous reaction product which is obtained is then subjected to the final finishing steps. This involves first mixing the reaction mixture with cold aqueous alkali. Preferably, a mixture of water, alkali and ice is used. In general, hydroxides and carbonates of monovalent metals, as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, etc., have been found to be well suited for use. Other alkalies, both organic and inorganic in nature, can be employed, however. The quality of alkali which is used should be sufficient to adjust the pH of the aqueous system to within the range of from about 7.5to 9.0. I Preferably, the alkali should be added ina sufficient quantity to adjust the pH of the product to within the range of 8.0 to 8.3.

It has been indicated heretofore that, in producing the preferred products of the invention, the reactants are heated at a temperature of from about 100 C. to about 110 C., for a period of about 7 to about 9 hours. At lower temperatures, longer heating periods may be required to obtain a product having the desired properties. If desired, ,one may determine, readily and accurately, by experimentation, the optimum duration of the; heating period in any particularembodiment of'the invention. The'ability: of the product produced to function eifectively as a dye leveling or dye retardant agent will be the most reliable indicia of whether a prescribed period of heating particular reactants at a given temperature has resulted in the production of the desired product. In a trial run, conducted prior to an actual plant run, samples may be extracted from the batch at regular intervals as the heating period progresses. These samples may then be finished 01f individually, in the manner disclosed heretofore, and each evaluated, on a laboratory scale, in a dye bath for its dye leveling and dye retardant properties. By means of a preliminary experiment such as this, one can readily establish the minimum amount of time a particular reaction mixture must be heated at a temperature within a specific range in order .to. produce a com- .pletely satisfactory product.

The products of this invention, since they were prepared in an aqueous system, are obtained in the form of aqueous solutions. They can be used assuch or they can be obtained as dry powdery products by any convenient means. Dry products having outstanding properties have been produced, for example, by spray drying the aqueous reaction mixture. The products of the invention, either in the form of dry powders or aqueous solution, will be found to possess excellent dye leveling and dye retardant properties. 'Moreover, theseproducts will exhibit little or no tendency to foam when used as assistants in dyeing. The present products are suitable for use both with direct dyes on fibers of cotton and rayon and with acid dyes on fibers of nylon, wool and silk. They are particularly effective for use where fiber uniformity and continuity is impaired, as, for example, in texturizedyarns and fabrics, waste nylons, novelty constructions and upholstery fabrics. Moreover, the present products have great utility as assistants in union dyeing, that is, in the coloring of combinations of fibers, for example, mixed fabrics containing wool and cotton; wool and rayon; cotton, viscose and silk; rayon and acetate; rayon and nylon; wool, and nylon; etc. In all such instances, excela lent fiber to fiber migration will be observed where the fibers are treated. with the products of this invention.

A noteworthy feature of the products of, the present invention is the fact that, ordinarily, their use will not necessitate any changes in the procedures or techniques presently utilized in conventional dyeing operations. In ordinary practice, the goods which are to be dyed will be wet out in an aqneous solution containing, on a dry weight basis, from about 1.0% to about 2.0%, based on the weight of the goods to be dyed, of the product of this invention. When the product is to be used as a leveling or retardant agent for a directdye, it is added to the bath comprising the normal ratio of to 30 parts by weight of liquor (water) for each part by Weight of fiber. However, when used with a direct dye, the product will be found to' function moreeffectivelywhen it is added to a dye bath, the liquor to fiber'ratio of which approximates 15bto l on aweight basis]; On the other hand, when the product is to be 'used asa leveling or retardant agent for an acid dye, it is added to. a'dye bath comprising a raito of about 10 to 30 parts by weight ofliquor (water) for each part by weight of fiber. Preferably, a liquor to fiber ratio of about to l on a weight basis will be usedinthe case of goods to be dyed using an be used in conjunction with certain wettingagents. Un-

der ordinary circumstances, however, the use of such wetting agents will not be necessary when the products of the present invention are in use. However,-regardless of whether a direct dye or an acid dye is in use, and

. regardless of whether an added acid or wetting agent is employed, maximum benefit will be derived from the use of the present products if the actual dyeing operation is carried out at a temperature of 200 F. or higher. The precise reason for this has not, as yet, been definitely established. One possible explanation is that the present products form unstable addition products with dyestuffs and that these break down at higher temperatures, for example, at temperatures of about 200 F. or higher. As a result of this, true leveling takes place rather thana .mere bloking- 1 For a fuller understanding of the natureand objects of this invention, reference may be had to the following examples which are given merely as a further illustration of the invention and are not to be construed in a limiting sense.- All parts given-in the examples areparts by weight unless otherwise indicated. a

" p p Example I Analiphatic alcohol derivative of beta-naphthalene sulfonic acid was first prepared by reacting approximately .equimolecular quantities of beta-naphthalene.sulfonic-acid and isopropyl alcohol (99%). In the preparation of the desired compound, the isopropyl alcohol was introduced intothe sulfonic acid compound over a period of about 3 hours. During the addition, the mixture was continuously heated at a temperaturewithin the range of from about 100 C. to about 1.05 C. Thereafter, the reaction was driven to completion by heating the reaction mixture for about 8 hours at a temperature of from about 100 C. to about C. During the entire heating operation, the reaction mixture was continuously stirred.

Concurrently with the production of the derivative of beta-naphthalene sulfonic acid, a resinous condensate was prepared as follows: Formaldehyde (37%) and an aqueous solution of ammonium sulfate were charged 'into a suitable reaction vessel. The reaction mixture was stirred and heated. to a temperature of. about 70C. When this temperature was reached, urea was slowly added to'the mixture, Sufiicient quantities of reactants were used .to provide the reaction mixture with a ratio of about 4.5

.mols of formaldehyde and 0.25 mol of ammonium sulfate for each mol of ureaused. Water comprised about 60.0% of the weight of the reaction mixture. The addition of the urea was carried out slowly and gradually with complete addition of that reactant being accomplished over a period of about one hour. The mixture was stirred and heated at a temperature of about 70 C. for two hours after the addition of .urea had been completed.

The dyeing assistant of this example was prepared by adding the aqueous resinous condensate, prepared as described heretofore, from formaldehyde, ammonium sulfate and urea, to the isopropyl alcohol derivative of betanaphthalene sulfonic acid. This mixture was stirred and heated at a temperature within the range of from about 100 C. to about C. for a period of about 8. hours. At-the end of that period of time, the reaction product was charged into a mixture comprising ice, water and a quantity of sodium hydroxide solution (40- B.) sufficient to adjust the pH thereof to within the rangeof from 8.0 to 8.3. The aqueous product was thereafter spray dried to yield a powdery product.

The product of this example was evaluated for use as an assistant for a direct dye in the dyeing of cotton fibers. The procedure used in this evaluation was as follows: Into a vat containing 2000 pounds of water and 2.0 pounds of the product of this example, 100 pounds of cotton material was placed. This was stirred at room temperature for about 20 minutes to insure complete wetting of the material. Thereafter, 0.5 pound of a direct dye was added to the vat. The direct dye, as added, had been previously dissolved in water and strained. Subsequently, heat was applied and the dyebath was brought to a boil. A small quantity of sodium chloride was added to the bath to facilitate exhaustion of the dye. Boiling was continued for a period of about one hour following which the dye liquor was removed from the vat. The dyed material was rinsed with cold water and then dried by conventional means.

The product of this example was evaluated for use also as an assistant for an acid dye in the dyeing of nylon fibers. The procedure used was the same as that used with a direct dye except that an acid dye was used in place of the direct dye and that 2.0 pounds of formic acid were added to the dye bath in place of the sodium chloride.

The results of these tests conclusively demonstrated the effectiveness of the product of this example as a dye leveling agent both for direct and acid dyes.

Example 11 In this example, 76.8 parts of anhydrous methanol were added slowly, over a period of about two hours, to 696 parts of beta-naphthalene sulfonic acid. During the addition of the methanol, and for a period of eight hours after the addition was completed, the mixture was heated at a temperature of from about 80 C. to 90 C.

Thereafter, the derivative of beta-naphthalene sulfonic acid, thus produced, was reacted with a resinous condensate. The same resinous condensate was employed in this example as was employed in Example I. Moreover, the reaction of the derivative of beta-naphthalene sulfonic acid with the resinous condensate was carried out in precisely the manner as was the reaction described in Example I.

The aqueous product obtained in this example was finished off as follows: The aqueous product was mixed with and dissolved in 500 parts of water. To this solution, 500 parts of ice are added. Thereafter, the aqueous product was treated with a sufficient quantity of sodium hydroxide solution (40 B.) to adjust the pH thereof to about 8.0. The aqueous product was then spray dried to yield a dry powdery product.

The product of this example was evaluated for use as an assistant for both acid dyes on nylon fibers and direct dyes on cotton fibers by the procedure described in Example I. Satisfactory results were obtained when this product was employed. The results of these tests demonstrated the effectiveness of the product of the example as a dye leveling agent both for acid and direct dyes.

Example III In this example, 120.0 parts of isopropyl alcohol (99%) were added slowly over a period of about 2 hours to 696.0 parts of beta-naphthalene sulfonic acid. During the addition of the isopropyl alcohol and for a period of about 8 hours after the addition was completed, the mixture was heated at a temperature within the range of from about 100 C. to 110 C.

At the end of that time, the reaction mixture was cooled somewhat and 500 parts of water and 30.0 parts of urea was added to, and mixed with, the reaction product. Subsequently, 17.5 parts of ammonium hydroxide and 25.0 parts of water were slowly added. During the addition of urea, ammonium hydroxide and water the temperature was maintained within the range of from about65 'C. to about 75 C. The mixture was then heated to a temperature of from about 100 C. to about 110 C. and 16 3.0 parts of formaldehyde (37%) was introduced therein gradually over a 2 hour period. The reaction mixture was stirred, and heated at a temperature within that range for an additional 8 hours after the addition of the formaldehyde had been completed.

The product was finished off as follows: 500.0 parts of water and 500.0 parts of ice were first added to the reaction product. Thereafter, the aqueous product was neutralized to a pH of about 8.0 by the addition thereto of approximately 5.00.0 parts of sodium hydroxide solution (40 B). The aqueous product was converted to a dry powder by spray drying.

The product of this example was evaluated for use as an assistant both for acid and direct dyes by the method described in Example I. In this instance, however, rayon fibers were dyed with a direct dye and Wool fibers were dyed with an acid dye. Completely satisfactory dyeing were obtained which indicated the effectiveness of the product of the example for use as a leveling agent for either direct or acid dyes.

Example IV In this example, a product was produced by the process described in Example III using the ingredients and the quantities thereof utilized in that example with but two exceptions. In producing the product of this example, 37.5 parts of urea were employed in place of 30.0 grams employed in the previous example. Moreover, in the production of the present product 204.0 parts of formaldehyde (37%) were used in place of the 163.0 parts of formaldehyde (37%) employed in Example III.

This product was finished in the same manner as was the product of Example III. It was evaluated for use as a dye assistant for both acid and direct dyes by the procedures described in Example I. In this instance, the direct dye was used on cotton fibers and the acid dye was used on silk fibers. The results which were obtained were completely satisfactory in every respect. The prodnet of the example proved to be an excellent leveling agent for both acid and direct dyes.

Example V In this example, 120.0 parts of isopropyl alcohol (99%) were added slowly to, and condensed with, 696.0 parts of beta-naphthalene sulfonic acid. The condensation reaction was carried out in the same manner as was the condensation in Example III, namely, at a temperature within the range of from about 100 C. to about C. for a period of about 8 hours.

At the end of that period of time, the reaction product was cooled to a temperature of from about 65 C. to about 76 C. and 40.0 parts of water and 17.5 parts of ammonium hydroxide were slowly added thereto. Thereafter, 60.5 parts of biuret were added to the mixture and the ensuing mixture was heated to a temperature of from about 100 C. to about 110 C. At that temperature, 163.0 parts of formaldehyde (37%) were introduced slowly and gradually into the reaction mixture. The addition of formaldehyde was carried out over a period of about 2 hours, during which time the mixture was continuously stirred and heated at a temperature of from about 100 C. to about 110 C. The mixture was heated and stirred at a temperature within that range for a period of about 8 hours after the addition of formaldehyde had been completed.

The aqueous product thus obtained was finished off in the following manner: 200.0 parts of water and 200.0 parts of ice were added to, and mixed with, the reaction product. The aqueous product was thereafter adjusted with sodium hydroxide solution (40 B.) to a pH of about 8.0. The aqueous product was converted to the form of a dry powder by spray drying.

The product of this example was evaluated for use as a dyeing assistant for acid and direct dyes by the procedures described in Example I. In the case of the direct dye, the material dyed was rayon fibers. In the case of 9 the acid dye, the material dye was a union of wool and nylon fibers.

In each instance, completely satisfactory results were obtained indicating that the product of this example was an outstanding leveling agent for both acid and direct dyes.

Having described my invention, what I claim is new and desire to secure by Letters Patent is:

1. A dyeing assistant which is the condensation product of heating, at a temperature of from about 80 C. to about 120 C., a mixture comprising (a) a resinous condensation product prepared by mixing, and heating at a temperature above about 60 C., a ratio of (1) from about 3.0 mols to 4.5 mols of formaldehyde, (2) from about 0.2 mol to about 0.5 mol of ammonium sulfate, and (3) about 1.0 mol of a compound selected from the group consisting of urea and biuret, said reaction being carried out in the presence of water, and (b) a naphthalene sulfonic acid derivative, and thereafter adding to the aqueous reaction product a quantity of alkali sufiicient to adjust the pH thereof to within the range of from about 7.5 to about 9.0 said ingredient (b) being the reaction product obtained by mixing in approximately equimolar proportions, at a'temperature of from about 80 C. to about 120 C. a naphthalene sulfonic acid with an anhydrous saturated aliphatic monohydroxy alcohol having from 1 to 3 carbon atoms in its chain there being about 0.3 mol to about 0.45 mol of said resinous condensation product for each 2.0 mols of said naphthalene sulfonic acid derivative.

2. A dyeing assistant which is the condensation prodnot of heating at a temperature of from about 80 C.

to about 120 C., a mixture comprising (a) a resinous condensation product prepared by mixing, and heating at a temperature of above about 60 C., a ratio of (1) from about 3.0 mols to 4.5 mols of formaldehyde, (2) from about 0.2 mol to about 0.5 mol of ammonium sulfate, and (3) about 1.0 mol of a compound selected from the group consisting of urea and biuret, said reaction being carried out in the presence of from about 45.0% by weight to about 80.0% by weight of water and (b) a naphthalene sulfonic acid derivative, and thereafter adding to the aqueous reaction product a quantity of alkali sufiicient to adjust the pH thereof to within the range of from about 7.5 to about 9.0, said ingredient (b) being the reaction product obtained by mixing in approximately equimolar proportions, at a temperature of from about 80 C. to about 120 C., a naphthalene sulfonic acid and an anhydrous saturated aliphatic monohydroxy alcohol having from 1 to 3 carbon atoms in its chain there being about 0.3 mol to about 0.45 mol of said resinous condensation product for each 2.0 mols of said naphthalene sulfonic acid derivative.

3. The composition of claim 2 wherein urea is employed.

4. The composition of claim 2 wherein biuret is employed.

5. A dye assistant which is the condensation product of heating at a temperature of from about 80 C. to 120 C. a mixture comprising (a) a pro-formed resinous condensation product prepared by mixing, and heating at a temperature of from about 60 C. to about 100 C., a ratio of (1) from about 3.0 mols to 4.5 mols of formaldehyde and (2) from about 0.2 mol to about 0.5'mol of ammonium sulfate and (3) about 1.0 mol of a compound selected from the group consisting of urea and biuret, said react-ion being carried out in the presence of from about 45.0% to about 80.0% by weight of Water, and (b) a beta-naphthalene sulfonic acid derivative, thereafter adding to the aqueous reaction product, a quantity of alkali suflicient to adjust the pH thereof to within the range of 7.5 to 9.0, said ingredient (b) being the reaction product obtained by mixing in approximately equimolar proportions, at a temperature of from about 80 v 10 v C. to 120 C., beta-naphthalene sulfonic acid and an anhydrous saturated aliphatic rnonohydroxy alcohol having from 1 to 3 carbon atoms in its chain there being about 0.3 mol to about 0.45 mol of said resinous condensation product for each 2.0 mols of said naphthalene sulfonic acid derivative. 7

6. A dye assistant which is the condensation product of a resinous condensate and a beta-naphthalene sulfonic acid derivative produced by adding ammonium hydroxide, water and a compound selected from the group consisting of urea and biuret to, and mixing same with a beta-naphthalene sulfonic acid derivative at a temperature of from about 60 C. to about C., whereby ammonium sulfate forms, heating said mixture at a temperature within the range of from about 60 C. to about C., while adding formaldehyde gradually thereto, maintaining such reaction temperature for a period of at least about seven hours and thereafter adding to the aqueous reaction product, a quantity of alkali sufficient to adjust the pH thereof to within the range of 7.5 to 9.0, said beta-naphthalene sulfonic acid derivative being the reaction product of approximately equimolar proportions of beta-naphthalene sulfonic acid and an anhydrous saturated aliphatic rnonohydroxy alcohol having from 1 to 3 carbon atoms in its chain and there being present in the reaction mixture a ratio of from about 3.0 mols to about 4.5 mols of formaldehyde and from about 0.2 mol to about 0.5 mol of ammonium sulfate for each mol of the compound selected from the group consisting of urea and biuret present therein, there being about 0.3 mol to about 0.45 mol of said resinous condensation product for each 2.0 mols of said naphthalene sulfonic acid derivative.

7. A dye assistant which is the condensation product of a resinous condensate and a beta-naphthalene sulfonic acid derivative produced by adding ammonium hydroxide, water and a compound selected from the group consisting of urea and biuret to, and mixing same with, a beta-naphthalene sulfonic acid derivative at a temperature of from about 65 C. to about 75 C., whereby ammonium sulfate forms, heating said mixture to a temperature of from about 100 C. to about 110 C. while adding formaldehyde gradually thereto and maintaining such reaction temperature for a period of from about seven to about nine hours and thereafter adding to the aqueous reaction product, a quantity of alkali sufficient to adjust the pH thereof to within the range of 7.5 to 9.0, said beta-naphthalene sulfonic acid derivative being the reaction product of approximately equimolar proportions of beta-naphthalene sulfonic acid and an anhydrous saturated aliphatic monohydroxy alcohol having from 1 to 3 carbon atoms in its chain and there being present in the reaction mixture a ratio of from about 3.0 mols to about 4.5 mols of formaldehyde and from about 0.2 mol to about 0.5 mol of ammonium sulfate for each mol of the compound selected from the group consisting of urea and biuret present therein, there being about 0.3 mol to about 0.45 mol of said resinous condensation product for each 2.0 mols of said naphthalene sulfonic acid derivative.

8. The product of claim 6 wherein the aliphatic monohydroxy alcohol used is methyl alcohol.

9. The product of claim 5 wherein the aliphatic monohydroxy alcohol used is ethyl alcohol.

10. The product of claim 5 wherein the aliphatic monohydroxy alcohol used is isopropyl alcohol.

11. The product of claim 7 wherein urea is employed.

12. The product of claim 7 wherein biuret is employed.

13. The product of claim 11 wherein the aliphatic monohydroxy alcohol used is methyl alcohol.

14. The product of claim 11 wherein the aliphatic rnonohydroxy alcohol used is ethyl alcohol.

15. The product of claim 11 wherein the aliphatic rnonohydroxy alcohol used is isopropyl alcohol.

16. The product of claim 12 wherein the aliphatic 2,193,630 monohydroxy alcohol used is isopropyl alcohol. 2,227,708 2,433,680 References Cited in the file of this patent 2,4 9 157 UNITED STATES PATENTS 6 2,884,

1,718,901 Garns et a1 June 25, 1929 2,134,235 Pollak Oct. 25, 1938 709,078

12 Howald Mar. 12, 1940 Cordier Jan. 7, 1941 Backman Dec. 30, 1947 Cordier May 3, 1949 Zorn et a1 Apr. 28, 1959 FOREIGN PATENTS Great Britain May 12, 1954 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,072,611 January 8 1963 Lucien Sellet I It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 10, line 62, for the claim reference numeral "6" read 5 Signed and sealed this 28th day of January 1964.

(SEAL) Attcst:

EDWIN Lo REYNOLDS ERNEST W. SWIDER Attesting Officer A ting Commissioner of Patents

Claims

1. A DYEING ASSISTANT WHICH IS THE CONDENSATION PRODUCT OF HEATING, AT A TEMPERATURE OF FROM ABOUT 80*C. TO ABOUT 120*C., A MIXTURE COMPRISING (A) A RESINOUS CONDENSATION PRODUCT PREPARED BY MIXING, AND HEATING AT A TEMPERATURE ABOVE ABOUT 60*C., A RATIO OF (1) FROM ABOUT 3.0 MOLS TO 4.5 MOLS OF FORMALDEHYDE, (2) FROM ABOUT 0.2 MOL TO ABOUT 0.5 MOL OF AMMONIUM SULFATE, AND (3) ABOUT 1.0 MOL OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF UREA AND BIURET, SAID REACTION BEING CARRIED OUT IN THE PRESENCE OF WATER, AND (B) A NAPHTHALENE SULFONIC ACID DERIVATIVE, AND THEREAFTER ADDING TO THE AQUEOUS REACTION PRODUCT A QUANTITY OF ALKALI SUFFICIENT TO ADJUST THE PH THEREOF TO WITHIN THE RANGE OF FROM ABOUT 7.5 TO ABOUT 9.0 SAID INGREDIENT (B) BEING THE REACTION PRODUCT OBTAINED BY MIXING IN APPROXIMATELY EQUIMOLAR PROPORTIONS, AT A TEMPERATURE OF FROM ABOUT 80*C. TO ABOUT 120*C. A NAPHTHALENE SULFONIC ACID WITH AN ANHYDROUS SATURATED ALIPHATIC MONOHYDROXY ALCOHOL HAVING FROM 1 TO 3 CARBON ATOMS IN ITS CHAIN THERE BEING ABOUT 0.3 MOL TO ABOUT 0.45 MOL OF SAID RESINOUS CONDENSATION PRODUCT FOR EACH 2.0 MOLS OF SAID NAPHTHALENE SULFONIC ACID DERIVATIVE.