US2043178A - Dye preparation - Google Patents

Description

Patented June 2, 1936 DYE PREPARATION Wolf Kritchevsky; Chicago, Ill., assignor to Kit Products Corporation, Chicago, 11]., a corporation of Delaware No Drawing. Original application December 9,

1932, Serial No. 646,496. Divided and this application October 7, 1935, Serial No. 43,925

7 Claims.

My invention relates to an improved packaged 'dye for home use and the method of producing the same.

f It is well understood that the art of dyeing fabrics is an exceedingly complicated and technical business. Regularly established dyeing industries are equipped to make use of all of the known chemicals, assistants, mordants and the like which the industry possesses; as-well as all of the equipment for turning out a first class re- I sult independent of the type of material or color.

The home dyer has none of the facilities available to the regular dyeing-establishments and so a dye 1 must be placed in his hands which, with the limited experience and ability availableto the amateur dyer, will turn out a first class product on all types of materials. The development of a W dye for home use, therefore, is an exceedingly I technical problem because the dye must have characteristics which the skilled dyer would never expect in his own product. i J

There has been an extensive development of dyes for home use. The so called soap dyes. were one of the early developments along this line. These took on different forms, all attempting to improve the product. The soap dyes have employed assistants with them such as sulphonated oils and other materials along this general line. Besides taking a considerably long time to dissolve, they possessed other disadvantages at times, well known to those skilled in the art. Applicants prior Patent No. 1,752,184 represented a development which was a great step forward in the art and consisted of substituting for the soap in the soap dyea material which would function as a soap in its desirable properties but which would avoid the disadvantages attending the use of soap. The resulting product had excellent solu- 4 bility, proper leveling; it did not precipitate outin the presence of hard water as soap did. The

principal disadvantage of this product, however, was that after dyeing with it the garments did nothave the proper finish and the proper feel.

45 In other words, the garment so dyed did not have the appearance of 'a new garment, which is one of the features expected in a newly dyed piece of fabric. It is well known that this finish and feel can be obtained in part from the use of an ole 50 aginous material in the dye bath, such as a sulmentioned patent by employing a mixture of sulphonated alkylated polynuclear hydrocarbons and the compound .having fatty properties such as sulphonated oil or a sulphonated soap. I found that this was impossible in a practical way be- 5 cause the presence of the oily material seemed to deprive the product of the desirable characteristics obtained by the use of the wetting agent. In other words, the resulting dye no longer dissolved readily and possessed some of the same 10 disadvantages attending the use of ordinary soap dyes. In spite of all of the developments, I still found that there was difiiculty due to the forming of lime salts and'the disadvantage of not being able to work in a slightly acid medium, which is 15 preferable for most dyeing. I

With this knowledge of the art before me, it was my object to produce an improved dye for home use which would have all of the advantages of such dyes heretofore used but would also avoid 20 all of the disadvantages thereof.

Another object is the provision of. an improved dye for home use adapted to be employed with different types of fabrics.

Another object is to place a packaged dye in the hands of the ordinary housewife which will permit her substantially to duplicate the results obtained inthe most up-to-date dyeing establishments.

Other objects and features of the invention will be apparent as the detailed description progresses.

In developing my improved product, I proceeded on the assumption that the carboxyl group in some of the compounds, soaps, sulphonated oil, etc., employed in home dyes was undesirable. for the reason that it forms insoluble precipitates with calcium and magnesium salts found in hard water. This was not a new concept as I knew 40 that considerable work had been done either to replace the carboxyl group with another group or to combine it chemically with some other com-- pound or compounds so that it would not exert its harmful efiect. In sulphonated oils, the carboxyl group is in the form of a glyceride, but being a triglyceride, the ratio of the esterifying alcohol to the total amount of the carboxyl groups is not sufiicient to keep it stable and for this reason when heated with water it hydrolyzes and forms lime salts and insoluble greases. A great advance was made by the realization that when the carboxyl group is ,esterified with a mono-valent or polyvalent alcohol or amidized with ammonia or an amine or their substitution products, the re- 66 suiting products become stable. In the case of the polyvalent alcohols, not all the valances are to use additional wetting agents of the type required previously.

To describe such compounds; I wish to cite the following references: Monovalent alcohol esters of-a sulphonated oil are the .butyl ester or benzyl ester of sulphonated oleic acid as described in the United States Patent No. 1,822,977, Example 3; two other patents 1,822,978 and 1,822,979 describe similar compounds and methods of making them. These compounds can be made by esterifying a sulphonated fatty acid or by sulphonating an esterified fatty acid which is esterifled with a monovalent alcohol.

Amids of sulphonated fatty acids can be characterized by the following compounds:

(0) Sulphonated'stearyl amid of the formula 8 OaNB ciinuc n-od-ma,

and the alkyl" and aryl substitution products thereof like benzyl stearyl amide sulphonic acid 8 OaNB Ci|Ha(.l HCONHCH:CcH| etc. (b) Sulpholeil amid or the formula C11Bn(OS0zNa)C ONE:

y In the case wheire divalent alcohols are used like ethylene glycol, diethylene glycol or trivalent alcohols like glycerol, then at least one of the hydroxy groups should remain free or positively substituted and preferably two. In other words, if sulpholeic acid is esterifled with ethylene glycol, diethylene glycol or glycerol leaving one of the hydroxy groups of the glycol free or positively substituted or one or two of the h'ydroxy groups of glycerol free or positively substituted, desirable compounds are obtained. These compounds can or monoleyl glycol or monostearyl glycerol or distearyl glycerol and then sulphonating the ester where the sulphuric acid group will go into the fatty acid nucleus or preferably form an ester with the hydroxy group. Phosphoric acid esters can be made which are just as efflcient. To illustrate, I wish to. refer to German Patent No. 193,189, where the distearyl glycerol phosphoric acid ester is described. Another compound belonging to the same class is the mono-oleyl ethylene glycol sulphonated as described in French Patent No. 721,340, Example 1.

The compounds described in the above paragraph are esters of alcohols and sulphuric or phosphoric acid. An advance in this was made in the United States Patent No. 1,881,172 in which case the acidic group is tied directly to the carbon atom of the esterifled alcohol giving a sulphonic acid group. In this case fatty acid esters of ethane sulphonic acid are obtained of the general formula RCOOCzH4SOaH In other words, fatty acid products of ethionic acid are obtained. Those compounds have all the desirable properties like wetting, stability in lime water and slightly acid solutions and also give the proper finish to textiles.

' Along with the line of development of making the carboxyl group harmless through esteriflcation or amidization, another method was devised 6 which is proving to be commercially very successful-and scientifically correct, viz: the carboxyl group is reduced to an alcoholic group' and the corresponding alcohol sulphated or phosphated.

In the industry, lauric acid has been successfully reduced to form the lauryl alcohol, stearlc acid to form the stearyl alcohol, oleic acid to form the oleyl alcohol. Cetyl alcohol is, of course, a natural product being obtained from the saponification of spermaceti.

Any one of these alcohols can be properly sulphated or phosphated to form the sulphuric or phosphoric acid esters of the corresponding alcohols. Those esters and their water soluble salts 20 are excellent penetrating agents, emulsifying agents, and also flnishing'materials. They are known in commerce under the name of Gardinols, Avirols", etc.

The development in the last line of work has 25 brought back to life another class of substances which, from the viewpoint of the chemical and physical action, replace soap with great advantage but were never considered commercially in view of the fact that the matter of preparation 30 was too involved and they could not be obtained in either commercial quantities nor at prices in which they could be serious competitors to soap. I am referring in this case to the straight sulphonic acid of aliphatic hydrocarbons having a 35 chain of eight carbon atoms or more. A representative of this class is cetyl sulphonic acid and its salts which were described in great detail by Reychler in the Kolloidale Zeitschrift, volume 12, page 277 in 1913. This compound is very soluble 40 I in water in the form of its free acid or salts, gives an excellent foam, penetrates well, and has fatty characteristics. It was of no commercial value until lately and Prof. Schrauth has published an article in the Chemiker Zeitung for 1931, P e 45 1984, in which he states that when sulphuric esters of aliphatic alcohols are treated with sodium sulphite, the sulphonic acids of the corresponding hydrocarbons can be obtained in good commercial quantities. This work was further followed up and described in English Patent No. 358,583, in which case unsaturated hydrocarbons with a chain of not less than eight carbon atoms are sulphonated, in whichcase true sulphonic acids are formed and the next carbon to the carbon that has the sulphonic acid group on it has a hydroxy group. As one product I can quote the hydroxy octadecyl sulphonic acid of the formula CH3 (CH2) i5CHOHCH2SOaH which was described in Example 1 of the above named patent. While all those above named chemicals will fall into a certain number of chemical groups depending upon their structure, yet from the viewpoint of the physical behavior, especially in regard to my application of them, they are all to be construed as one class.

Chemically we may say those substances are either sulphonic or phosphonic derivatives of long chain aliphatic hydrocarbons or they are sulphuric or phosphoric acid derivatives or for that matter derivatives of oxygenated inorganic acids of amids of higher aliphatic fatty acids and their derivatives or esters of higher aliphatic acids esterifled in the carboxyl group either with 25 pcse.

- mono-valent alcohols or polyvalent alcohols in which not all of the hydroxy groups are esterifled with carboxylic acids.

On the other hand, from a physical viewpoint and from a viewpoint of application, they have the following in commonz-They are chemicals having polar and non-polar groups connected {together in the same molecule in a very balanced ratio in which the non-polar group is strongly oleophillic due to the fact that it has a chain of at least eight carbon atoms or more and has affinity for fats, oils, or different organic compounds. The polar group is a strong oxygenated inorganic acid that makes the compound as a 5 whole strongly hydrophillic, makes the compound easily soluble in water and thereby the whole compound as such becomes a very good penetrating agent, an ideal emulsiflenbeing in a position to disperse fats and greasesin water and give a fatty feel to compounds with which it is penetrated from a purely water medium.

I In the above description I have given an idea of the different classes of compounds and representative examples that are suitable for my pur- I have done it only for the purpose of teaching the art to the extent where it would be easy for any qualified chemist to arrive at other classes of the same general characteristics.

In general, I found that the proper types of compounds that are necessary for my purpose must be 'quite soluble by forming a true solution or colloidal solution or form at least a very fine stable dispersion in water without precipitating departing from the true scope of the invention.

The following examples are illustrative of my invention Example 1 g 20% direct black, color index #581 10% of the sodium salt of the sulphuric ester of lauryl alcohol of the general formula cumacrlo o-some commercially known as Gardinol WA 70% common salt.

Example 2 5% of cyanone blue 5R, color index #289 5% direct blue BB, color index #406 90% of the sodium salt of the sulphuric acid ester.

of oleyl alcohol of the general formula CrzHaaCHz-O-SOaNa otherwiseknown es Gardinol CA Example 3 t 25% of direct green, color index #593 5% of chrystophenin, index #365 25% of the sodium salt of the sulphuric acid ester of cetyl alcohol of the general formula CmI-IarCI-Ia-O-SOaNa otherwise known as Avirol 142 76' 45% ammonium sulphate 10% chrysamine', C. I. #365 Example 4 3% of methylene blue, color index #922 3% of sodium salt of the sulphuric acid ester of reducedcoconut oil fatty acids, commercially known as Gardinol R 5 I 94% dextrine f Example 5 5% acid Rhodamine 3R, Manual 534 5% sodium cetyl sulphonate 10 45% alcohol 45% g ycerin Example 6 20% Catechu GN, color index 420 3% hydroxy-octadecyl-sulphonic acid, general formula 30% Alizarine blue, color index #1054 sodium salt of the sulfation product monooleyl ethylene glycol of theformula 25 Cl'lI-BaCO -OCHaCHzO-SO3Na 55% common salt.

Example 8 5% of cyanone blue 5R, color index #289 direct blue BB, color index #406 15% of the sodium salt 'of the sulphuric acid ester of oleyl alcohol of the general formula otherwise known as Gardinol CA of Glauber salt Example 9 10% Pontamine Bordeaux 3, color index #375 9% Cyamine blue 5R, color index #289 20% Dark blue BI- I, color index #401 11% sodium salt of ricinoleic acid of ethionic acid of the general formula 45 C1'lHs2(OH)CO--OC2H4SQ3N9.

50% Glauber salt v Example 10 20% algol scarlet G, color index #1129 20% benzyl ester of sulpholeic acid of the general formula CnHaMOSOzN a) COOCHzCcHs 10% of sodium hydroxide 20% of sodium hydrosulphite 30% of sodium carbonate Example" 11 10% of lithol rubin BN, color index #163 10% of the salt of the phosphoric acid ester of distearyl glycerin of the formula 1 10% soda ash 70% Glauber salt I Example 12 10% of sulphonated oleyl amide of the general formula Cl'lHa4(OSOaNa) CONH:

salt 76.

Example 13 10% Pontamine Bordeaux B, color index #375 10% Lecithin 20% salt 60% sugar it some oily feel which is accomplished by these particular chemicals having an alkyl group of not less than eight carbon atoms or its derivatives like hydroxy, halogen derivatives, acidic derivatives. alkyl group still not having less than seven carbon atoms.

The degree of the oleophillic properties of these compounds can be regulated by the length of the hydrocarbon chain. Those from Ca up to C12 have the oleophillic properties not as pronounced as those begining with Cm, and depending upon the desirability of the degree of oiliness required those compounds can be chosen to suit the product, but it must be understood that in no case can the product be useful unless it is still quite hydrophillic.

In describing the invention, it is understood that the examples and illustrations given are to be taken in a descriptive sense rather than in a limiting sense. As far as the specific examples of the dye products are concerned, these are meant to show different types of wetting and combining agents. I

. I have referred hereinabove to the solubility of the class of chemicals which I employ by stating that they should be freely soluble, colloidally soluble or form very fine dispersions in aqueous media. The terms soluble and "solubi1ity as employed in the claims, therefore, are used in the broadest sense to refer either to true solutions or to colloidal solutions or very fine dispersions which, as far as my purpose is concerned, have substantially the same function as true, solutions. It should also be borne in mind that many terms employed in the specification are used in a descriptive sense rather than in a limiting sense and the details are given for illustration so that those skilled in the art may be able to practice the invention. The novelty is defined in the appended claims.

Water soluble" as employed in the claims is used in a broad sense to include the characteristics of either molecular or colloidal dispersibility.

This application'is a division of my application Serial No. 646,496 filed December 9, 1932.

What I claim as new and desire to protect by Letters Patent of the United States is:

1. A home dye composition in solid form comprising an intimate admixture of a normally water soluble. dye and a chemical compound corresponding to the general'formula R-co-NY-R' They also may have an aralkyl group, the

wherein R is a radical of the class consisting of aliphatic hydrocarbons with at least eight carbon atoms and their hydroxy or oxygenated sulphur or phosphorus substitution products, R is a radical of the class consisting of hydrogen, alkyl, aralkyl, and allgvlol, and their oxygenated sulphur or phosphorus substitution products, and Y is hydrogen, an alkyl or an alkylol radical, there being at least one oxygenated sulphur or phosphorus radical in the final molecule, said dye composition possessing the properties of imparting an oily" feel to fabrics (Bred therewith and producing even, level shades under any of the conditions normally encountered in home dyeing operations.

2. A home dye composition in solid form comprising an intimate admixture of a normally water soluble dye and a chemical compound corresponding to the general formula wherein R is an aliphatic radical with at least eight carbon atoms and containing at least one oxygenated sulphur or phosphorus group, said dye composition possessing the properties of imparting an oily feel to fabrics dyed therewith wherein Y is hydrogen or an alkali metal, said dye composition possessing the properties of imparting an oily feel to fabrics dyed therewith and producing even, level shades under any of the conditions normally encountered in home dyeing operations.

4. A home dye composition in solid form comprising an intimate" admixture of a normally water-soluble dye and a chemical compound of the class consisting of oxygenated sulphuror phosphorus-containing acid derivatives of higher aliphatic acid amides and their K-alkyl, N-arallwl, or alkylol substitution products, said dye composition possessing the properties of imparting an "oily feel to fabrics dyed therewith and producing even, level shades under any of the conditions normally encountered in home dyeing operations.

5. A home dye composition in solid form comprising an intimate admixture of a normally water soluble dye and a chemical compound of the class consisting of a sulphonated higher fatty acid amide, said dye composition possessing the properties of imparting an oily feel to fabrics dyed therewith and producing even, level shades under any of the conditions normally encountered in home dyeing operations.

6. A home dye composition in solid form comprising an intimate admixture of a normally water-soluble dye and a chemical compound hav ing the formula C1|HaCHCO-NH1 OaY wherein Y is hydrogen or an alkali metal, said dye composition possessing the properties of imparting an oily feel to fabrics dyed therewith and producing even, level shades under any of the conditions normally encountered in home dyeing operations.

7. A home dye composition in solid form comprising an intimate admixture of a. normally water-soluble dye and a. chemical compound of the class consisting of a sulpholeyl amide, said dye composition possessing the properties of imparting an oily feel to fabrics dyed therewith and producing even, level shades under any of the conditions normally encountered in home dyeing operations.

WOLF KRITCHEVSKY.