US2043179A

US2043179A - Dye preparation

Info

Publication number: US2043179A
Application number: US43926A
Authority: US
Inventors: Kritchevsky Wolf
Original assignee: RIT PRODUCTS CORP
Current assignee: RIT PRODUCTS Corp
Priority date: 1932-12-09
Filing date: 1935-10-07
Publication date: 1936-06-02
Anticipated expiration: 1953-06-02

Description

Patented June I 2, 1936 PATENT OFFICE 2.643.179 pm PREPARATION Wolf Kritchevsky,

Chicago, Ill., assignor to Kit Products Corporation, Chicago, Ill., apcorporation of Delaware No Drawing.

1932, Serial 10 Claims.

My invention relates to an improved packaged dye for home us and the method of producing the same, I

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 result 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 must be placed in his hands which, with the limited experience and ability available to the amateur dyer, will turn out a first class product on all types of materials. The development of a dye for home use, therefore, is an exceedingly technical problem because the dye must have characteristics which the skilled dyer would never expect in his own product. i There has been an extensive development of dyes for home use. "The so called soap dyes were one of the early developments These took on diiferent forms, all attempting to improve the products. The soap dyes have employed assistants with them such as sulphonated oils and other materials along this general line. Besides taking a considerably longtime to dissolve, they possessed other disadvantages at times, well known to those skilled in' the; art. Applicant's 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 dye a material which would function as a soap inits desirable properties but which would avoid the disadvantages attending the use of soap. The resulting product had exproper leveling;v it didnot precipitate out inthe presence of hard water as soap did. The principal disadvantage of this product, however, was that after dyeing with it the garments did not have the proper finish and the proper feel. 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 oleaginous material in the dye bath, such as a sulphonated oil or similar oleaginous substance, it being known that the more oleagincus the product, the greater the improve- Jmentjin so far as the finish and feel. I attempted to improve the dye product produced in accordance with the above mentioned patent by emuct of the desirable along this line.

' obtained in the most Original application December '9, Y No. 646,496. plication October '7. 1935,

Divided and this ap- I Serial No. 43,926

ploying 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 because the presence of the oily material seemed to deprive the prodcharacteristicsv obtained by the use of the wetting agent. In other words, the resulting dye no longer dissolved readily and possessed some of the same disadvantages attending the use of ordinary soap dyes. In spite of all of the developments, I still found that there was difi'iculty due to the forming of lime salts and the disadvantage of not being able to work in'a slightly acid medium, which is preferable for most dyeing.

With this knowledge of the art before me, it

' 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 up-to-date dyeing establishments. I

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 that considerable work had been done eitherto replace the carboxyl group with another group or to combine it chemically with some other compound or compounds so that it would not exert its harmful effect. In sulphonated oils, the carboxyl group is in the form of a glyceride, but being a tri-glyceride, the ratio of the esterifying alcohol to the total amount of the carboxyl groups is not sufficient to keep it stable and for this reason when heated lime salts and insoluble greases. A great advance was made by the realization that when the carboxyl group is esterified with a mono-valentor polyvalent alcohol or amidized with ammonia or an amine or their substitution products, the resulting products become stable. In the case of with water it hydrolyzes and forms the polyvalent alcohols, not all the valences are ester-ified with the carboxyl groups and at least one hydroxy group is left either free or positively substituted. The compounds obtained are quite stable and surprisingly also excellent wetting agents and I have found that compounds of this kind have all the desirable properties when employed with a dye for home use without having 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 esteriiied fatty acid which is esterified with a monovalent alcohol.

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

(a) sulphonated stearyl amid of the formula soms 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 oneor two of the hydroxy groups of glycerol free or positively substituted, desirable compounds are obtained. These compounds can also be made by first esterifying the fatty acid and making compounds like monostearyl glycol 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 efllcient. To illustratefl 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 esterified alcohol giving a sulphonic acid group. In this case fatty acid esters of ethane sulphonic acid are obtained of the general formula RCOQCzHsSOsH In other words, fatty acid products of ethioni 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. 1

Along with the line of development of making the carboxyl group harmless through esterification or amidization, another method was devised which is proving to be commercially very successful and scientifically correct, viz: the carboxyl 5 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, stearic 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 are excellent penetrating agents, emulsifying agents, and also finishing materials. They are known in commerce under the name of Gardinols, "Avirols, etc.

The development in the last line of work has 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 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. 3 I am referring in this case to the straight sulphonic acid of aliphatic hydrocarbons having a 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 35 Reychler in the Kolloidale Zeitschrift, volume 12,

. page 277 in 1913. This compound is very soluble 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 40 until lately and Prof. Schrauth has published an article in the Chemiker Zeitung for 1931, page 1984, in which he states that when sulphuric esters of aliphatic alcohols are treated with sodium suiphite, the sulphonic acids of the corresponding 45 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 sul- 50 phonated, in which case 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 cnucmi isCHOHCI-IrSOaH which was described in Example 1 of the above chain aliphatic alcohols; or sulphuric or phos- 70 phoric 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 monovalent alco- 75 Eli at least eight carbon atoms or more and has afiinity for i'ats, oils, or different organic compounds. inorganic acid that makes the compound as. a 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 emulsifier, being in a position to disperse fats and greases in water and give a fatty feel to compounds with which it is pene-" trated from a purely water medium.

In the above description I have given an idea of the diiferent classes of compounds and representative examples that are suitable for my purpose.

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 with other agents under any condition in which they may be used. In other words, the compound employed must be strongly hydrophillic and have great penetrating value but at the same time it must also possess oleophillic properties to the point where it will be a good finishing agent, leaving the textile material treated pliable with a soft "feel. Any compound answering this description will naturally fall within my disclosure.

It is understood that also solvents, diluents, fillers, and other assistants may be used without departing from the true scope of the invention.

The following examples are illustrative of my invention:

Example 1 direct black, color index #581 v of the sodium salt of the sulphuric ester of lauryl alcohol of the general formula commercially known as Gardinol WA common salt.

Example 2 mula C11HaaCH2-O-SO3N8. otherwise known as Gardinol CA.

Example 3 of direct green, color index #593 of chrystophenin, index #365 of the sodium salt of the sulphuric acid ester of cetyl alcohol of the general formula CmHarCHe-O-SOaNa otherwise known as Avirol 142 ammonium sulphate.

The polar group is a strong oxygenated Example 4 of methylene blue, color index #922 of sodium salt of the sulphuric acid ester of reduced coconut oil fatty acids, commercially known as Gardinol R 5 dextrine.

Example 5 acid Rhodamine 3R, Manual 534 sodium cetyl sulphonate alcohol glycerin.

Example 6 20% Catechu G N, color index #420 15% sodium salt of the sulphation product mono= oleyl ethylene glycol of the formula I cunaco-owrrhcnhosoma common salt.

Example 8 of cyanone blue 5R, color index #289 direct blue BB, color index #406 of the sodium salt of the sulphuric acid ester of oleyl alcohol of the general formula C11HaaCH;OSOaNa otherwise known as Gardinol CA of Glauber salt.

Example 9 CilHaz (OH) COOC2H4SO3Na Glauber salt.

Example 10 50 algol scarlet G, color index #1129 benzyl ester of sulpholeic acid of thegeneral formula CHHM (OSOaNa) COOCHzCsHs of sodium hydroxide of sodium hydrosulphite of sodium carbonate.

Example 11 of lithol rubin BN, color index #163 of the salt of the phosphoric acid ester of distearyl glycerin of the formula soda ash Glauber salt.

Example 12 10% 10% of sulphonated oleyl amide Ci'1H34 OSOsNa) CONHz 80% salt.

chrysamine, C. I. 365 7 70 simple 1;

10% Pontamine Bordeaux B, color index #375 10% Lecithin 20% salt 60% sugar.

My preparation may be in either solid, liquid, or paste form, using diluents, fillers, or assistants of various kinds. The penetrating chemicals must have a very strong hydrophillic group such as a strongly acidic group, like sulphonic acid group, phosphoric acid group or similar groups.

They must have an excellent wetting out action,-

derivatives like hydroxy, halogen derivatives,

acidic derivatives. They also may have an aralkyl group, the 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 C3 up to C12 have the oleophillic properties not as pronounced as those beginning with Cu, 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 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 med a. The terms soluble" and ,solubility 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 dis-' persions 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.

Wherever the term'alkionic acid" is used, it will be understood to cover ethionic acid and also sulphonic acid derivatives of aliphatic hydrocarbons such as methylene, ethylene, propylene, butylene, et cetera.

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 normallywater-soluble dye-and a chemical compound corresponding to the general formula RC0O--R' carbon atoms and their hydroxy and oxygenated sulphur or phosphorus substitution products, R is a radicalof the class consisting of alkyl, aralkyl, and alkylol, and their oxygenated sulphur or phosphorus substitution products, there being at least one'oxygenated sulphur or phosphorus group in the final -mo1ecule containing an hydroxy group or salt thereof, 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 dye operations.

2. A home dye composition in solid form comprising an intimate admixture of a normally water-soluble dye and an alkionic acid ester of a higher aliphatic acid, 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 dye operations.

3. A homedye 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 R is an alkionic radical, 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 dye operations,

4. 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 8 carbon atoms and 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 dye operations.

6. 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 R is the residue of an aliphatic polyhydric alcohol wherein the hydrov sulphur or phosphorus acid radical, 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 dye operations.

7. A home dye composition in solid form comprising an intimate admixture of a normally water-soluble dye and an inorganic oxygenated sulphur or phosphorus acid derivative of a fatty acid, having at least eight carbon atoms,esterified at the carboxyl group with a mono-valent alcohol, said dye composition possessing" the properties of imparting an oily feel to fabrics dyed therewith and producing eve level shades under any of the conditions normally encountered in home dye operations.

8. A home dye composition in solid form comprising an intimate admixture of a normally water-soluble dye and a chemical compound having the formula 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 dye op-. eratlons.

9. A home dye composition in solid form comprising an intimate admixture of anormally water-soluble dye and an inorganic oxygenated sule phur or phosphorus acid ester of van aliphatic polyhydric alcohol, said alcohol being partially.

esterifled with a fatty acid containing at least eight carbon atoms, 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 dye operations.

10. A home dye composition in solid form comprising an intimate admixture oi. a normally water-soluble dye and a chemical compound having the formula v dm- -osoir v wherein Y is hydrogen or an alkali metal, said dye composition possessing the properties oi. imparting an oily feel to fabrics dyed therewith and producing even, level shades under any of the conditions normally encountered in home dye operations.

' WOLF KRITCHEVSKY.