US2042473A - Dye preparation - Google Patents

Description

Patented June. 2, 1936 DYE PREPARATION Wolf Kritchevsky, Chicago, 111., assignor to Bit Products Corporation, Chicago, 111., a corporation of Illinois No Drawing. Application December 9, 1932,

Serial No. 646,496

10 Claims.

- the same.

It iswell understood that the art of dyeing fabricsis 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.

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 inthe'jart. 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 dye a 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 solubility, proper leveling; it did not precipitate out in the 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 otherlwords, 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 knownthat 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 ole'aginous substance, it being known that the more oleaginous the product, the greater the improvement insofar as the finish and feel. .I attempted to improve the dye product produced in accordance with the above mentioned patentby 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 because the presence of the oily 5 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 disadvantages attending the 10 use of ordinary soap dyes. In spite of all of the developments, 1 still found that there was difii culty due to the forming of lime salts and the disadvantage of not being able to work in a slightly I acid medium, which is preferable for most dyeing. 15

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 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 25 permit her substantially to duplicate the results obtained in the most up-to-date dyeing establishments.

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

vIn developing my improved product, Iproceed-' ed 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 either to replace the carboxyl group with another group 40 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, theratio of the esterifying alcohol to the total amount of the carboxyl groups is 'not sufilcient 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 substitutionproducts, the resulting products become stable. vl'n the case of the polyvalent alcohols, not all the 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 Three; 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 esterified with a monovalent alcohol.

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

(a) Sulphonated stearyl amid of the formula- I SOzNa I C ioHazCH-C O-NH: Y and the alkyl and aryl substitution product thereof like benzyl stearyl amid sulphonic acid SOaNa omwn-oormcmcm, etc. (to Sulpholeil amid of the formula 11 s4(OSO Na)CONH In the" case where divalent alcohols are used like ethylene glycol, diethylene glycol or trivalent alcohol like glycerol, then at least one of the hydroxy groups should remain free or positively sub-'- stituted and preferably two. In other words, if

. sulpholeic acid is esterified 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 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 eflicient. 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. 1,881,172in which case the acidic group is tied directly to the car,- bon atom of the esterified alcohol giving a sulphonic acid group. 4 In this case fatty acid'esters of ethane sulphonic acid are obtained .of the general formula- 1 L Rcoocnhsom In other words, fatty acid productsof 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 'est'eriflca- I tion or amidization. another method was devised which is proving to be commercially very successful and scientificially correct, viz: the carboxyl group is reduced to analcoholic group and the corresponding alcohol sulphated or phos-- phated.

In the industry, lauric acid has been successare 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 viewpointof 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 1 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 chain of eight carbon atoms or more. A representative of this class is cetyl sulphonic acid and its salts which were described in greatdetail by Reychler in the Kolloidale Zeitschrift, volume 12, page 2'77, 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 until lately and Prof. Schrauth has published an article in the Chemik'er Zeitung for 1931, page 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 notless than eight carbon atoms are sulphonated, in which casetrue sulphonic acids are formed and the next carbon to the carbon that has thev sulphonic acid group on it has a hydroxy group. As one product I can quote the hydroxyoctadecyl sulphonic acid of the formula- CH1(CH2) 15CHOHCH2SO3H which was described in Example One 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.

Chemicallywe may say those substances are either sulphonic or phosphonic derivatives of long chain aliphatic hydrocarbons or theyare sulphuric or phosphoric acid esters or for that matter esters of oxygenated inorganic acids of long chain aliphatic alcohols} or, 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 monovalent 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 common:-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 oleophilic 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 whole'strongly hydrophilic, 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 andgreases in water and give a fatty feel to compounds with which it is penetrated from a purely water medium.

In the above description I have given an idea of the different 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 maybe used. In other words, the compound employed must be strongly hydrophilic and have great penetrating value but at the same time it must also possess oleophillc properties to the point commercially known as Gardinol WA 70 commonsalt. I

j Example 2 Per cent 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 otherwise known as Gardinol CA Example 3 Per cent 1 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 C1sHa1CH-.--0--SO3N9.

otherwise known. as Avirol 142 ammonium sulphate Example 4 Per cent 3 of methylene blue, color index #922 3 of sodium salt of the sulphuric acid ester'of reduced coconut oil fatty acids, commercial- 5 ly known as Gardinol' R 94 dextrine.

Example 5 Per cent 5 acid rhodamine 3R, Manual 534 5 sodium cetyl sulphonate 45 alcohol 45 glycerin Example 6 Per cent 20 Catechu G N, color index 420 3 hydroxy-octadecyl-sulphonic acid, general formula 4 Gila-(CH2) 15CHOH-CH2-SO3NG 77 ammonium sulphate I I Example? Percent I 30 alizarine blue, color index #1054 15 sodium salt of the sulfation product monooleyl ethylene glycol of the formula C1-1Haa'C0-OCH2CH=OSOaNa 55 common salt Example 8 Percent 5 of cyanone blue 5R, color index #289 5 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 75 of Glauber salt a Example 9 Percent 10 pontamine bordeaux B, color index #375 9 cyanine blue 5R, color index #289 20 dark blue BH, color index #401 11 sodium salt of ricin'oleic acid of ethionic acid of the general formula C11H32 (OH) COO-C2H4SO3Na Glauber salt Example 10 Percent 20 algol scarlet G, color index #112 20 benzyl ester of sulpholeic acid of the general formula t CrzHadOSOsNa) COOCHzCsH:

10 of sodium hydroxide 20 of sodium hydrosulphite 30 of sodium carbonate Example 11 Percent 10 of lithol rubin BN, color index #163 10 of the salt of the phosphoric acid ester distearyl glycerin of the formula cnHacoo-cm-cmococnmn CHzO-PO(ONa)z 10 soda ash Glauber salt g,

Example 12 Percent 10 chrysamine, C. I. 365 10 of sulphonated oleyl amide of the general formula CnHmOSOaNa) CONH:

80 salt so I Percent Example 13 10 pontamine bordeaux B, color index #375 10 lecithin 20 salt 60 sugar.

' phosphoric acid group or similar groups. They must have an excellent wetting out action, should preferably dissolve completely in water, make true or colloidal solutions or at least disperse completely to form stable dispersions. They must also have properties that will give the article with which they are distributed stability and give 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. They also may have'an aralkyl group, the alkyl group still not having less than seven carbon atoms.

- It will be noted that this general formula will take in any of the compounds discussed previously in the specification and define it to the point where everyone skilled in the art will be able to use it as a guide for his work.

The degree of the oleophilic properties of these compounds can be regulated by the length of the hydrocarbon chain. Those from Cs -up to Cu have the oleophilic properties not as pronounced as those beginning with Cu, and depending upon thedesirability 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 tltigl iiroduct be useful unless it is still quite hydro- D In describing the invention, it is understood that the examples and illustrations given are to be taken in a descriptive sense rather than ins. limiting sense, Asfar as the specific examples of the dye products are concerned, these are meant to show different types of wetting and combining agents expressed by the general formula.

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 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 dispersions which as far as my purpose is concerned have substantially the same fimction 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 abroad sense to include the characteristics of either molecular or colloidal dispersibility.

acid ester of an aliphatic alcohol having a chain of not less than 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 horne dyeing operations.

2. A home dye compomtion in solid form comprising an intimate admixture of a normally water-soluble dye and a salt of an inorganic oxygenated acid ester of an aliphatic alcohol having a chain of not less than eight carbon atoms said dye composition possessing the properties of imparting an oily feel to fabrics dyed there-- with and producing even, level shades under any of the conditions normally encountered in home dyeing operations.

3. A home dye composition in solid form com-- prising an intimate admixture of a normally water-soluble dye and a sulphuric acid ester of an aliphatic alcohol having a chain of not less than 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 dyeing operations.

4. A home dve composition in solid form comprising an intimate admixture of a normally water-soluble dye and a salt of a sulphuric acid ester of an aliphatic alcohol having a chain of not less than 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 dyeing operations.

5. A home dye composition in solid form comprising an intimate admixture of a normally water-soluble dye and a salt having the general formula- CnHQHICM-SOZX water-soluble dye and the sulphuric acid ester of lauryl alcohol, 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 com prising an intimate admixture of a normally water-soluble dye and the sodium salt of the sulphuric acid ester of lauryl alcohol, 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.

,8. A home dye composition in solid form comprising an intimate admixture of a water-soluble dye and a salt of theisulphuric acid ester of clay] alcohol, 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.

9. A home dye composition in solid form comprising an intimate admixture of a normally water-soluble dye and an inorganic oxygenated acid ester of cetyl alcohol, said dye composition possessing the properties of imparting an oily feel to fabrics dyed therewith and producing 'i even, level shades under any of the conditions normally encountered in home dyeing operations.

10. A home dye composition in substantially solid form comprising an intimate admixture of a normally water-soluble dye and a sulphuric acid ester of oleyl alcohol wherein the sulphuric acid group is esterified with the hydroxy group of the oleyl alcohol, 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 5 encountered in home dyeing operations.

wow KRI'ICHEVSKY.