Patented Aug. 17; 1943 SOAP COMPOSITION Harry Robert Dittmar, Wilmington, Del., as-
Signor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware N Drawing.
Application J111y13 1940,
serialize-345,411
I 3Claims. (cl.,252-.-132) This invention relates to water-treating agents, and more particularly to hard-water treating agents, for the purpose of converting hard water to water having the inherent advantages of soft water, the invention likewise relating to the agents per se and the use of the agents as detergent assistants.-
The water-treating agents of the invention may be characterized as detergent assistants, hard water softening agents, and dye assistants, and are employed for the purpose of avoiding or delaying the formation of hard-water precipitates, redissolving the precipitates already formed, or alternatively forming precipitates of such nature that they have no deleterious effect on the particular operationv of cleaning, dyeing, foaming, or the like.
tergents as detergent assistants in others. They may be used in either capacity in hard or soft water; More marked effect is noticeable, however, when they are used with hard water. In some cases the acids are efiective as such while in others the acids may be added and the salts formed in situ by the addition of an alkali.
An object of the present invention is to provide new water-treating agents. A further object of the invention is to provide a process for cleaning textiles, clothes, comestibles, ceramics, and all materials, articles, or products contaminated with fats, oils, dirt, and the like. Anotherobject is to provide .1 highly efficient detergent assistants. Yet another object of the invention is to provide a new composition which may be effectively used in dye baths to aid in the dyeing of natural or artifleialfibers or fabrics without streaking and/or discoloration due to insoluble metal salts. Other objects and advantages of the invention will hereinafter appear.
The invention is based upon the discovery of new water-treating agents which include the water-soluble salts, salts of basic reacting organic compounds, and especially the ammonium,
substituted ammonium and alkali metal salts, of the inorganic substituted polycarboxylic acids such as the alpha halogen substituted polyacrylic acids e. g., poly alpha chloracrylic poly alpha. fiuoracrylic acid and interpolymers thereof with other polymerizable organic compounds such as vinyl chloride, styrene, maleic anhydride, fu-
When employed as detergent assistants it is preferable that the pI-I'be adjusted to that at which the detergent used is most effective. Accordingly, when used with soaps, a sufiicient amount of base should be present to give a pH of from 9 to 12, i. e., the range in which soap is an efiectivedetergent. These agents may be used in conjunction with asuitable detergent such as, for example, ordinary soapsf that is, thealkali salts of the higher fatty acids. They may also be used with other detergents as the salts of the sulfonic acid derivatives of aliphatic or aromatic hydrocarbons, for instance, alkylated naphthalene sulfonic acids; water-soluble salts of acid sulfuric acid esters of higher aliphatic alcohols, such "as, of lauryl, cetyl, or oleyl alcohol and the like, and similar salts of condensation products of fatty acids with, for instance, hydroxy acids or aminoalkylsulfonic acids and the like. Other ingredients may also be added, ifdesired, to the detergent assistant ,and the detergent, such, for example, as sodium sulfate, sodium carbonate, the silicates, or phosphates together with oxidizing or reducing agents such as the perborates, hydrosulfides, and organic solvents.
These agents if ,uscdwith detergents may, if desired, be added with the detergent prior to or during the washing operation, or may be added maric anhydride, butadiene, chloroprene, vinyl' r acetate, unsymmetrical dichlorethylene, methyl vinyl ketone, methyl methvinyl ketone, vinyl isobutyl ether, ethylene, and the acids, esters, salts, and amines of methacrylic or acrylic acids, etc.
Accordingly, the invention comprises essentially a process involving the addition of the above designated salts as water-treating agents to water and especially hard water to be used during the final rinsing operation. Such agents -may also be previously mixed with the detergent and the resulting mixture then added to the water or the single ingredients may be added in any sequence and in suitable proportions.
, Furthermore, thesewater-treating agents may be employed for preventing the precipitation of insoluble salts from hard Waters, during dyeing;
for cleaning, dyeing, and other purposes. Moreover, these agents may be usedalone as detergents, in some instances, or combined with deas a water softener for boiler-feed water or in other operations where hard water forms contaminating or undesirable insoluble salts. In other words these agents, while mainly used for the purpose of and as an aid in cleaning and in the prevention of the precipitation of lime, calcium, aluminum, iron, zinc, or magnesium salts and the like from solution during cleaning and dyeing, are applicable to all processes wherein these salts precipitate, and it is desirable to prevent their precipitation, or if this" is was added tel-500 ml. hard water of about 21 grains per gallon total. hardnesa: The solution was heated to 150 F. and 1 gram-of soap added with stirring. A .clear, 'stronglyioaming solution with good detergent properties was obtained. A piece of standard soiled blanket felt was cleaned easily by washing'it in this solution at Examples will now be given illustrating by specific embodiments theuse and outstanding ad vantages of the water-treating agents. Unless otherwise indicated, parts given are by weight.
Example 1.-To 20 ml, of 1% soap solution was added 0.1 gram sodium poly a chloracrylate and the resultant solution adjusted to pH 11 by addition of dilute caustic. Titration of this solution at 120 F. with 0.18% calcium chloride solution as described by Hart (American Dyestufi Reporter," page 646, November 19, 1934) required 15 ml. of the calcium chloride to give an end point where a piece of newsprint fastened to the other side of the beaker was no longer legible. There was no appreciable precipitation of calcium salt up to the addition of between Sand 10 ml. of the calcium chloride solution, the solution remaining clear up to this point.
The titration of a soap solution similar in every respect to that described except for the presence of 0.1 gram of sodium or polychloracrylaterequired 5 ml. to give the same end point.
Example 2.To ml. of hard water of about 21 grains per gallon total hardness was added 0.1 gram sodium poly oz chloracrylate. The solution was heated to 120 F.and then titrated with 1% soap solution to apermanent foaming end point. Not more than 1 ml. of. the soap solution (0.01 gram soap) was required to give a clear,
strongly foaming detergent solution. In the absence of the sodium oz chloracrylate 7 ml. of the soap solution was' required to give permanent foaming.
Example 3.-1.5 grams of poly a chloracrylic acid and sufiicient sodium hydroxide to neutralize the acid and raise the pH of the solution to 9.5
In ,the'absence' of the reagent, .l-gram of soap in 500 ml. of hard water containing 21 grains per gallons total hardness produced a typical calcium soap precipitate and no lather could be obtained even-with violent agitation;
The water-treating agents may be used for, in addition to the uses described above, wetting out of gray goods, assistant in peroxide bleaching,
scouring rayon yarns and fabrics, wetting out of cotton goods that are to bepre-shrunk, scouring of lime-pulled wool, degumming, preparation of raw stock for dyeing, as a dispersing and penetrating agent in dyeing, penetrating agent in warp sizing, and in alkaline fulling.
They may also be used, preferably with a detergent, in removing grease from other-greaseladen articles. For example, the palm oil used in the cold-rolling of steelsheets may be removed by scrubbing the sheets with hotwater containing a detergent and the treating agent. In this case the detergent has a saponifying action upon the palm oil and thewater-treating agent used here as a detergent assistant prevents the formation of objectionable calcium or magnesium precipitates. A similar bath may be used for the washing of parts prior and/or subsequent to electroplating, painting, lacquering, finishing, and the like. 1 v
I claim:
1. Hard water having incorporated therein a precipitate-inhibiting amount of an alkali metal salt of a halogen-substituted polyacrylic acid.
2. Hard water having incorporated therein a precipitate-inhibiting amount of the sodium salt of aIpha-chloropolyacrylic acid.
3. A detergent soap normally forming a precipitate in hard water having incorporated therein a precipitate-inhibiting amount of the sodium salt of alpha-chlo'ropolyacrylic acid as a watersoftening agent.
HARRY ROBERT DI'I'TMAR.