US2393866A

US2393866A - Metal tarnish remover

Info

Publication number: US2393866A
Authority: US
Publication date: 1946-01-29
Anticipated expiration: 1963-01-29

Description

Patented Jan. 29, 1946 UNITED STATES PATENT OFFICE METAL TARNISH REMOVER No Drawing. Application January 19, 1943, Serial No. 472,903

13 Claims.

This invention relates to a tarnish remover and the object of the invention is to provide an improved composition in this class of materials.

As usually made, metal polishes comprise an abrasive material together with a carrier such as petrolatum, hydrocarbon oils, glycerine or water, with or without soap or an emulsifying agent. The use of carriers of these types of materials is disadvantageous in certain respects. The petrolatum, hydrocarbon oils, glycerine and water are substantially inert with respect to the tarnishes, for instance metallic oxides or sulphides which are to be removed from the metal. Moreover, an oil or grease cannot be washed from the polished article unless a special solvent or emulsifying agent is used as the grease or oil is insoluble in water. Additional difficulties with water-soluble soaps and similar materials are that they tend to react with a number of abrasive materials, for instance iron salts or calcium salts, to form water-insoluble soaps which decrease the efiiciency of the abrasive compositions and are difficult to remove from the cleaned metal. The tarnish removers of the present invention should not be confused with the usual so-called polishes, for instance shoe polishes or floor polishes, as the action of the compositions of the present invention is to remove tarnish films from the metal while the action of a shoe polish or floor polish is merely to provide a masking covering or a lustrous film.

A tarnish, as the term is used in the present description, is intended to define that film discoloration of the metal surface which occurs by a change in the metal, for instance by the formation of a sulfide or oxide film which is apparently integral with the metal surface and may be likened to a metal corrosion; it is distinct from the mere surface layer of dust or dirt or other foreign matter which may deposit on a metal surface and dull it. While the tarnish removers of the present invention will remove surface dirt, their action is more than a mere detergent action and is different from a mere scouring or abrasive or buffing action. A detergent action is exemplified by the action of soap and water, the surface dirt merely being washed away. In a scouring or buffing action, undesirable surface adhesions are merely cut away from the surface by the abrading or grinding or cutting action of the scouring or abrasive material. With the compositions of the present invention, there appears to be a breaking down or change in either or both of the physical and chemical structure of the tarnish whereby the tarnish is removed with a minimum of mechanical effort. The action of the essential ingredient, a polyoxyethylene diol, is not wholly chemical as it may be permitted to remain in contact with the tarnish without removing the tarnish and Without apparent change in the tarnish; but the action is more than a mere abradant action as a solution of the polyoxyethylene diol in water removes tarnish better than a mixture of only abradant and water, and the action is apparently not a combination of detergent and abradant action nor a mere detergent action as a solution of the said diol in water removes tarnish better than a mixture of soap and water while a composition of the said diol, abrasive and water removes tarnish better than a composition of soap, abrasive and water. The pglyoxyethylene diols appear to act on the tarnish iii'an'ianner which enables the tarnish to be removed mechanically, as a solution of 15% of the polyoxyethylene diol in of water is effective when forcefully rubbed on the tarnish although the most pronounced effect is obtained when an abradant is included. Furthermore, water must be present when the composition is used to remove tarnish and the polyoxyethylene diol must be present as a free substance in an amount not less than about 15% by weight of the total composition. When applied to the tarnish, for effective removal thereof, the polyoxyethylene diol must be in solution in water so that the diol molecule is carried into and can attack the tarnish, for example if a buffing cake composed of a solid polyoxyethylene diol and an abrasive is rubbed against a tarnished metal surface, the action appears to be purely an abrasive action, the polyoxyethylene diol acting merely as a carrier for the abrasive; but if a composition containing the polyoxyethylene diol, abrasive and water is used so that the said diol is in a condition of molecular distribution in the solvent and can attack the tarnish, the tarnish is easily removed with a minimum of mechanical effort and abrasive action and hence with a minimum of scratching the metal surface.

The tarnish removing composition of my invention comprises as an essential ingredient at least about 15% by weight of a polyoxyethylene diol of the 1,2 series, preferably 'bne containing sulficient chemically combined oxyethylene radicals to be normally solid, and a solvent for the diol. The tarnish remover preferably also contains an abrasive and may contain other and additional ingredients, which may conveniently be referred to as addends, to assist in removing the tarnish which forms the undesirable discol- 2 asoaaee oration on the metal surface. The basic ingredients of the tarnish remover, i. e. the polyoxyethylene diol and its solvent. are, in combination, an efiective tarnish remover yet they are not greasy, they do not form water-insoluble films nor precipitates and, after the tarnish is removed, the compound may easily be removed from the metal merely by flushing with water. Thus, the entire operation of removing the tarnish and the iinal cleansing of the treated article is reduced to a very eflicient but simple operation.

These and other objects and features of the invention will more fully appear as obvious or will be pointed out in the following description and accompanying claims.

The polyoxyethylene diols may be formed by the reaction of ethylene oxide with ethylene glycol in the presence of an alkaline catalyst, and with the degree of the addition of the ethylene oxide controlledto produce the molecular size desired. For instance, ethylene oxide may be reacted with ethylene glycol or other alkyiene glycols ,oflow molecular weight and of the 1,2- series to give the polyoxyethylenediols. when the polyoxyethylene diols are referred to as having given molecular weights or average molecular weights, it is understood that the mass may be a mixture of polyoxyethylene diols of different molecular weights. For instance, ethylene glycol has a molecular weight, in round numbers, of 62 and each ethylene oxide radical has a molecular weight of 44. Polyoxyethylene diol composed of 19 ethylene oxide radicals added to one ethylene glycol molecule has a molecular weight of 898. A polyoxyethylene diol having an average molecular weight of 900 may thus be a mixture of polyoxyethylene diols wherein, for instance, there may be some polyoxyethylene diol molecules containing 18 or less, and some containing 20 or more ethylene oxide radicals, but the molecular weight or the average molecular weight of the mass as determined by test is about 900. Polyoxyethylene diols having an average molecular weight of about 900 are normally solid, having a fusion or melting point of about 30 C. to 40 C. Polyoxyethylene diols having an average molecular weight of about 400 are fluids. For the purposes of this invention, I prefer to use a polyoxyethylene diol composition of the type disclosed herein, containing sufl'ic'ient oxyethylene radicals to form a normally solid polyoxyethylene diol, such preferred polyoxyethylene diol composition having an average molecular weight of approximately 900. For the purpose of this disclosure, the term polyoxyethylene diol" i s intended to include the polyoxyethylene diol composition indicated, and the term solid" is intended to refer to materials which are semi-solid and will hold their shape at normal temperatures of approximately 20 C. as distinguished from those which are distinctly liquids and incapable of holding a given shape at normal temperatures.

The polyoxyethylene diols previously described are sufiiciently soluble for the purposes of this invention, in many different solvents, for inand soft water and thus there is always ready at hand a low cost solvent. Furthermore, the water and polyoxyethylene diols appear to have a cooperative action, particularly with an abrasive and addends hereinafter described, in removing tarnish from metals.

The polyoxyethylene diols having the higher average molecular weights are harder than those of the lower average molecular weights and have higher melting points. A polyoxyethylene diol having an average molecular weight of approximately 900 (as determined by the Menzies and Wright method of determining molecular weights, described at page 2314, volume 43 (1921) of the Journal of the American Chemical Society) has a density of approximately 1.151 grams per 0. c. at C., a melting point of approximately C. to 0., a viscosity of approximately to 90 Saybolt Universal seconds at 210 F., and a flash 20 point of approximately 430 F. A polyoxyethylene diol having an average molecular weight of approximately 3,500 (determined by the same method) has a density of approximately 1.204, a melting point of approximately 54 C. to 57 0., a viscosity of approximately 400 to 600, and a flash point of approximately 535 F. A polyoxyethylene diol having an average molecular weight of approximately 6,000 has a melting point of about 60-65 C. The liquid polyoxyethylene diols have average molecular weights beginning in the neighborhood of 200 and running up to about 500 when they begin to assume the consistency of the 900 molecular weight material previously described. In preparing the compositions contemplated herein, I may use the polyoxyethyl. ene diols which are liquids and those which have molecular weights substantially higher, say a molecular weight of approximately 2,500, but prefer those which have a molecular weight of approximately 900, these being soit solids. Polyoxyethylene diols having molecular weights of approximately 900 appear to be more efiective, when used with water and an abrasive as a tarnish remover,

than the fluid polyoxyethylene diols and those which have molecular weights of approximately 4,000. Tarnish may be removed merely by applying to the tarnish, by means of a wet applicator, for instance a cloth, onge or brush. a normally solid polyoxyethylene diol having a melting point between about 30 C. and 40 C. and then forcefully rubbing the tarnish. This particular diol is of a petrolatum-like consistency and readily soluble in water and is so effective in removing tarnish, that whether it be applied directly to the tarnish and then rubbed with a wet applicator or the wet applicator first be rubbed on the diol,

suilicient of the diol is normally applied to give at least the 15% minimum concentration (with "the water of the applicator) to provide an eifective tarnish remover. If desired, the diol may have abrasive mixed with it.

stance both hard and soft water aswell as aro- All of these polyoxyethylene diols may be prepared free from odor and have the property of forming clear, colorless and stable solutions, with either hard or soft water. Those which are solids may be used to form compositions having the consistency of thick or thin creams, by the addition of suitable amounts of water or liquid polyoxyethylene diol or other liquid ingredient. Thepolyoxyethylene diols which have an average molecular weight of approximately 900 are slightly hygroscopic and take on a moist appearance under humid conditions. The range of average molecular weights of the polyoxyethylene diols for the most eflectlve polishes is from approximately 700 to 2,500. These polyoxyethylene diols are almost immediately dissolved in water when rubbed therewith between the fingers and those having higher average molecular weights are dissolved somewhat like hard soaps. However, the polyoxyethylene diols are soluble in hard and soft, hot and cold water, the solutions are clear as distinguished from the colloidal solutions which have the opalescent effect produced by soaps, and they do not form a precipitate or curd in hard water. Thus, the polyoxyethylene diols remain in solution and remain effective as an ingredient of the tarnish remover whereas oils and soaps may not.

The polyoxyethylene diols are usually considered to be quite inert with-respect to metals and to the materials usually used in metal polishes. In mere admixture with water, abrasive materials such as chalk, diatomaceous earth, metal salts, silica, rouge and the like, or other ingredients such as acids, for instance oxalic acid, citric acid, tartaric acid and the like, alkalis, for instance sodium hyposulfite, potassium tartrate or bitartrate, alkyl or alkylol amines, for instance ethanol amines or reaction products of these materials, forinstance triethanol amine acid oxalate, and monoethanolamine acid tartrate, the polyoxyethylene diols appear to be inert with respect to the other ingredients when combined in the proportions used in my tarnish removers and at ordinary room or atmospheric temperatures.

However, when applied to oxidized, sulphurized or otherwise tarnished metal and rubbed on the tarnished area in conjunction with water, with or without an abrasive, the polyoxyethylene diols have an action which removes the tarnish. Thus, in a composition comprising a normally solid polyoxyethylene diol, chalk and water, ther appeared to be no reaction between the ingredients (except that the water dissolved the polyethylene glycol) at room temperature yet, when the composition was forcefully rubbed on tarnisn on steel dies, the tarnish was removed better than with metal polishes currently on the market. A composition comprising the normally solid polyoxyethylene diol, chalk and water, also was more effective than would be expected from comparative tests either with a mixture of the said diol and chalk, or chalk and water. A mix comprising only the normally solid polyoxyethylene recognized. For instance, if the abrasive is chalk (calcium carbonate) or rouge (iron oxide), the probability of a chemical reaction must be recognized if an acid is used as an addend. But if it be desired to formulate a tarnish remover which is particularly effective on a certain metal or alloy, fgr instance copper or brass, and an acid, for Instance dilute hydrochloric acid, is a desirable addend, the abrasive may be powdered silica or other material which is substantially unafl'ected by the acid.

Addends of general utility are materials such as wetting agents and penetrating agents. The

polyoxyethylene diols have the action of spreading and levelling agents and they appear to work particularly effectivel in tarnish removers with the addition of a small amount of a wetting agent or a penetrating agent. Wetting or penetrating agents which have emulsifying characteristics may, of course, be incorporated but such use of these agents is due primarily to other characteristics which they may posses and not to their emulsifying characteristics. In a broad aspect of the invention, a wetting or penetrating agent of general wetting or penetrating characteristics may be used but a particularly effective class of wetting and penetrating agents are those containing organic radicals and combined sulfur and, in particular, the wetting agents next described which have been found to give exceptional results with the polyoxyethylene diols when used for removing v tarnish. These agents are, in general, basically diol and water appeared to be more efficient than glycerine or a mix comprising only glycerine and water.

The molecular size of the polyoxyethylene dicl appears to have a relation to the efficiency of the compositionin its action in removing tarnish as in comparing the effect of compositions which were identical in weights of ingredients, and differed only in that polyoxyethylene diols having average molecular weights of 400, 900 and 3,500 were used in the respective compositions. the composition containing the 900 molecula weight polyoxyethylene diol appeared to be more efficient than the other two.

Withthe basic formula of polyoxyethylene die.

and water mains used other; materials (in addi tion to the abrasive) of general are: specific utility and a feature of the invention is a basic formula of neutral ingredients with which substantially any added material orfaddend" may he u sed. The preferred addends are chemically or physically active either on the tarnish or as wetting or penetrating agents. Of course. the possible chemical reactions between the abrasive and the addend or between the addends must be esters carrying combined sulfur in the form of a sulfite, sulfate, or sulfonate group. The said substances may be alkyl or aryl metal sulfates, the metal preferably being an alkali or an alkali earth metal. The substances also may be classed as salts of oxysulfur organic compounds. They include the salts of the sulfated high molecular weight alcohols, sulfonated esters of dibasic acids and higher alcohols, and alkylated aryl sulfonates. Salts of the sulfate ester derivatives of the higher saturated, branched-chain aliphatic alcohols including both the primary and secondary alcohols, are suitable. These sulfate esters may be those of the alkali metal hydroxides, the ethanol amines and of other bases. Sulfate ester derivatives of the higher saturated branched-chain aliphatic alcohols which are described in the United States patent to Wickert No. 2,088,019, dated July 27, 1937, are satisfactory for my purposes.

Other salts of oxysulfur organic compounds which may be used include salts of various sulfonated higher fatty alcohols obtained from fats and oils of animal and vegetable origin, salts of the alkylated aryl sulfonates, and the salts of the diaryl esters of sulfosuccinic acid, such as for example, the dioctyl ester and the dihexyl ester of sodium sulfosuccinie acid. Surface active wetting agents of the type of fatty alcohol sulfates are also contemplated. In general, good results may be obtained with these previously described surface active wetting agents having from 8 to 20 carbon atoms per molecule. Salts of the sulfate ester derivatives of the saturated branched-chain aliphatic alcohols are preferred, however, and especially good results were obtained from those having from 8 to 17 carbon atoms to the molecule.

These substances are all miscible with water in sufficient amount to act as extremely effective surface-wetting agents when used in conjunction with the said diols, even though minute quantities are incorporated.

addends of specific utility are those which are particularly"eiilaclbusfor the tarnish on any speciiic metal. For instance; chloride of lime, bicarbonate of soda or magnesia, sodium chloride or dilute acids, for instance, inorganic acids such a hydrochloric acid or sulfuric acid or organic acids, such as acetic acid or oxalic acid, may be used in conjunction with the polyoxyethylene diols for removing the tarnish from gold. In the case of tarnished brass and co the tarnish removers may contain addends such as oxalic acid, hydrochloric acid, sulfuric acid,=, chromic acid, nitric acid, tartaric acid, citric acid, cream of tartar, alum, sodium chloride, and ammonium chloride.

Silver-tarnish removers may contain such addends as borax, ammonium carbonate, paris white,fj so dium or potassium hyposuliit; sodium chloride, potassium cyanide, nitric acid. calcium chloride, sodium or potassium hypochlorite, alum, potassium or sodium nitrate, camphor, ammonia, potassium or sodium sulfate, oxalic acid, subcarbonate of iron, silver nitrate, sodium or potassium carbonate, citric acid and the like.

Tarnish removers for iron and steel and other (base metals may contain substantially any of the addends previously listed, for instance blue vitriol,

borax, prussiate of potash, arsenous acid, antimony trichloride, sodium carbonate, sulfuric acid, nitric acid, oxalic acid and the like.

. Substantially any abrasive may be used in the tarnish remover, for instance charcoal, chalk, rouge, tripoli, pumice, brick, pipe clay, yellow ocher, emery, rotten stone, silica, sand, flint. infusorialearth, red lead, white lead, and the like. These abrasives are water insoluble.

Although substantially any amount or kind of abrasive may be used'in the tarnish remover, abrasives such as chalk and the like may also serve as thickening agents to produce a thickor thin cream type product as desired. The presence of the polyoxyethylene diols renders the tarnish remover so efllcacious that only relatively small amountsof the addends need be used. This is desirable as the usual addends are frequently hard on the skin but theopposite is true of the polyoxyethylene diols. Also. due to the eiilcacy of a tarnish remover containing a polyoxyethylene diol and the fact that the necessity for mechanical effort and abrasive action is reduced over that required for a product which contains none of the said diol, a soft abrasive, for instance chalk or rouge, or an abrasive of smaller particle size can be used if the tarnish remover contains a polyoxyethylene diol, in cases where a hard, coarser abrasive such as emery or silica has heretofore been required. The soft or fine abrasive does less harm and leaves less scratches on the metal than does a hard, coarse, sharp abrasive.

In further explanationof the invention, reference may be had to the following formulae which, it should be understood, are given merely by way of example and without intent to limit the invention to theingredients or the proportions thereof which are specifically disclosed.

Example 1 Twenty parts of water, 38 parts of polyoxysulfate ester derivative of 3,9-diethyltridecanol- 6). It is a stable, water-soluble liquid. Other wetting agents containing sulfur in chemical combination may be used instead of the one given. For instance, any of the following may be used; sodium octyl sulfate (monosodium sulfate ester derivative of 2-ethyl hexanol-l); sodium tetradecyl sulfate (sodium sulfate ester derivative of 'l-ethyl, 2 methyl undecanol-S); dioctyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; a fatty alcohol sulfate; sodium tetradecyl sulfate (sodium sulfate ester derivative of 'l-ethyl, 2 methyl undecanoli). Into these ingredients are incorporated 39 parts of finely ground chalk orwhite rouge. The mixture forms a still cream type product which may be made thicker or more fluid by adjusting the amount of the said polyoxyethylene diol or the abrasive or the water. A thinner product may also be made by substituting a fluid polyoxyethylene diol for all or a portion of the solid polyoxyethylene diol which has an average molecular weight of 900, referred to in the first part of this example. Also, a thicker product may be made by substituting a polyoxyethylene diol having an average molecular weight which is higher than 900, for instance a polyoxyethylene diol having an average molecular weight of 3,500 or 6,000, for all or a portion of the polyoxyethylene dio1 which has an average molecular weight of 900. The tarnish remover of this example is particularly effective on silver.

Example 2 4,0 This formula is also recommended for a silver polish and the stifi product which is formed may be made thicker or more fluid in the manner described in'Example 1.

Example 3 Thirty-seven parts of the polyoxyethylene diol of Example 1, 3 parts of the wetting agent of Example 1, and 18 parts of water are mixed as described in Example 1. With these ingredients there may then be incorporated 12 parts of triethanolamine acid oxalate. When the triethaethylene diol having an average molecular weight of about 900 and a melting point from about C. to C. and 3 parts of a wetting agent of the class described (allparts by weight) were stirred together until the polyoxyethylene diol dissolved. Heat may be applied to facilitate the solution of the polyoxyethylene diol but is not necessary. The wetting agent in this case was a 25% aqueous solution of sodium heptadecyl sulfate (sodium nolamine acid oxalate has been incorporated in the mixture, 30 parts of diatomaceous earth may be incorporated. The triethanolamine acid oxalate may be made by mixing one mol of oxalic acid with one mol of triethanolamine, the heat of the reaction being su'fllcient to initiate and complete the reaction. The triethanolamine acid oxalate increases the speed of action of the tarnish remover in removing tarnish, especially on copper and brass but the composition is not so hard on the hands as if straight oxalic acid were used. As the triethanolamine acid oxalate is still an acidic salt, the abrasive, in this case, may be silica but preferably is the softer diatomaceous earth instead of chalk which might react with the acid oxalate. The wetting agent not only facilitatesthe action of the composition in removing tarnish from the metal but enables the composition to be removed very easily from the cleaned and polished metal merely by flushing the metal with water and thus is a particularly desirable ingredient for tarnish removers, for instance those for use on silver, or copper, or brass, which are intended for use in the home. The

consistency of the product formed in the manner stated above, may be changed in the manner stated in Example 1.

Example 4 A composition of cream-like viscosity may be made with 2 parts of the polyoxyethylene diol of Example 1, 1 part of water and suflicient white rouge to give the consistency desired. Such a product has been found to be very effective in removing from steel tool dies the tarnish occasioned by reason of the dies having been subjected to fire when the building in which they were located was burned. Usually, polishes for a hard metal such as steel require the presence of a hard, sharp cutting abrasive such as emery or silica.

Example 5 Thirty-seven parts of a normally solid polyoxyethylene diol having an average molecular weight of approximately 3500 and a melting point from about 54 C. to 57 C., 3 parts of the wetting agent of Example 1, and 21 parts of water are stirred together until the diol is dissolved. If desired, the mix may be heated to facilitate solution of the diol or the diol may be melted prior to stirring'in the wetting agent and the water. Into the fluid mass, either hot or cold, are thoroughly mixed 39 parts of chalk. At room temperature the composition has the consistency Of. Detrolatum and will hold its own shape. It is an efficient tarnish remover for use on brass and silver.

Example 6 Thirty-eight parts of the normally solid polyoxyethylene diol of Example 1, 3 parts of a fatty Example 7 Thirty-seven parts of the polyoxyethylene diol of Example 1, 5 parts of a sulfated aromatic ether alcohol wetting agent, 16 parts of water, 12 parts of triethanolamine acid oxalate and 30 parts of abrasive silica are mixed in the manner stated in the previous examples. The composition of this example has the consistency of petrolatum and is an efllcient tarnish remover for use on brass and copper.

Example 8 Example 9 Thirty-five parts of the polyoxyethylene diol of Example 1, 3 parts of a 25% aqueous solution of sodium tetradecyl sulfate (the sodium sulfate derivative of 3,9-dlethyltridecanol-6), 5 parts of citric acid, 5 parts of sodium chloride, 25 parts of water and 27 parts of diatomaceous earth are mixed in the manner stated in previous examples. The composition of this example has the consistency of petrolatum and is an eiiicient tarnish remover for use on aluminum, brass and copper.

In case it be desired to market a more concentrated composition intended to be used only with an applicator wet with water, the composition of the following example may be prepared. Under normal circumstances the amount of water on an applicator will not reduce the proportion of the polyoxyethylene diol lower than the 15% minimum which is necessary to provide an emcient tarnish remover.

Example 10 Forty parts of a polyoxyethylene diol having an average molecular weight of about 400, and 3 parts of the wetting agent of Example 6 are mixed. A polyoxyethylene diol of this molecular Weight is normally a liquid. Into the mass is then incorporated suiiicient rouge to make a paste or the liquid may be added to the abrasive if so desired. When applied by means of a wet applicator, the composition is a good tarnish remover for general household use on silver and brass as the rouge is a relatively soft abrasive,

Example 11 A paste adapted to be used with a wet applicator may also be made by following the procedure of Example 10 in mixing 40 parts of the polyoxyethylene diol of Example 10, 3 parts of the wetting agent of Example 9, 9 parts of triethanolamine acid oxalate and incorporating suflicient abrasive silica to make a paste. This composition contains a slight amount of water and is a good tarnish remover for general household use although the silica will cut the metal to a greater extent than will rouge of a similar particle size.

Example 12 A tarnish remover without abrasive but containing a chemically active addend and adapted to be used with a wet applicator may be prepared by mixing 75 parts of the polyoxyethylene diol of Example 1 with 25 parts of triethanolamine acid oxalate. This composition has a consistency similar to that of soft petroiatum and is useful for removing tarnishing from brass and copper.

Example 13 A tarnish remover without abrasive but containing water and chemically active addends may be prepared by mixing 50 parts of the polyoxyethylene diol of Example 1, 7 parts of citric acid, 7 parts of sodium chloride and 36 parts of water. This composition is a slightly viscous liquid and is useful for removing tarnish from brass, copper and aluminum.

In general, the tarnish removing compositions should contain from 15 to 60 parts of the polyoxyethylene diol, a polyoxyethylene diol having a. melting point between about 30 C. and 40 C. being preferred as it appears to be the most active and, being normally a solid, allows the incorporation of water in the composition without requiring too much filler or abrasive to keep the composition in the cream-like condition; from 10 to 50 parts of abrasive; from a small quantity to 30 parts of water; and addends up to 20 parts; the weight of the polyoxyethylene diol being not less than 15 parts by weight of the total composition.

It is to be understood that the compositions may contain suitable perfumes, colors and fillers as desired provided their incorporation does not decrease the proportion of polyoxyethylene diol below the 15% minimum and preferably does not decrease the abrasive below the 10% minimum. However, the use of adulterants is not recommended. If fillers or extenders are used, they should be discrete particulate non-filming materials. for instance wood flour and not materials which leave water-insoluble fllms on the metal,

for instance water-insoluble oils and waxes. The compositions should be tree from water-inaok uble film forming materials or materials which form water-insoluble films or scum.

From the previous description it will be seen that, by the use of the pclyoxyethylene diols, I am enabled to provide an emcient metal cleaner, Polish and tarnish remover, including either hard or soft water; one which is substantially nonrlammable and non-poisonous; one which is not greasy; one which does not form a waterinsoluble scum or fllm on the metal to be cleaned: one which does not foam; one which may easily be removed from the cleansed metal merely by flushing with water; one which may contain a minimum of addend and one'which has a minimum of deleterious eflect on the person using the product, thereby rendering unnecessary special protective devices, such as waterproof gloves and the like.

What is claimed is:

1. A composition for removing tarnish from metals comprising water, abrasive particles, a polyoxyethylene diol having an average molecular weight of not less than about 400, a tarnishremoving substance chemically active in attacking the tarnish and acting to chemically remove the tarnish in conjunction with said diol, and a metal-wetting agent eflective in causing the composition to wet the tarnish, said diol being not substantially less than about percent by weight of the composition.

2. A tarnish-remover base composition adapted to be mixed with water to form a composition for removing tarnish from metals, said base composition comprising abrasive particles, a polyoxyethylene diol having an average molecular weight of not less than about 9100, a tarnish-removing substance chemically active in attacking the tarnish and acting in. said tarnish-removing composition to chemically remove the tarnish in con- Junction with said diol, and a metal-wetting agent effective in causing said tarnish-removing composition to wet the tarnish, said diol being not substantially less than about 15 percentby weight of the base composition.

3. A tarnish-remover base composition adapted to be mixed with water to form a composition for removing tarnish from metals. said base cornposition comprising abrasive particles, a polyoxyethylene diol having an average molecular weight oi'not less than about 400, and a tarnish, removing substance chemically active in attacking the tarnish and acting in said tarnish-removing composition to chemically remove the tarnish in conjunction withsaid diol, said diol being not substantially less than about 15 ,percent by weight'ci the base composition.

4. A tarnish-remover base composition adapted to be mixed with water to form a composition ior removing tarnish from metals, said base composition comprising abrasive particles, a poly oxyethylene diol having an average molecular weight of not less than about 400, and a metalwetting agent effective in causing said tarnishremoving composition to wet the tarnish, said diol being not substantially less than about 15 percent by weight of the base composition.

5. A fluid tarnish-remover base composition adapted to be mixed with water to form a composition tor removing tarnish from metals, said base composition comprising a polyoxyethylene diol having an average molecular weight of not less than about 400, and an acidic ammonium salt chemically active in attacking the tarnish and acting in said tarnish-removing composition to chemically remove the tarnish in conjunction with said diol, said diol being not substantially less than about 15 percent by weight of the base composition.

6. A fluid tarnish-remover base composition adapted to be mixed with water to form a composition for removing tarnish from metals, said base composition comprising a poly-oxyethylene diol having an average molecular weight of not less than about 400, and an acidic tarnish-removing substance comprising an acid and a salt and chemically afctive in attacking the tarnish and acting in saidtarnish-removing composition to chemically remove the tarnish in conjunction with said diol, said diol being not substantially less than about 15 percent by weight of the base composition.

7. A fluid tarnish-remover base composition adapted to be mixed with water to form a composition for removing tarnish from metals, said base composition comprising a polyoxyethylene diol having an average molecular weight 0! not less than about 400, and a tarnish-removing substance comprising an amine acid salt and chemically active in attacking the tarnish and acting in said tarnish-removing composition to chemically remove the tarnish in conjunction with said 'diol, said diol being not substantially less than about 15 percent by weight of the base composition.

8. A fluid tarnish-remover base composition adapted to be mixed with water to form a composition for removing tarnish from metals, said base composition comprising a polyoxyethylene diol having an average molecular weight of not less than about 400, and a tarnish-removing substance comprising an alkylol amine acid salt and chemically active in attacking the tarnish and acting in said tarnish-removing composition to chemically remove the tarnish in conjunction with said diol, said diol being not substantially less than about 15 percent by weight of the base composition.

9. A fluid tarnish-remover base composition adapted to be mixed with water to form a composition for removing tarnish from metals, said base composition comprising a polyoxyethylene diol having an average molecular weight of not less than about 400. and a tarnish-removing substance comprising an ammonium compound and chemically active in attacking the tarnish and acting in said tarnish-removing composition to chemically remove the tarnish in conjunction with said diol, said diol being not substantially less than about 15 percent by weight of the base composition.

10. A tarnish-remover base composition adapted to be mixed with water to form a composition for removing tarnish from metals, said base composition comprising a polyoxyethylene diol having an average molecular weight of not less than about 400, abrasive particles, and an acidic tarnish-removing substance comprising an organic acid and a salt and chemically active in attacking the tarnish and acting in said tarnish removing composition to chemically remove the tarnish in conjunction with said diol, said diol being not substantially less than about 15 percent by weight of the base composition.

11. A composition for removing tarnish from metals comprising a poiyoxyethylene diol having an average molecular weight of not less than about 400, a solvent for said diol, an acidic tarnish-removing substance chemically active in attacking the tarnish and acting to chemically remove the tarnish in conjunction with said diol, a metal-wetting agent, and a tarnish-cutting abrasive non-reactive with the other ingredients of the composition, the amount of said diol being not substantially less than about 15 percent by weight of the composition.

12. A composition for removing tarnish from metals comprising approximately 37 parts of a polyoxyethylene diol having a melting point between about 30 C. and 40 0., approximately 12 parts of a water-soluble tarnish-removing substance chemically active in attacking the tarnish and acting to chemically remove the tarnish in conjunction with said diol, approximately parts of an abrasive, approximately 1 part of sodium heptadecyl sulfate and sufficient water to make 100 parts, all parts by weight.

'13. A composition for removing tarnish from metals comprising between about 15 parts and 60 parts of a polyoxyethylene diol having a melting point between about 30 C. and 40 C-, from a small quantity up to about 20 parts 01' triethanol amine acid oxalate, from about 10 parts to about parts of diatomaceous earth, approximately 1 part of sodium heptadecyl sulfate, and from a small quantity up to about 30 parts of water, all parts by weight, the amount of said diol being not substantially less than 15 percent by weight of the composition.

HELEN E. WASSELL.