2,411,938 Patented Dec. 3, 1946 UNITED STATES PATENT OFFICE 2,411,938 CLEANING AND POLISHING COMPOSITIONS Jacob Ratner, Brooklyn, N. Y. No Drawing. Application May 19, 1941, Serial No. 394,225 5 Claims. (Cl. 260—19) 1 This invention relates to cleaning and polishing compo-sitions particularly suitable for automobiles. and all types of household furniture. This application is a continuation-in-p-art of application Serial No. ‘76,079, ?led April 23, 1936, entitled Cleaning and polishing compositions. A very great number of different types of clean ing and polishing compositions have beenused and suggested in the prior art. While such wide variety of polishes have been known, they are 10 open to a large number of difficulties and de? ciencies both from the standpoint of manufacture cleaning and polishing compositions are produced which deposit on the treated surface a very thin, delicate, invisible, transparent preservative ?lm which dries rapidly, is lustrous in and of itself without the need of buiiing or rubbing, is readily applied in uniform manner by mere wiping on as with a cloth, is resistant to dust, ?nger marks, water spotting, etc., and is of substantial dura bility, is freely and readily distributable over a large area of surface and does not lead to unde sirable accumulations even after frequent appli cations, and permits the composition to contain high percentages as much as 85 to 92% of a and in use. Many of them are expensive to make. petroleum diluting cleaning vehicle without causy Many are in?ammable and give rise to hazardous . conditions in both manufacture and use. Many 15 ing bloom on the treated surface. In such compositions in accordance with the of them require heat during processing and man present invention, a ?lm-forming component is ufacture. Many of them while useful on one type employed but the proportions of such ?lm-form of surface, injure other types of surfaces so that ing component are such as ‘not to produce an they are not capable of general application. Many of them are not homogeneous resulting in 20 ordinary substantial resinous or lacquer type coating which could not be applied with a cloth segregation of components on standing which and would not be suitable for frequently repeated cannot be readily made compatible even by violent applications. Of the ?lm-forming components shaking. Many of them require rubbing or available in the art, there are two outstanding bu?'ing in order to develop the luster required. Many of them give rise to a surface bloom. Many 25 materials‘of unique value in cleaning and polish ing compositions produced in accordance with the of them do not dry rapidly enough and are not present invention, those outstanding ?lm-form resistant to ?nger marks. Many of them'are ing components being phenol formaldehyde resins Among the objects of the present invention is 30 on the one hand, and substantially pure metallic organic compounds illustrated by the heavy metal the production of cleaning and polishing compo derivatives of fatty acids, particularly those from sitions generally applicable on coatings contain the’ glyceride oils, namely, linoleates, oleates and ing a vegetable oil or even on cellulose ester coat stearates, and also those produced from resinic ings normally susceptible to injury when treated subject to spotting by water or rain. acid which may be called resinates and from with a polish containing substantial amounts (as naphthenic acid as well as the metal butyl 35 over 33%) of cellulose ester solvents, as in con phthalates. These ?lm-forming components may nection with automobiles and household furni be utilized individually or in combination, and .ture, which compositions are economical to man particularly important results are obtained by ufacture, may be produced from components employing combinations of the phenol formalde readily available, and have unique properties eliminating the difficulties and deficiencies of 40 hyde resins with the metallic organic compound prior art compositions. , Many other and further objections and advan tages will appear from the more detailed descrip as will be further illustrated below. Of the phenol formaldehyde resins, a most im portant one for present purposes are the oil solu tion given below, it‘ being understood, however, 45 ble phenol formaldehyde resins readily available today and produced generally from substituted that this more detailed description is given by alkyl phenols. Such oil soluble phenol formalde way of illustration and explanation only, and not hyde resins may be utilized to-produce homogene by way of limitation, since various changes ous compositions by the utilization of the ve therein, may be made by those skilled in the art, hicles and modifying liquids of the present inven without departing from the scope and spirit of 50 tion. The alcohol soluble phenol formaldehyde the present invention. resins and polybasic acid-polyhydric alcohol res In accordance with the present invention, 2,411,938 3 . ins may also be employed. In coating composi tions such resins require the use of not less than 40% of a cellulose ester solvent and such com tetrachloride which is most suitable for use in the higher ratios. Other chlorinated hydrocar bons having a higher boiling point and which are positions containing those proportions of cellu lose ester solvent would be injurious if applied as a cleaner or polisher for surfaces carrying cel lulose ester coatings. In accordance with the to the direct alcoholic solvents, can be employed in the lower ratios, such other chlorinated hydro used or usable in lacquers as solvents auxiliary present invention such resins are used in a much carbons including ethylene dichloride, trichlor ethylene, tetrachlorethylene, orthodichlorben smaller quantity, and by employing a mild mod zene, etc. ; as well as chlorhydrins like dichlorhy ifying liquid, 1. e., an oil containing ester or a 10 drin and ethylenechlorhydrin can be used. Even the lower (than carbontetrachloride) boiling methyl chlorine compounds such as methylene chlorinated or aromatic hydrocarbon, as an aux iliary solvent, the quantity of cellulose ester sol vent can be kept to about 25% of the composi tion, thus facilitating the use of these resins in cleaning and polishing compositions. In producing the polishing and cleaning com positions of the present invention the desired ?lm-forming component is utilized in a composi tion whichvcontains a relatively major amount even up to .80 or 85% and more of the composi tion, of a mild or neutral diluting cleaning vehicle and generally also there is present in the com position, a_ substantially lesser proportion of a chloride, can be used in the polishes in a propor tion of say 25% for the purpose of reducing the 15 proportion of direct alcoholic or ester solvent or for the purpose of enabling the use of a very . slowly evaporating petroleum diluent such as kerosene. Further there can be used as the modi fying liquid oil containing ester such'as pine oil, 20 essential oils such as Siberian pine-needle oil or Venice turpentine, either the synthetic or natural, the natural product being pasty and slow drying being used in proportions generally of not more modifying liquid particularly useful in combining than about 4% compounded with from 10 to 16% and homogenizing the resin with a diluting clean 25 of other members of the hereinmentioned ing vehicle consisting of a petroleum derivative groups. Or cellulose ester solvents may be used, which when used alone (without the modifying such as alcohols, esters particularly the acetic liquid) tends to precipitate or to settle out even and benzoic acid esters, glycol solvents, such as an oil soluble phenol resin and to produce bloom ethylene glycol, butyl cellosolve, etc., as well as on a treated surface. Generally a phenol form 30 solvents produced by hydrogenation such as hy aldehyde resin when employed is used in an ‘drogenated phenol. Particularly important for amount of from 1 to 10% of the composition inclusion in this group are the mobile pure or while the organic metallic component may be . ganic metallic compounds, such as cobalt, lead, etc., linoleates, naphthenates, etc., particularly used in an amount of from 1 to 20% of the com position, and mixtures of the phenol formalde 35 those which are soluble directly in petroleum and hyde resins and metallic organic components may may be utilized with the oil soluble phenol form be employed in the same composition within the limits referred to. aldehyde resins in a petroleum vehicle to serve as an individual solvent (requiring the aid of no The mild or neutral diluting cleaning vehicle , other solvent or modifying liquid) for the resin is desirably chosen from the group which consists 40 and as a modi?er of the petroleum diluent by re of volatile petroleum hydrocarbons such as pe ducing the disagreeable odor and preventing sur troleum naphtha, Stoddard solvent, etc., which face bloom; and they may also be used as an can be referred to as light petroleum liquids, auxiliary solvent with an alcohol soluble resin volatile liquid chlorinated hydrocarbons, such as for the purpose of minimizing the proportion of carbontetrachloride which is the most preferable cellulose ester solvent to less'than 30% of the composition. These mobile organic metallic com and ethylene dichloride, and volatile liquidmy pounds also serve as a lubricity agent thus en drocarbons, such as xylol as well as turpentine; or various mixtures and combinations of these abling ‘thesolvent for the alcohol soluble resin to ~ stated components. The light petroleum compo be non-sirupywnon-viscous, and non-dense, such asa simple alcohol, which is most economical for nent or the carbontetrachloride are the most de sirable components for these compositions for rim-use. general application, while the xylol and the In connection with these various vehicles it ethylene dichloride-aremore eifective vehicles in should _be noted that any of the volatile liquid compositions particularly useful on varnished or chlorinated hydrocarbons are suitable for use as painted surfaces. Turpentine may be included a modifying liquid in a ratio of from 10 to 25% to reduce the high luster and to produce a semi 55 of the composition; but when used as a diluting dull or dull ?lm, as for example, when desired on cleaning vehicle in the ratios above that amount, antique furniture. carbontetrachloride is the most suitable although For most desirable results, the phenol formal ethylenedichloride can also be used in the higher dehyde resin is used in an amount of from 1 percentages. Similarly, in connection with the to 5% of the composition, together with the dilut-' 60 ‘coal tar aromatic hydrocarbons, all are suitable ing cleaning vehicle, the latter constituting the for use in a proportion of 10 to 25% but when major proportion or bulk of the composition. used as a diluent, in the high ratios only xylol Where the resin is not soluble in the petroleum should be employed and then only for composi derivative or cleaning vehicle employed and for tions for application to oil coatings. ‘ other purposes as well, a modifying liquid is em 65 Various examples may be given to illustrate ployed, particularly in proportions of from 10 ' compositions produced in accordance with the present invention, the ?rst group of examples Such modifying liquid is desirably chosen from relating to compositions produced with phenol the following groups. Volatile liquid aromatic hy 70 formaldehyde resins. drocarbons may be used, such as benzol, toluol Example I and xylol, and their derivativessuch as benzyl Parts benzoate, benzyl alcohol, and benzyl acetate, and Oil soluble phenol formaldehyde resin____ 1 to 5 also turpentine. Or a volatile liquid chlorinated AHmodify'Fng liquid _____________ __'____ __ 20 to 25%. ~ ' hydrocarbon may be employedsuch as carbon 75 Petroleum naphtha __________________ __ 80 I 2,411,988 5 . , may be employed. In this as in other examples set forth below the components may be mixed in any desired order unless otherwise indicated and the com Particularly there may be mentioned in this connection Venice turpentine in combination with another modifying liquid which can be used in a larger ratio than the position is readily produced by combination of the stated components. In order to reduce the 5 ‘ slowly penetrating and drying and very pasty Venice turpentine. The latter should desirably inflammability of the compositions where the be limited to an amount of 1 to 4% or may be volatile petroleum diluents are employed, sub used in combination with about 8 to 16% of an stantially non-in?ammable compositions may be acetate ester, alcohol, or benzyl alcohol, benzyl ' produced by utilizing carbontetrachloride, for example, in an amount equal to that of the light 10 acetate or benzyl benzoate, or pine oil, or sec ondary or tertiary butyl acetate, or a mobile pure petroleum components. This is illustrated in the orgigiic metallic compound, or viscous sirupy sol following example: ven Example II Parts Phenol formaldehyde oil soluble resin____ 1 to 5 Pine oil _____________________________ __ 12 Stoddard 42 solvent ____________________ __ Carbontetrachloride _________________ .._ _ 42 In lieu of the pine oil a mobile pure organic . Asindicated above, drying oils and waxes are generally avoided and unnecessary. For some purposes, however, limited amounts of such vege table drying oils and of saponiflable hard waxes may be employed, particularly where the com position is to be utilized for specialized purposes. 20 When so employed the amount of vegetable dry ing oil such as tung oil or saponi?able hard wax such as carnauba wax should not exceed the metallic compound, more particularly described below, may be employed or the modifying liquid may be chosen from the ingredients given above. amount of resin present in the composition. Such tung oil or other vegetable drying oil contain The Stoddard solvent and carbontetrachloride 25 ing compositions are particularly useful for ap constitute the diluting cleaning vehicle. plication to cracked coating while the wax con Alcohol soluble resins of the phenol formalde taining compositions are more particularly use hyde or polybasic acid-polyhydric alcohol type ful for cracked leather furniture. may be employed, the quantities being ‘substan Compositions containing the higher propor tially less than that ordinarily employed for coat 30 tions of resin such as 8% and a modifying agent ing purposes; such compositions containing dilut including a cellulose ester solvent are particularly ing vehicles including petroleum derivatives as useful in removing accumulated dirt and grease set forth is thus made possible even by using or perspiration marks from leather furniture and minor proportions of a cellulose ester solvent, the simultaneously to deposit a ?exible preservative ' ‘ amount of the latter being substantially less than ?lm of resin. Metallic naphthanates may simie that ordinarily required in producing coating larly be used in such compositions. compositions. The following example illustrates such combination: cleaning and polishing purposes may desirably be made from the phenol formaldehyde resins and 40 particularly by the inclusion of the metallic or ' Example III ganic compounds of the character described Parts Alcohol soluble resin ______ __' _______ __ . While as set forth above, compositions for 1 to above, polishes can be produced including the me tallic organic compounds as the ?lm-forming agent without any inclusion of resins whatsoever, 5 Cellulose ester solvent ______________ __ 24 A modifying liquid as set‘ forth above__ 16 or the inclusion of resins to a very small extent only as from 1/g to 11/2% of the composition, to give even more greatly improved polishing and cleaning compositions based on ‘such utilization Petroleum naphtha _____ __ __________ __ 55 to 60 This composition is not injurious when used as a cleaning and polishing composition, even on of the metallic organic derivative as the ?lm 50 forming agent using such material in the ratio of about 4 to 20% of the composition. Exemplify ing such material, the following compositions are Cleaning and polishing ~compositions of the noted: character set forth above are particularly impor I Example IV tant and have unique properties. Immediately ' Parts after any excess of applied polishing composition 55 Oil soluble phenol formaldehyde resin_____ 11/2 has been wiped off, these compositions are resist quite sensitive surfaces and produces a. remark able ?lm of the character set forth above. ant to dust, in a relatively vshort time, as for exam One or more pure organic metallic com ple,,the space of one hour, they become substan tially dry and resistant to ?nger marks, give a Naphtha or Stoddard solvent __________ __ pounds soluble in petroleum __________ __- 4 to 6 _ high luster on automobile surfaces comparable 60 with newly sprayed film, they are homogeneous ' and do not require agitation or shaking before The organic metallic compound may be, for ex ample, equal parts of cobalt and lead naph thenates. The composition makes a ?ne polish. use, and they avoid lubricity agents such as greasy An even better polish is obtained when modify non-drying oils or even vegetable drying oils and saponi?able waxes which act to reduce luster and 65 ing liquids are included which consists of a wider combination of ingredients and especially when interfere with other desirable properties in vsuch there is included a cellulose ester solvent such as an acetic ester as indicated in the following composition necessitating the use of buffing. They do not result in any appearance of bloom . Certain modi?cations of these compositions may be referred to.‘ When the vehicle consists example: 70 Example V - Parts Resin ___ 1% of carbontetrachloride alone, there should be in Metallic compounds_________________ __ 4 to 8 cluded about 20% of a slower drying and higher Butyl acetate or ethyl alcohol ________ __ 4 to 8 density modifying agentv for which purposes mod ifying agents of the character set forth above 76 Naphtha or Stoddard solvent........ -.. 82 to 100 2,41 1.988 . Referring to the organic metallic derivatives,‘ r 8 volves treatment of 1 part cobalt acetate with 3/15 part potassium hydroxide and 18 to 20 parts linoleic acid. Naphthenic acid is the most effective the linoleates are desirably used but the best re sults are obtained with the naphthenates. The metallic compounds should be dilutable in a pe reagent to give metallic compounds soluble in troleum distillate to a clear transparent liquid even in the cold without the necessity of previous solution in turpentine (heretofore required in the prior art), (1) to the smallest concentration, as for example, %% for the purpose of merely giv ing color to the composition, or (2) to concentra 10 tions as high as 16 or even 20% to serve as a film forming agent. Only such a pure organic metallic compound can be used in this way. petroleum derivatives and forms such derivatives even in the cold. For example, 1 part lead acetate reacted with only 8 parts naphthenic acid in the cold form the desired derivative and such prod uct is nearly colorless and suitable as a polish for light colored automobiles. The pure metallic organic compounds even of colorless lead or zinc, are colored per se and they give a fine color to the polishing compositions even when used in a The organic metallic derivative employed may concentration of merely 1/i%. be produced in a variety of ways as illustrated by 15 However produced, the product ‘should be pure the following. It may be produced by thorough and free from contaminating ingredients which reaction of an inorganic metallic compound of lead to difllculties in solubility and other char the character desired such as a salt of cobalt, acteristics. These pure organic metallic com pounds are soluble to' give a ?ne transparent magnesium, manganese, lead, aluminum, etc., particularly a water soluble salt such as the sul 20 color, in petroleum hydrocarbon including even phate, acetate, etc., utilizing an excess of liquid fatty acid or reagent for reaction with such metallic salt, the excess of the liquid fatty reagent being substantially beyond that nec essary for metathetical reacting proportions 25 and may actually be as much as 20 to 35 times greater in weight than the corresponding metal derivative. The actual proportion of liquid fatty the non-saponifiable and non-drying para?ln and mineral oils, such solution being readily pro duced in the cold, and in varying proportions without the necessity of solvents, such as turpen tine or added ingredients like vegetable oils. These liquid organic metallic compounds are referred to as mobile because of their liquidity and they give exceedingly important character reagent depends on its acidity, the alkalinity of istics to the cleaning and polishing compositions the metal compound, the acid number of the 30 in which they are employed, among which there organic reagent, the degree of heat emp1oyed,'and may be noted that they do not result in any pre the hardness of the metal of the compound, that cipitation in the desired composition and thereby is, whether a hard metal like cobalt or a soft produce homogeneous materials which are readily metal like lead. Such mobile metallic compound distributed in a uniform manner over the sur-, acts as a solvent for the oil soluble resin, as an 35 face to be treated. Because of their homogeneity auxiliary solvent for the alcohol soluble resin, as they are readily packaged for sale in glass con a lubricity agent, as a modi?er for the petroleum tainers. They reduce or completely mask the diluent to prevent bloom and as an independent disagreeable odors of the petroleum or turpentine ?lm-forming agent which is better than a solid vehicles, particularly when used in the higher metallic compound derived from a solid fatty acid 40 proportions referred to, and they modify the like stearic acid or from rosin. Or the desired petroleum vehicles so that the latter do not ex compound can be produced by a double decom hibit bloom or ?owers on surfaces to which they position as set forth above and the precipitated are applied. They are compatible with oil soluble metal compound subjected to a repetition of treat resins and combine with the latter in producing ment. Or reaction may be carried out using 45 uniform homogeneous compositions even in vola naphthenic acid which reacts more effectively tile petroleum vehicles, they dissolve all solid oil and spontaneously with the desired metal ingre soluble resins and modify them so that they are dient, as for example, lead acetatae, giving re lubricous and freely distributable by a cloth, action in the cold to a pure organic compound they enable relatively low cost or low grade oil particularly useful in polishes for light colored 50 soluble resins to be employed, they enable the automobiles and furniture. Or the metal com pound may be ?rst treated with alkali, as for example, 1 to 3 parts to 15 parts of the metal, and then reacted with the liquid fatty reagent amount of solvent necessary for the resins to be materially reduced because they have a solubiliz ing effect on the resins, and particularly they act as ?lm-forming agents which produce a very or the alkali may be present during the reaction thin light transparent metallic preservative ?lm of the other components. The character of the of very delicate character. These metallic deriva inorganic acid from which the reacting metal tives may be used in the petroleum or chlorinated salt was derived requires consideration. The hydrocarbons without precipitation even with stronger inorganic acids like sulphuric or hydro chloric give compounds which are more acid in 60 the lead derivatives which usually give precipi tation in the presence of chlorinated hydro-. character than salts derived from weaker acids carbons. The ?lm produced from the metal such as acetic acid and reduce the alkalinity of the’composition. Consequently alkaline reagents derivative does not mask the grain of woods ' used 1/15 part of the alkali, enabling conversion solvents for alcohol soluble resins, they enable the higher-ratios of petroleum diluents to be em such as mahogany, red wood or oak. Even when may be incorporated to get more complete re action.‘ For example, 2 to 4 parts of potassium 65 used in the highest proportions they produce no sediment and are not affected by light even when hydroxide or strong ammonia may be added for‘ exposed in ordinary glass containers. They may each part of cobalt sulphate and reacted with 15 to 20 parts of the organic acid followed by wash be used as a. solvent for oil soluble resin to elimi ing of the product and then drying. For treat nate the necessity for cellulose ester solvents so ment of lead acetate which is a salt of a softer 70 that the resulting composition is not injurious metal, less alkaline reagent may be employed, even to imitation hard wood ?nishes which are thus for each part of lead acetate there may be the most sensitive coatings. Used as auxiliary into the pure organic derivative by a small excess of the organic reagent. Another example’ in 76 2,411,938 . 10 liquids which are stable even on long standing and do not require agitation or shaking before use. They eliminate ?re hazards. They are non-in As an example of such types of compositions, the following is given: Example VI jurious to oil coatings and even on sensitive lac 8 to 16 parts of one or more mobile pure organic CI quer ?lms may be readily used so that they are directly suitable for use on automobiles, pianos, metallic compounds, particularly those soluble ‘ radios and other household furniture, ‘and for directly in volatile petroleum hydrocarbons. painted, varnished, and enameled surfaces. They 80 parts of a diluting cleaning vehicle consisting are free from acids, alkalies, soaps, water, abra of a volatile petroleum hydrocarbon, carbon tetrachloride, ethylene dichloride, xylol or tur 10 sive powders, and from any ingredients which pentine. give rise to injury to surfaces particularly when - used in the proportions herein set forth. Having thus set forth my invention, 1 claim: 5 to 20 parts of a modifying liquid such as an oil containing ester, a cellulose ester solvent, 1. A cleaning and polishing composition suit a liquid chlorinated hydrocarbon of higher density than carbontetrachloride, or a combina 15 able for automobiles and furniture, capable of producing a very thin transparent lustrous pre tion of such components. servative ?lm reducible by repeated applications Cleaning and polishing compositions produced with a cloth and thus non-accumulative to a in accordance with the present invention are par ticularly valuable in polishing metal and wood thick layer, said composition comprising from 1/2 20 to 5% of an oil-soluble phenol formaldehyde surfaces such as automobiles and household fur resin and from 1 to 8% of a petroleum soluble me niture. They are readily applied to the surface to tallic salt of a carboxylic acid as ?lm forming be cleaned and polished and are freely distribut components, the ?lm forming components being able thereon, rapidly, producing a lustrous ?nish present in limited proportions sufficient to form without the need of buffing or rubbing. a very thin delicate transparent ?lm insu?icient A simpler type of cleaner for automobile sur 25 of itself to act as a protective ?lm, the remainder faces which may be readily used for cleaning such of the composition being petroleum hydrocarbons surfaces even more thoroughly than by washing boiling in the range of Stoddard solvent, and up may be composed of from 8 to 16 parts of a metal-. ‘ to 25% of a compatible organic volatile liquid lic naphthenate with 84 parts of Stoddard solvent solvent for the resin and salt. or slow volatile ‘naphtha equal in character to 30 2. A composition as set forth in claim 1 which Stoddard solvent. contains said compatible solvent and said solvent A simple polish for common wood work may be boils above the petroleum hydrocarbons. composed of from 8 to 20% of a metallic naph 3. A cleaning and polishing composition com thenate with 85 parts of para?ln oil. The metal prising from V2 to 5% of an oil-soluble phenol lic compound greatly reduces the greaslness of formaldehyde resin, from 1 to 8% of a petroleum the oil and to some extent gives it drying proper soluble metallic soap, the remainder of the com ties and a lustr'ms ?nish. position being petroleum naphtha, and up to 25% Cleaners and polishers produced in accordance of a compatible organic volatile liquid solvent with the present invention exhibit many note for the resin and soap. ‘ worthy advantages over prior art types of mate 40 4. A composition as set forth in claim 3 which rials. They are directly applicable as by a cloth contains said compatible solvent and said solvent and readily dissolve and remove accumulated boils above the petroleum naphtha. grease and hardened dirt. They are of unusual 5. A cleaning and, polishing composition com economical cost because the lower grades of pe 45 prising 11/2 parts of oil-soluble phenol-formalde troleum naphthamay be utilized and may con hyde resin, from 4 to 8 parts of petroleum solu stitute as indicated as much as 85% of the com position. They are' readily made by mixing the stated ingredients without the use of heat to produce homogeneous substantially transparent ble metallic soap, from 4 to 8 parts of butyl ace tate, and from 82 to 100 parts of naphtha. JACOB RA'I'NER.