Patented Aug. 27,’ 1946 2,406,336

UNITED STATES PATENT OFFICE

‘ - V ‘ 12,406,336" ' ' WAXES taszIeA-uer, South Orange, J. No‘ Drawings ‘ ‘Application’ August 21, 1942, Serial No. 455,613 r0" claims. (CL 106-40) - I 2 FIELD or INVENTI‘ON J anon This invention relates to the modi?cation 0f the properties of Waxes. The invention is par a. Main constituents: ticularly concerned with treatment of organic 1’. Palm-itin ester-type waxes or waxlike materials, as dis 2. Palmitic acid tinguished from certain hydrocarbons which are b. Subordinate constituents: L Dibas-ic' acids sometimes termed waxes. For instance; while 2-. Soluble acids paraf?n, montan wax and cere‘sin,ua're= sometimes referred'to as waxes, they are not “true” waxes‘. Bayberry was: In contrast, the invention is concerned with- the 10 treatment of ester-type waxes such, for instance, as listed just below: , Beeswax Although some of the'f'oreg‘oing lis‘t'are o'f ani Inal and some of vegetable origin, I believe them, Carnauba wax 15 Spermaceti wax all to“ be‘ organic~ is'oc‘olloids, i. e., colloidal sub Candelilla wax stances‘ in‘ which; the dispersed phase and the Japan Wax ' dispersion‘ medium‘ are: both of the same chemical Bayberry (Myrtle)v Wax composition; though present in different physical states: ' v i These waxes are esters of long chain aliphatic 20 There‘ are» other wax ,or wax-like materials alcohols with long chain aliphatic fatty acids,‘ as which are‘ organic; isoco'l-loi'ds andwhich may be is indicated in the following listing of some of treated in accordance with the“ invention'jfor the major constituents of various oi the: waxes instance, synthetic wax-11x6- products containing above mentioned. either a natural wax alcohol or a natural wax Beeswax‘ : 25 acid or their homologues, derivatives and- substi a. Main constituents: t‘ution' products; ' ' 1. Cerotic acid The“ term‘ “ester-type waxes," as used‘ herein, 2. Myricyl palmitate is’ intended to ‘comprehend. not‘ only the natural b. Subordinate constituents: ester-type" waxes‘, but‘ also‘ synthetic products of I. Melissic acid 30 the type‘ in'entionedjust above; 1 2'. Myricyl' alcohol I‘ have found that bycispersing treating‘ or 3". Ceryl alcohol"v ' frfod'iiyihg'ag'ehts‘in tnevvaxes, changes may be c. 13%‘ hydrocarbon brought‘ about in" a number or different charac teristics‘ or properties, thereby rendering‘ the C'arnaubu- was‘ ' treated waxes better suite'd'to many purposes than . Carriaubic acid _ are'tne" same‘ untreated‘ wastes. The changes or . Ceryl, myricyl alcohols‘ nm'di?cations brought about‘ in accordance with . Other alcohols the present invention are apparently colloidal . A hydroxy acid and/or chemical in; nature, in many instances . A hydrocarbon 40 changes of both typesio‘ccurriiig' asra result of the treatment. For instance, a change inrtne relative Spermac‘eti wax? proportions of the dispersed phase andadispersion a. Main constituents: medium may be brought about. 1. Gem palmitate - Whatever may be the exact mechanism» by’ b. Subordinate constituents: 45. which the changes occur, I have found thatthe l. Glycerides of lauric, stea'ric, and myristic present invention may be utilized to bring about acids : changes in such physical characteristics as melt Cc‘mdelilla war" ing point, acid value, sa‘ponii’ication value, iodine value, solubility characteristics in various sol a. 56%unsaponi?able (hydrocarbon) 50 vents, and. physical consistency at various diii’er b; Remainder (ester) enttemperatures . 2,406,336 3 Modi?cation in certain respects noted above is Many of the compounds falling in certain‘ important for some purposes, and for other pur classes mentioned above are also of the type poses, modi?cation is desirable in other respects. which I have termed “two-radical” compounds, i. e., compounds having within the molecule an ‘Because of common uses of various waxes, for instance, in ?oor polish, furniture polish, shoe acidic inorganic residue and an organic residue. polish, and the like, it is frequently desirable to By an acidic inorganic residue I mean a residue employ a wax having a relatively high melting capable of yielding an inorganic acid upon the 3 point. Although the melting point need not nec addition of one or more hydrogen atoms, OH 1essarily be changed in all instances, it is of im groups, or water molecules, or upon the applica portance that the invention is well suited to the 10 tion of heat. ‘raising of the melting point of waxes, for in Such two radical type compounds may desir ably contain a sulpho-, halo..v or nitro-group, stance, of beeswax andrcertain others, which, in Typical examples of certain of the foregoing . their normal condition have a relatively low melt 1 ing point and therefore have not heretoforebeen' classi?cations are given just below: lconsidered as practicable to employ for certain Metal salts of inorganic acids: Sodium bisulphite ' ' I1 purposesstance, that in whichof carnauba a higher wax) melting is preferred. point (for in-v‘ v Sodium 'hydrosulphite ‘ The foregoing is cited as illustrative of the ‘ Sodium sulphite manner in which the present invention may be‘ I Ammonium iodide ‘ utilized to adapt certain waxes to uses for which 20v;v Magnesium chloride they are not well suited in their natural state. ‘ Zinc carbonate ‘In this way, in some instances the invention 7' _Lead chromate 3 makes possible the utilization of a less expensive ‘v Metal salts of organic acids: , wax to replace a more expensive one, without ap Sodium oxalate 7 preciable sacri?ce of quality of ?nished-product 25 G-salt (sodium beta hnaphthol-?, S-disulpho such, for instance, as ?oor or furniture polish. nate) In addition to some of the uses'already men Salts of organic amines: ‘ tioned, waxes are adaptable for many other pur Diphenylamine trichloracetate ‘ poses among which might be mentioned metal Inorganic acids: ' polishes, automobile body polishes, carbon paper Sulphuric acid i and typewriter ribbon impregnating compounds, Phosphoric acid' 1 dental waxes, sealing waxes and ski ‘waxes. A .Hydrochloric acid 1 wide variety of properties and characteristics are Organic acids: , ; desired for many of the several commercial uses _ Tartaric acid and the invention, in its broad aspect, hasin mind Maleic acid ' adapting various waxes to the several commercial Acetic acid ‘ uses, thereby better ?tting them for such pur Oxalic acid ‘ poses. Before ‘considering in, detail the nature'of the Salicylic acid process andthe treating agents employed, the Phthalic acid 40 Citric acid process is ?rst brie?y summarized as follows: Metal alcoholates: The ‘wax to be treated is preferably heated in Sodium amylate I the presence of the modifying agent for a sub stantial period of time and at a temperature con~ ‘ Amines: Benzidine base _ ‘ V siderably above normal room temperature, it be- ‘ ing of importance to secure thorough dispersion a-Naphthylamine ' V 'I‘wo-radical compounds: of the treating agent in the wax. Sulphosalicylic acid Moorr'vmc AGENTS Nitro-anthraquinone p-Toluene sulphochloride ' Modifying agents of 'quite'awide variety of 50' ' types may be employed. Many of such agents p-Toluene sulphonic acid are polar compounds, 1. e., compounds contain o-Nitrophenol ing a positive charge in one part of the molecule p-Nitrophenol and a negative charge in another part of the I have found certain“ groups of modifying molecule, or capable of orienting their different agents“ to be particularly effective in the treat; radicals in opposite directions on an interface of ment of waxes—for instance, metal salts; amines, liquid-gas, solid-gas, liquid-solid or liquid-liquid. particularly diprimary amines; and two radical VMany polar compounds which are electrolytes . type compounds, especially those. containing ‘ have been found to be useful. ‘ . sulpho- and nitro-grcups. ' The modifying agents may be classi?ed in vari Hereinafter examples are given of the treat ous Ways, for instance under the following ment of waxes with modifying agents selected headings-—- ’ ' . from various of the classes above discussed.’

Metal salts of inorganic acids TREATMENT CONDITIONS , Metal salts of organic acids Inorganic acids Although the treatment conditions‘ may be Organic acids varied in accordance with a number of factors such as the particular wax being treated, the . Metallo-organic compounds: treating agent selected and the characteristics Metal alcoholates _ desired, in general, the treatment conditions Aryl-metal compounds .70 should conform with the following: Organic salts of inorganic acids With respect to temperature, it is ?rst noted Inorganic salts of organic bases that while some modi?cation may be brought Organic esters ' about by dispersing the modifying agent in the Amines also constitute a useful class,‘ particu- '" ‘Y wax at normal room temperature, in general, the ‘ larly the, poly-amines, for instance, di-a’mines.‘ ' " treatment temperature should'be above the melt 2,406,336 5 6 ing point of the wax though not above the point and treating agent together. Obviously, however, at which any appreciable decomposition occurs. from the standpoint of the broader aspects‘ of the Usually it is found that a temperature between invention, the wax and the treating agent may about 100° C. and 310°’ C. is eifective; Increase be brought together in any desired manner. Agi-‘ in temperature is usually accompanied by more 5‘ tation may be useful for this purpose in some in rapid and/or more extensive modi?cation, al stances. though as just noted, the temperature is desir Beyond the foregoing, it is contemplated that ably kept below the point at which any decom the modifying agent may be produced in siti, position occurs. Particularly good results are se by introducing materials which will react under cured with many waxes at temperatures between 10 the conditions of treatment to produce the mod about 250° C. and 310° C. ifying agent desired. - ‘ The duration of the heating will again depend somewhat on the materials used and the results EXAMPLES desired. Usually the heating should be continued In a series of comparative experiments, a bees- at least until thorough dispersion of the treating 15 wax was treated with a number of different mod agent is obtained. Ordinarily it is found that ifying agents. The initial untreated beeswax had treatment for a period of at. least 30 minutes is a melting point of 64° C., an acid value of 20.2 required for this purpose. and a saponi?cation value of 93.3. The wax was . The quantity of modifying agent employed will of medium light color. also depend somewhat, on the Wax being treated, 20' For purposes of comparison, in one experiment on the modifying agent selected‘ and on the par this wax was heated without any modifying ticular characteristics desired. For various pur agent, under exactly the same conditions as em— poses a relatively wide range is suitable, for in ployed for the heating in the following experi stance, from an appreciable trace (such as .01%) ments using various di?ferent modifying agents. up to about 30%. Ordinarily, however, a range 25 This heated wax had a melting point of ‘75° 0., from .l% to 10% is found to be effective. With an acid value of .75, and a saponi?cation value many treating agents more than a fractional per of 100.5. The product was black. centage is required to secure an appreciable mod The treatment conditions employed not only ification, although as will appear from certain for the heating of the wax without modifying examples given hereinafter, .5% is shown to be 30 agent, as above mentioned, but. also in each of su?icient for some purposes. the following experiments of this series were as The nature of the atmosphere in contact with follows: ’ the reaction mass will in?uence the modi?cation The wax was placed in an open beaker under a which occurs. With many waxes and with treat blanket of CO2 and maintained, at about 300° C. ments for a number of purposes, it may be found 3 5 for a period of ?ve hours. desirable to exclude air from the reaction. This The following table indicates the modifying may be accomplished by employing vacuum, agents and percentages thereof used in each of and/ or introducing certain gases into the reaction the comparative experiments, and also various vessel to blanket the surface of the batch. Gases ‘of the resulting characteristics: .

Example Modm. 1. mg agent Per-cent Meltingpoint valueAcid valueSap. bilitySolu

° C’. Untreated______. 64 20 .2 93 .3 l Heated ______-_ 75 ‘.75 100 .5‘ > ,1 1a~__ _ Sodnlm bisulphite ______1A 82 2 .75 96 .4 1+ 1b______.. 5 137 1.95 77 .5 2+ 2a_ Sodium hydrosulph1te y, 75 1 .15 89 .7 1 2b______: ______5 140 2 .8 66 .7 4+ 3@_ Sodium sulph1te_ __ y, 90 l .75. 79 .9 1 4a“, Benzidine base._ _ V2 75 > 1 .98 88 .1, I 4z,_ . o ______-. 5 121 .7 92 .4 2+ 5a ______N itro-anthraquinone .... __ % 73' .7 91 .85 1+ 51;, .-_._do ______- 5 74 .7 83.2 2 ea_ Sulphosalicylic acid M, 76 .7 92 .8 1 6b_ _.__.do; ______5 75 .8 100.5‘ 1. 7a_ p-Toluene sulphochlo % 70 .3 89.7 1+ 71;______do ______-_ 5 68 54.5 85.5 1+ p-Toluene sulphonic acid__ %' 75 0 .8 92 .6 l d 6 80 2.1 74 .4 3+ % 75 .7 100 .6 1 — 5 74 4 .9 92.5 1 % 74 .8 94 .6 l 5 75 4 .03 85 .8 l

suitable for this purpose are ‘nitrogen, CO2, S02, From the above it will be seen that certain H28, amongst others. ' 60 classes of treating agents are of especial advan Pressures above atmospheric may also be em tage in raising the melting point of the waxes. ployed to advantage for some purposes. Note for instance that a very marked increase in In addition to employment of gases for pur melting point is secured by the use of metal salts poses such as mentioned just above, certain gases (seei'Examples 1a, 1b, 2a, 2b and 3a) and also by may also be utilized by bubbling the same through 65 the reaction mass during the treatment, so as to the use of an amine,such as the benzidine base bring about further or supplemental modi?ca-l ' of. Examples 4a and 41), this amine being a di tions. S02 and H28 may be utilized for a pur primary amine. pose such as this. Under certain conditions a Analysis of the foregoing table will further show sulphurized product may be. obtained by com- 70 that in many instances the higher percentage of bined use of S02 and HzS. modifying agent produces a greater degree of Since wax-es are ordinarily solid or paste-like modi?cation. v ' , materials at normal room temperatures, admix- " The comparative results above also indicate ture of the wax and modifying agent is, inmost" ' the. possibility ofsecuring' appreciable changes cases, desirably accomplished by melting the wax 75' not only in acid value but. also in the saponi?ca 2,406,336 8 ‘tion value, depending upon the treating agent Analysisv of'the foregoing again shows quite employed and the percentage used. surprising results in modi?cation of various prop The column in the above table under the head erties. Note for instance the exceptional result . ing of “Solubility” indicates the consistency of a secured 'from the. standpoint of melting point ‘ mixture of the wax with turpentine, in the ratio when employing sodium bisulphite as in Example of 50% wax and 50% turpentine. The numerals 11; .Sodium hydrosulphite, benzidine base and P in the column represent an arbitrary scale, the p-nitrophenol also substantially increased the ' higher numerals indicating stiffer wax-turpentine melting point. 7 , mixtures. For example, numeral 2 indicates a - The modi?cations in color are also signi?cant, mixture of stiffer consistency than numeral 1. 10: it being of interest to note that a number of the ‘ 2+ indicates a still stiifer mixture, and so forth. products treated with modifying agents had a Thus/from the “Solubility” column it will be color lighter than the batch which was heated ' , seen that most of the treated waxes yield wax without any modifying agent. 7 In fact, nitro ‘ turpentine mixtures which are at least as stiff as anthraquinone and p-toluene sulphonic acid of those secured with the untreated wax (and also ' Examples 14 and 17 yielded a product having a with the wax which was heated without modify color approximating that of the original un ; ing agent) . Many of the modi?ed waxes yielded treated and unheated candelilla wax. ‘ wax-turpentine mixtures considerably stifferithan The above table also shows considerable modi? ‘the same mixture incorporatingthe untreated cation in certain instances in-the consistency of , wax; note, especially, the waxes treated with 5% '1 wax-turpentine‘ mixtures, this characteristic j of sodium hydrosulphite and with 5% of p ‘again being indicated in the “Solubility” column. . ‘ toluene sulphonic acid. 9 Various of the foregoing waxes were incorpo Although the color of all of the products was rated in several different polish‘formulas in order ‘ darker than the untreated and unheated beeswax, to secure comparative data as between treated 1 it is interesting to note that the color of certain 25” and untreated waxes and also as between the ef- ' 3 of the products resulting from use of modifying ‘fect of different modifying agents. With this pur agents was lighter than the color of the beeswax pose in view the waxes were used in a furniture, which had been heated without modifying agent. polish, in a floor polish and in.a shoe polish. Thus, the‘ products of Examples 4a, 6a, 6b, 7a., 7b, 8a and 9a were all lighter in color than was the 30' Furniture polish ' 1 product of the’ beeswax when cooked without A typical furniture polish formula was selected, ‘ modifying agent. , this being as follows (all parts being by weight) : With respect to the color of the waxes, it is to be noted that for many purposes the color is im "Replacement ingredient” ______10 ' 3 material. In instances, however, where it is de ‘,. Beeswax ______‘___' ______4 Ceresin ______'____‘ ______'4 ‘ siredmodifyingagent to retain as should light bea colorselected as possible,accordingly. the Stearic acid ______8 In another series of comparative experiments Triethanolamine _____' ______4.8 V. M. & P. naphtha 1__*__~ ______'__;.____ 80 ‘ candelilla wax was treated with various modifyf ‘ "ing agents, the treatment conditions being the,‘ Water (boiling) ______200 same for each example. In this series-treatment , 1Varnish maker’s and painter’s naphtha. ‘ was eifected in a closed beaker (having only a small outlet to the atmosphere), without intro» 1 . In formulating the foregoing polish, the several ‘ duction of any gas and at atmospheric pressure. wax ingredients (including stearic acid) were , The temperature was maintained in each case at . .melted'in the order listed above, the ‘freplacement 1 about 300° C. for ?ve hours. 'In all experiments ingredient” being different .in each polish pre ‘ of this group 5% of the treating agent was em-~ > pared, i. e., being selected from various of the un I ployed. ’ ' @ treated and treated waxes’discussed above. After The initial untreated candelilla wax‘ had a. melting of the waxes together, the triethanol 1 melting point of 73°, an acid value of 16.9, saponié 50 amine was added. Then followed slow addition _ ?cation .value of 52.5, the initial color being - of the naphtha with agitation. Agitation was , medium light. . ‘ ‘ continued during very slow addition of the boiling For purposes of comparison one batch of they“ water, until a uniform'emulsion was produced, the I 'wax was trea ed under the foregoing conditions .. fa'gitation being continued until the polish had, f but without the presence of any modifying agent. "i cooled. , The product of this experiment had a' melting Q 'The untreated and also the heated (without 1 point of '74" C., an acid value of 9.9, a saponi?ca modifying agent) beeswax and candelilla wax 3 tion value of 48, and the color was medium dark. , were substituted in plaoeof the “replacement in The following table indicates the reagent used gredien ,” in addition to the employment of var ‘ in the several experiments of this series, and also 60 ious of the waxes modi?ed with treating agents. 1 various characteristics: . For convenience in the following analysis of re

Example’ Modifying agent lgaglg Acid value 553;, giggly Color

Degrees _ Untreated ______._ 73 52. 5 l L1ght. I i ______48. 0 l Fairly, dark. Sodium bisu1phite_ _ _ _ _ 16. 9 3+ Black. Sodium hydrosulphite 22.0 1+ Quite dark. Benzidine base _ . 29.3 4+ Black. _ Nitroanthraquinon 25.1 V 1- Light. Sulphosalicylic acid" -. 46.4 17 ' Fairly dark. p-Toluene sulphochloride ______>39. 6 1 Do. p-Toluene sulphonic acid ______29. 1 1+ Quite light. o-Nitrophenol ______._ 7 . . 33.1 1 Very dark. p-Nitrophenol ______. 89 ._.__do___.‘___ _ 40. 7 1+ Black. 7 2,406,336 “10 sults, the beeswax which was used in untreated ‘and the triethanolamine ‘is slowly added, with condition and the beeswax which was heated constant stirring. Next the borax of part A was without modifying agent are referred to, respec dissolved in one-quarter of the water (heated tively as beeswax controls A and B. The cande to boiling), and this borax solution was then lilla wax (untreated, and heated without modify added to the wax solution. The resulting mass ing agent) are similarly referred to as candelilla controls A and B. was stirred for two minutes, after which the remainder of the water (of part A) was added This series of furniture polish experiments and the mixture stirred until cold. showed some very interesting improvements as'a Part B was prepared by boiling the first part result of the use of modifying agents, as com 10 of the water thereof and then dissolving the pared with the several controls; and while ad borax therein, after which the shellac was added justment of other ingredients in the formulation to the borax solution with stirring. Finally the would normally ‘be desirable, for properly bal remainder of the water (boiling) was added. anced polishes when one 'Wax is substituted for Preferably after permitting the solutions (A another, the formulation was kept the same and B) to stand for a day, 18.5 parts of B are throughout the series of experiments in order to added to 100.9 parts of A, with stirring. clearly demonstrate the effect of substitution‘ of As in the experiments with furniture’ polish, the modi?ed wax for the unmodi?ed wax. various of the modi?ed and unmodi?ed waxes Various characteristics of the polishes were were substituted in the position of the “replace then determined and compared. The following 20 ment ingredient,” and the polishes were then are some of the more important improvements analyzed for various characteristics, for ‘purposes which were noted. of comparison. , First, with respect to the beeswax furniture Here again, not withstanding the fact that for polishes, many of them indicated an improvement properly balanced ‘polishes when one wax is sub both with respect to'rubbing qualities and with stituted for another the formulation would ordi respect to stability (stability of the emulsion). narily be altered, in order to secure better com Thus, polishes prepared with waxes treated with parisons, the formula was kept the same in each sodium bisulphite, sodium hydrosulphite, benzi instance, thereby clearly demonstrating the effect dine base, nitroanthraquinone, all disclosed im of substitution of the modi?ed waxes for the proved rubbing qualities, as compared with both unmodi?ed waxes. of the beeswax controls A and B. Numerous of the ?oor polishes made with The stability of the polishes prepared with modi?ed waxes showed improvements ‘over pol modi?ed beeswax also compared very favorably ishes made wit the beeswax and candelilla wax with the beeswax controls, most of the polishes controls A and B. ‘ showing up better in this respect than the bees With respect to ease of emulsi?cation, it is wax control A, many also being equivalent to ?rst noted that most of the modi?ed beeswaxes beeswax control B. were at least equal to or better than the beeswax The gloss of the modi?ed beeswax polishes also controls A and B. Moreover, certain of the modi compares favorably with the controls, beeswax fying agents yielded polishes in which the emul treated with 5% sodium bisulphite, being marked 40 sion stability was at least equal to or better than 1y better than both of the controls A and B. the controls. Sodium bisulphite and sulphosali With respect to the use of candelilla wax, it is ,cylic acid were both effective in yielding good noted that various of the polishes containing stability characteristics. . modi?ed candelilla wax showed improvement in With respect to the properties just mentioned, rubbing qualities and stability of the emulsion as " the polishes made with modi?ed candelilla wax compared with candelilla controls A and B. . The also showed up in a similar way. Sulphosalicylic metal salts showed particularly good results with acid showed good results not only from the stand respect to rubbing qualities and stability, espe point of ease of emulsion and stability of emul cially sodium bisulphite and sodium hydrosul sion, but also with respect to polish or gloss phite. secured. This reagent (sulphosalicylic acid) was Although there was considerable variation in in fact particularly good with respect to gloss. color as between the Various polishes, it may be mentioned that o-nitropheno-l and sulphosalicylic Shoe polish acid, both with beeswax and with candelilla wax , The shoe polish formula employed for test pur yielded polishes of quite light color. 55 poses was as follows (all parts being by weight) : Floor polish “Replacement ingredient” ______8 The following formula was selected for pur Beeswax ______- ______8 poses of testing the several waxes in a floor polish. Montan ______5 (all parts being by weight) : Para?in ______15 60 Turpentine ______68 A. “Replacement ingredient” ______13.2 In preparing the shoe polishes, the “replace Oleic acid ______1.5 ment ingredient” (the wax) was ?rst melted after Triethanolamine ______2.2 100.9 which the montan, beeswax and paraffin were Borax ______1.0 65 added. Then, with agitation the turpentine was Water ______83.0 added. Here again, both the beeswax and can delilla controls A and B, as well as the modi?ed B. Borax ______2.1 waxes, were substituted in the position of the Water ______14.2 185 replacement ingredient. Shellac ______7.2 ' The results with the beeswax polishes indicated Water ______24.2 70 that almost all of the polishes made with modi In formulating the foregoing polish, portion A ?ed beeswax were at least harder than beeswax is prepared by ?rst melting the "replacement controlA, and in some instances, even appre ingredient,” i. e., the wax, and then adding the ciably harder than beeswax control B. oleic acid. The temperature is brought to 95° C. With respect to gloss, improvement was noted with most of the polishes made with modi?ed 2,406,830 I . 12 11 ‘ 'addition'of at least one of the group consisting ' beeswax; sodium blsulphite, sodium hydrosulphlte fof hydrogen atoms, O-H-groups, and water mole and p-toluene sulphochloride yielding polishes of cules, said'modifying agent being a member of particularly good gloss in comparison with the the class consisting of aromatic sulfonic acids, controls. ' ‘ ' > - ‘ aromatic sulfochlorides, and nitro-substituted ' ‘ With respect to polish consistency, it is worthy aromatic compounds, capable of yielding an of note that ingeneral the waxes treated with inorganic acid which is a member of the group 1/2% of the modifying agents yielded harder pol consisting of sulfuric acid, chlorsulfonic acid and ' i‘she’s'‘ than those with 5% of modifying agent. However, the metal salts showed up well with nitric acid. ‘of-claim- 1, ' in whichI said wax' respect to consistency, even where used in 5% a 4. The process concentration; 5% sodium bisulphite and 5% is beeswax. V r sodium hydrosulphite both yielding quite hard 5. A process in accordance with claim 1 in whichsaid wax is candelilla wax. polishes in comparison with the beeswax controls 6. A process in accordance with claim]. where A and B. ' ' . a '7 in the treatment temperature is from 250° C. LMany of the polishes made with modified can to v310° C. ' - ' a delilla wax also showed up‘ satisfactorily with '7. A polish comprising a modi?ed wax product respect to consistency and gloss, sodium bisul phite being particularly good for both of these ‘and a volatile dispersion medium and being characteristics. p-Toluene sulphochloride also characterized by a materially greater ?lm tough yielded notably improved viscosity (a harder 20 ness than characterizes a polish ?lm made from ‘ the same ingredients but in which the waxis paste) than did the candelilla controls A and B. modi?ed, said modi?ed wax product comprising 1 I1. claim:The process ’ of modifying‘ at least one of' the‘ thereaction product of av natural ester-type wax ‘following physical properties of ester-type waxes: 1 with from 0.5% to 10% ofa compound having 25. within the molecule an acidic inorganic residue consistency, melting point, rubbing characteris and an organic residue, and said compound being ‘tics, which process comprises dispersing in the ' a member of the class consisting of aromatic wax from 0.5% to 10% of a compound having sulfochlorides, and within the molecule an acidic inorganic residue 'sulfonic acids, aromatic and an organic residue and heating the wax to nitro-substituted ‘aromatic compounds. 30 8. A heat-treated ester-type natural wax hav a temperature between about 100° C. and the ing dispersed therein from 0.5% to 10% of a decomposition point of the wax, until the wax . treating compound having within the molecule "manifests properties which are substantially dif an acidic inorganic residueand an organic resi ferent in .at least one vof the respects herein due, said wax having a melting point, appreciably named, as compared to the properties of a similar 35 higher than that of the same natural wax heat material subjected to the same treatment but 7 treated alone, and said treating compound being absence of the treating compound, said treat a member of the class consisting of aromatic :ing compound‘being a member of the class ‘con sulfonic acids, aromatic sulfochlorides, and nitroi lsisting of aromatic sulfonic acids, aromatic sulfo substituted aromatic compounds. 7 I ‘chlorides, and nitro-substituted aromatic "com-7 9. A polish comprising, as wax ingredient, the ‘pounds, capable of yielding an inorganic acid ‘modified wax product of claim 8, and manifesting ‘which is a'member of the group consisting‘, of an increased hardness in its ?nal ?lms, as com sulfuric acid, chlorsulfonic acid and nitric acid pared to a polish made in the same way and from under the conditions of the treatment. Y the same ingredients but in which-the wax come . 2. The process in accordance with claim 1' in 45 ponent does not comprise a treating compound, which the treatment temperature is from about said polish also containing water as volatile dis 250° C. to 310° C’. V 7 a persion medium. ' 3. The process which comprises dispersing 10. A polish comprising, as wax ingredient the from 0.5% to 10% of a compound in an ester 'modi?ed wax product of claim 8. and manifest 7 type wax and heating the wax and treating com ing an increased hardness in its ?nal films, as ‘pound to ‘atemperature between about 100° C. 50 compared to a polish made in the ‘same way and ‘and the decomposition point of the wax 'for at from the same ingredients but in which the wax ‘least 30 minutes to modify the solubility of the component does not comprise a treating com. wax in organic solvents, which process is, char pound, said polish also containing an organic acterized in‘v that the treating compound em solvent as volatile dispersion medium. = ployed comprises an acidicinorganic residue and 55 3 an organic residue, said inorganic residue'being LASZLO AUER. capable of yielding an inorganic acid upon the