2,975,062 United States Patent Office Patented Mar. 14, 1961 1. 2 when the dilation at 20° C. is at least 1300 and the 2,975,062 softening point is not over 43 C. Because of the rela COMPOSTIONS CONTAINING COCOA-BUTTER tive cost of cocoa-butter and the substitute according to SUBSTITUTES the invention, a substitution of even 5% of the cocoa butter by the tallow fraction is useful and at such a Cornelis Johannes Soeters, Rotterdam, Netherlands, Her proportion the softening point of the substitute may be mann Pardun, Keve, Germany, and Antony Crossley, even higher than 43° C. Wallasey, and Stanley Paul, Prenton, Birkenhead, Eng The tallow fraction can be mixed with cocoa-butter land, assignors to Lever Brothers Company, New York, prior to incorporation in chocolate, and the invention N.Y., a corporation of Maine 0 accordingly includes mixtures of cocoa-butter and a frac No Drawing. Filed Oct. 29, 1956, Ser. No. 618,682 tion of mutton or beef tallow having the characteristics set out above. - Claims priority, application Great Britain Oct. 31, 955 In order to obtain the specified fraction from the tal 7 Claims. (CI, 99-118) low, it is essential to remove from the latter a substantial 15 low melting point fraction. It is also preferable, but not always necessary in the case of fractions to be used in This invention relates to cocoa-butter substitutes, to low proportion to cocoa-butter to remove a high melting processes for preparing the same and to products con point fraction. The yield of tallow fraction having the taining them. specified properties appears to be between 20 and 35%. The main use of cocoa-butter is in chocolate. In the 20 Roughly 35 to 55% of low melting fractions have to be manufacture of good quality chocolate, the "nib,” or removed from the tallow. The high melting fraction . decerticated cocoa bean, is ground and to it are added to be removed may be as much as 20 to 30%. sugar, flavourigs and additional cocoa-butter, together The fractionation of the tallow may be carried out by with milk powder in the case of milk chocolate. The crystallising fractionally in the presence of a solvent. amount of additional cocoa-butter depends upon the type 25 When only the lowest melting glycerides are to be re of chocolate and is usually between 25% and 100% of moved a single crystallisation may suffice, but it may the amount of cocoa-butter already present in the ground be advantageous to carry out the removal in two or more "nib.” The cocoa-butter content of such chocolate is crystallisations; similarly, when the highest and lowest largely responsible for its physical characteristics; cocoa melting glycerides are to be removed two or more crys butter is unusual among naturally-occurring fats in that 30 tallisations can be used. In the following description of it is normally a brittle solid to about 25 C., has a rela fractionation procedure, substantially anhydrous acetone .. tively narrow melting range and is almost completely is used as the solvent but other suitable solvents such as liquid at 35°C. ". . . ether and light petroleum may be used. Cocoa-butter is expensive. and many attempts have In order to remove the lowest melting glycerides in a been made to find a cheaper fat to substitute for at least 35 single crystallisation, an amount of acetone between 3 part of the cocoa-butter which is added to the ground and 10 mls. per gm. of fat can be used. The larger the "nib." In addition, attempts have been made to find a number of crystallisations or washes, the lower will be fat which can be used to make chocolate from partly or the ratio of acetone to fat that can be used. The tem completely defatted cocoa, perature of crystallisation depends-on the conditions used, The present invention is based on the discovery that 40 in particular the solvent ratio. With ratios of the order certain fractions obtained from mutton or beef tallow given and with a single crystallisation, a temperature of can be used as partial or complete substitutes for cocoa from -5° C. to about 10 C. may be used. butter in chocolate, and also in other products in which Various cooling procedures may be used. The tallo cocoa-butter is normally used, for example, couvertures may be dissolved in acetone at 25 C. or higher and then for confectionery. 45 the solution cooled to the desired temperature. The The present invention provides a process for preparing solution may be allowed to cool undisturbed, but the a cocoa-butter substitute which comprises fractionally time required is shortened considerably (20-30 minutes crystallizing mutton or beef tallow from a solvent to instead of many hours) if it is stirred throughout. Cool remove at least 35%, by weight of the tallow, of the ing may also be effected by distilling off part of the sol- - - , lowest melting glyceride fraction. 50 vent under reduced pressure. An alternative procedure The present invention also comprises a method of in to mix cold acetone with hot-tallow, the temperatures preparing products in which cocoa-butter is normally of these being such that the mixture is at the desired incorporated, characterised in that cocoa-butter is re crystallisation temperature. . . . . placed by a mutton or beef tallow fraction having an All crystallisations, are preferably left at the crystallisa iodine value within the range of about 28 to 40, pref 5 5 tion temperature until no further precipitation takes place. . . . - erably 28 to 35, and more particularly 28 to 33, a soften The precipitate may then be filtered off, preferably with ing point in the range of about 30 to 45° C., and pref the application of vacuum or pressure, and then washed,

erably not higher than 40 C., and a dilation at 20. C. of not less than 1200, and preferably not less than 1400. either on or after removal from the filter, with chilled More preferably, the dilation at 20° C. for the mutton 60tionacetone temperature. at a temperature 1-2 lower than the crystallisa or beef tallow fraction is not less than 1500. . . An alternative procedure which has been found The actual value of the dilation at 20° C. which the ticularly satisfactory is to draw off the mother. tallow fractions to be used according to the invention and washing liquids instead of filtering. In o should possess depends upon the desired quality of the product and the degree of replacement of cocoa-butter 65. obtain crystals in a suitable form for this procedur by the tallow fraction. When used to replace between coolingtallow-in-acetone commences solution and gentle should stirring be above should 40°C. be b 25 to 30% of the cocoa-butter in the final product useful out throughout cooling. Under these con results with mutton or beef tallow can be obtained when crystals settle rapidly and the mother liquor can be the dilation at -20°C. is at least 1400 and the softening off. The degree of removal of the lowes point not over 40 C. When even smaller proportions 70 glycerides from the solid crystals will depend or of substitute are used, for example, 10% of the total, number of washes, but normally 4-8 will be su. a useful results can be obtained with mutton or beef tallow . After each wash the acetone is drawn off and the acetone 2,975,062 3 4. used in washing can conveniently be used for the crystal 1.5 ml. of well boiled distilled water containing a little lisation of the next batch of tallow. A combination of blue ink is pipetted into the bulb of the dilatometer. The filtration and drawing off may conveniently be used. dilatometer is then weighed. A sample of the fat to be The tallow may be refined before or after fractionation. examined is thoroughly de-gassed by heating at 100 C. The removal of the highest melting glycerides may be 5 under vacuum. The fat (at about 60° C.) is then poured carried out by means of similar techniques. When a into the bulb of the dilatometer and the ground glass solvent is used, the ratio of acetone to tallow is pref stopper is inserted, care being taken not to include any erably in the range of 5-20 mis. per gm. of fat and air. The amount of fat added is such that, during the the crystallisation temperature in the range of 20 to determination, the level of water never falls below the 30 C. This can be carried out before or after the 10 lowest of the graduations and never rises above the top removal of the lowest melting glycerides, and may like of the graduations. If the initial water level on filling is wise be carried out as two or more separate crystallisa about two-thirds of the height of the graduated capillary, tions. these conditions are usually fulfilled. The dilatometer It has been found that the usefulness of the tallow is re-weighed to obtain the weight of fat added. The fractions specified can be increased by mixing them with 5 hollow stopper is then partly filled with lead shot. It a palm oil fraction having an iodine value not exceed is then placed in a water bath maintained at 60° C. ing 42, a softening point in the range of about 30° C. to (-0.1) and a reading of the level of the water in the 45 C., preferably not more than 43 C., and a dilatation capillary is made. This is the "base reading,' Rs. at 20° C. of not less than 1000. Preferably, the palm The filled dilatometer is chilled in an ice water bath oil fraction has an iodine value of 30 to 36, a soften 20 for 1/2 hours. It is then allowed to warm in an air ing point in the range of about 30° C. to 40° C., prefer bath to 26 C. at which temperature it is maintained for ably not more than 38 C., and a dilatation at 20° C. of 40 hours. It is then again chilled in an ice water bath not less than 1600, more preferably not less than 1700. for 1% hours and then placed in a water bath at 20° C. Such fractions are described in co-pending application (-0.1 C.), the dilatometer being immersed to such a Ser. No. 565,758, filed February 15, 1956, and now 25 depth that the water level is above the middle of the abandoned. ground glass stopper. The usefulness of the tallow fractions specified may The position of the water meniscus in the capillary also be increased by mixing them with a lard fraction is read every half hour until two successive readings having an iodine value within the range of about 25 to differ by no more than 2 mm.3. The final reading (R) 40, and preferably 30 to 40, a softening point in the 30 is used in the calculations. range of about 35° C. to 45° C., and a dilatation at 20 A similar procedure is adopted for each temperature C. of not less than 1200. Preferred lard fractions are it at which the dilatation is required. Thus R2, R25, those having a softening point of not less than 43 and R30 and R35 are successively determined. a dilatation at 20° C. of not less than 1500, more par Finally the dilatometer is heated again to 60° C. and ticularly those having a softening point within the range 35 the "base reading' is re-determined. If the initial and 35 to 40, and a dilatation of not less than 1800. final "base reading” differ by more than 2 mm., the whole The usefulness of the tallow fractions specified may also operation must be repeated. be increased by mixing them with both the above men-- The calculation: tioned palm oil fractions and the lard fractions. The value of the dilatation is calculated from the For the determination of dilatations for the purpose 40 following formula: of this specification, there are used a method and ap paratus similar to those given in Section C-IV, 3e (52) 25(Rio - R). A. of the "D.G.F. Einheitsmethoden,' published by the Deutsche Gesellschaft für Fettwissenschaft e.V. where In the melting of fats a characteristic change of volume 45 D=dilatation at t C. is observed which, especially in the case of fats solid W=weight of fat taken at the normal temperature, manifests itself in a sudden R60=base reading (mm.8) increase in the volume. R=reading of the capillary at t C. (mm.3), and The dilatation or isothermal melting expansion of a A is given in the table below: fat is the volume increase, which is expressed in mm.8, determined under the conditions of the following pro cedure and referred to 25 g., the reference temperature being given. The dilatometer is of glass and consists of a vertical graduated capillary tube joined at its lower end by a U-shaped capillary tube to a glass bulb surmounted by a neck which is internally ground to take a hollow ground glass stopper. The height (above the lowest point of The softening point is determined after stabilising the the U-shaped capillary) of the top of the graduated fat by a modification of the method published by Barni tube and the top of the mouth of the bulb are 350 mm. 60 coat in "The Analyst' 69, pages 176-178. In this modi and 70 mm., respectively. The graduations extend over fied method 0.5 ml. of mercury is placed in a lipped a length of 250 to 290 mm., and start 1 cm. from the 6 X 1 cm. test tube and the tube and contents chilled for upper end of the tube. The graduations are marked in 5 minutes in crushed ice and water. 1 ml. of fat melted intervals of 5 mm.8 (accurately calibrated) and cover at 100° C. is poured on to the mercury and the filled a total volume of 900 mm.3. The internal diameter of the tube allowed to stand in ice and water for 90 minutes. bulb is 20 mm. and it has a volume of 7 ml. (tolerance A% inch diameter ball bearing is placed in the depression -0.5 ml.). The internally ground neck of the bulb in the fat surface which forms when the fat is cooled. tapers downwards from an internal diameter of 15 mm. The fat in the tube is then stabilised in the same man to an internal diameter of 12 mm. and is 26 mm. long. ner as described for the dilatometer, allowing the tem The bulb of the instrument is thus below the level of the 70 perature to rise gradually to 26° C. and keeping it at graduations on the capillary tubing. The stopper to 26 C. for 40 hours. The tube is then attached to a be inserted in the mouth of the bulb is about 95 mm. thermometer graduated in A0 of a degree so that the in length (including the ground portion), and is hollow fat column is on a level with the thermometer bulb. This and is partly filled with lead shot to hold it firmly in is conveniently done by attaching a metal plate to the position while a dilatation is being determined, 75 thermometer, the plate having several holes in which 2,975,082 5 6 a tube or tubes may be suspended by the lip or lips. The stirring and then filtered through a Bichner funnel and thermometer and tube or tubes are immersed in a water the cake pressed and washed with 240 ml. of acetone at . . . bath equipped for stirring so that the tube or tubes are 22°C. on the funnel. The filtrate and wash liquor were immersed to a depth of 4.5 cms. The determination combined and the acetone removed by distillation under is commenced with the water bath at 20° C., at which vacuum. The yield was 155 g. of a fraction having an temperature it is maintained for 20 minutes. The tem .V. of 39.6. perature of the water bath is then raised at the rate of (c) 155 g. of the product of stage; (b) were mixed 0.5° C. per minute, whilst stirring vigorously. The tem with 930 ml. of acetone and the mixture warmed to 45° perature when the steel ball has fallen half way through C. The resultant solution was cooled to -2° C. whilst., the fat column is recorded as the softening point. (All 10 being gently stirred with a glass rod. It was allowed to references in this specification to softening points and stand for 15 minutes at -2° C. when the clear mother dilatations are to be construed as measured by the liquor was syphoned off. 700 ml. of acetone at 0° C. were methods described above.) then added and the mixture stirred for several minutes. The following examples illustrate the invention or the The mixture was allowed to stand for 30 minutes at 0° C. manufacture of fractions to be used according to the in 5 and then filtered through a cooled Bichner funnel with vention: vacuum. The cake was pressed and washed with 400 Example I ml. of acetone at 0° C. Residual acetone was removed (a) 800 g. of mutton tallow .V. 47.3 were mixed with from the cake by distillation under vacuum. The yield 3700 ml. of acetone and the mixture warmed to 45° C. was... 102 g. of a fraction having an I.V. of 30.9. The The solution was then cooled to -5° C. over 1 hour 20 dilatation at 20° C. and Barnicoat softening point of whilst being gently stirred with a glass rod. It was al the fraction were 1485 and 35.2° C. respectively. lowed to stand for 15 minutes at -5°C. and then filtered Example 3 through a cooled Bichner funnel with vacuum. The cake was pressed with a glass plunger and then washed with (a) 670 g. of mutton tallow I.V. 47.3 were mixed 1% litres of acetone at -5° C. The cake was then re 25 with 3350 ml. of acetone and the mixture warmed to moved from the filter and stirred for 10 minutes with 2 45 C. The solution was then cooled to 0° C. over litres of acetone at -5°C. It was then filtered through 1 hour whilst being gently stirred with a glass rod. It a Bichner funnel and the cake washed on the filter with was then allowed to stand for 15 minutes at 0° C. and 500 ml. of acetone at -5° C. Residual acetone was re then filtered through a cooled Bichner funnel with moved from the cake by distillation under vacuum. The 30 vacuum. The cake was pressed with a glass plunger and yield was 445 g. then washed with 1200 ml. of acetone at 0° C. The cake (b) 415 g. of the product of stage (a) were mixed with was then removed from the filter and stirred for 10 3 litres of acetone and the mixture warmed to 45° C. The minutes with 2300 ml. of acetone at 0° C. It was then resultant solution was cooled to 22° C. whilst gently filtered through a Bichner funnel and the cake washed stirring using a glass rod. It was allowed to stand at 35 on the filter with 1000 ml. of acetone at 0° C. Residual this temperature for 30 minutes with occasional stirring acetone was removed from the cake by distillation under. and then filtered through a Bichner funnel and the cake vacuum. The yield was 331 g. of a product having an pressed and washed on the funnel with 500 ml. of acetone I.V. of 26.7. at 22° C. The filtrate and wash liquor were combined (b) 309 g. of the product of stage (a) were mixed and the acetone removed by distillation under vacuum. 40 with 1850 ml. of acetone and the mixture warmed to 45° The yield was 237 g. of a fraction having an I.V. of C.. The resultant solution was cooled to 23°C, whilst 37.2. - gently stirring with a glass rod. It was allowed to stand (c) 174g. of the product of stage (b) were mixed at this temperature for 30 minutes with occasional stirring with 870 ml. of acetone and the mixture warmed to 45° and then filtered through a Bichner funnel and the cake C. The resultant solution was then cooled to '--3 C. 45 pressed and washed on the funnel with 200 ml. of acetone whilst being gently stirred with a glass rod. It was al at 23° C. The filtrate and wash liquor were combined lowed to stand for 15 minutes at -3° C. and then and the acetone removed by distillation under vacuum. filtered through a cooled Bichner funnel with vacuum. The yield was 173 g of a fraction having an I.V. of The cake was pressed and washed with 500 ml. of acetone 35.9. at 2 C., Residual acetone was removed from the cake 50 (c) 170 g of the product of stage (b) were mixed by distillation under vacuum. The yield was 148 g. with:1020 ml of acetone and the mixture warmed to 45° of a fraction having an I.V. of 34.1. The dilatation at C. The resultant solution was then cooled to 2 C, whilst 20 C. and Barnicoat softening point of the fraction . being gently stirred with a glass rod. It was then allowed were 1480 and 36.0° C. respectively. to stand for 15 minutes. at 2 C. and then filtered through 55 a cooled Büchner funnel with vacuum. The cake, was Example 2 then pressed and washed with two portions of 350 ml. (a) 550 g. of beef tallow I.V. 47.0 were mixed with acetone at 2. C. Residual acetone was removed from the 2750 ml. of acetone and the mixture warmed to 45 C. cake by distillation under vacuum. The yield was 116 g. The solution was then cooled to --2 C. over 45 minutes of a product having an I.V. of 31.5. The dilatation at whilst being gently stirred with a glass rod. It was al 60 20 C. and Barnicoat softening point of the fraction were lowed to stand for 15 minutes at --3 C. and then 1620 and 37.3° C. respectively. ". filtered through a cooled Bichner, funnel with vacuum. The cake was pressed and washed with 1 litre of acetone Example 4 at 0° C. I. The cake was then removed from the filter and (a) 650 g. of beef tallow I.V. 41.3 were mixed with stirred for 10 minutes with 1% litres of acetone at 0° C. 65 3900 ml. of acetone and the mixture warmed to 45° C. ' s: it was then filtered through a cooled Bichner funnel and The solution was then cooled to 0°C. over 1 hour whilst the cake washed on the filter with 500 ml. of acetone being gently stirred with a glass rod. It was then allowed at 0° C. Residual acetone was removed from the cake to stand for 15 minutes at 0° C. and then filtered through by distillation under vacuum. The yield was 250 g. of a cooled Bichner funnel with vacuum. The cake was a fraction having an I.V. of 31.0. 70 pressed with a glass plunger and then washed with 1000 (b) 241 g. of the product of stage (a) were mixed ml. of acetone at 0° C. The cake was then removed with 1450 ml. of acetone and the mixture warmed to 45 from the filter and stirred for 10 minutes with 1500 ml. C. The resultant solution was cooled to 22 C. whilst of acetone at 0°C. It was then filtered through a Büchner gently stirring using a glass rod. It was allowed to funnel and the cake washed on the filter with 1000 ml. stand at this temperature for 30 minutes with occasional 75 of acetone at 0°C. Residual acetone was removed from

2,975,062 7 8 the cake by distillation under vacuum. The yield was 2. The chocolate composition of claim 1 wherein the 293 g. fat phase additionally contains a minor amount of milk (b) 293 g. of the product of stage (a) were mixed fat. - with 1760 ml. of acetone and the mixture warmed to 3. A chocolate composition comprising decorticated 45 C. The resultant solution was cooled to 23 C. 5 cocoa bean, sugar and additional fat, the fat phase of the whilst gently stirring with a glass rod. It was allowed composition consisting essentially of cocoa-butter and a to stand at this temperature for 30 minutes with occasional tallow fraction obtained by removal from a tallow of stirring and then filtered through a Bichner funnel and the group consisting of mutton and beef tallow of from the cake pressed and washed on the funnel with 200 ml. about 35% to about 55% by weight of the lowest melt of acetone at 23° C. The filtrate and wash liquor were ing glyceride fraction, the tallow fraction being present combined and the acetone removed by distillation under in the mixture of cocoa-butter and tallow fraction at a vacuum. The yield was 167 g. of a fraction having an level of from 5% to 30% by weight of the mixture. I.V. of 31.1. The dilatation at 20° C. and Barnicoat 4. The chocolate composition of claim 3 wherein the softening point of the fraction were 1650 and 35.0° C. fat phase additionally contains a minor amount of milk respectively. 15 fat. Example 5 5. The product of claim 1 wherein the tallow fraction has an iodine value within the range 28 to 35, a soften Samples of plain chocolate were prepared from the ing point within the range 30 to 40 C., and a dilatation following formulae at 20° C. of not less than 1500. (i) 6. A fat composition for use in making chocolate and 400 g. plain "refiner paste" (containing 112 g. cocoa confectionery which consists essentially of a mixture of butter) cocoa-butter and a tallow fraction obtained from a tallow 39 g. additional cocoa-butter of the group consisting of mutton and beef tallow, said 27 g. mutton tallow fraction (I.V. 31.5, D20 1620, and fraction having an iodine value in the range of 28 to 40, Barnicoat softening point 37.3' C. prepared as in Ex 25 a softening point in the range of 30 to 45 C., and a dilatation at 20° C. of not less than 1200, and said tallow ample 3c) fraction being present in said mixture at a level of from (ii) 5% to 30% by weight of the mixture. 400 g. plain "refiner paste' (containing 112 g. cocoa 7. The fat composition of claim 6 in which the tallow butter) 30 fraction has an iodine value in the range of 28 to 35, 21 g. additional cocoa-butter a softening point in the range of 30° to 40 C., and 45 g. beef tallow fraction (I.V. 31.1, D20 1650, and a dilatation at 20° C. of not less than 1500. Barnicoat softening point 35.0° C. prepared as in Ex ample 4b) References Cited in the file of this patent The fat in Formula i contained 1.5 parts of mutton 35 UNITED STATES PATENTS tallow fraction per 8.5 parts of cocoa-butter and the fat in Formula ii contained 1 part of beef tallow fraction 2,468,799 Ziels ------May 31, 1949 per 3 parts of cocoa-butter. 2,586,615 Cross ------Feb. 19, 1952 The samples were satisfactory in appearance, taste, FOREIGN PATENTS melting and texture characteristics in the mouth and 40 on manual fracturing gave a characteristic "snap.' 590,916 Great Britain ------July 31, 1947 The tallow fractions were refined, bleached and de OTHER REFERENCES odorised before use. We claim: Riemenschneider et al.: “Oil and Soap,' 1946, pp. 1. A chocolate composition comprising decorticated 276 to 282. cocoa bean, sugar and additional fat, the fat phase of Lord: "Everybody's Cookbook," pp. 121 and 231. the composition consisting essentially of cocoa-butter and Copyright 1937 by Harcourt, Brace and Company, New a tallow fraction obtained from a tallow of the group York. consisting of mutton and beef tallow, said fraction hav Bailey: “Industrial Oil and Fat Products,” 2nd Ed., ing an iodine value within the range of 28 to 40, a 1951 (pp. 139 and 140). softening point within the range of 30 to 45 C., and Jensen: “The Chemistry, Flavoring and Manufacture a dilatation at 20° C. of not less than 1200, the said of Chocolate Confectionery and Cocoa,' pp. 190-192 tallow fraction being present at a level of from 5% to (2nd Edition), 1951. 30% by weight of the mixture of cocoa-butter and tallow fraction.