CA1194889A - Structural fat and method for making same - Google Patents

Abstract

Abstract A structural fat particularly suitable for margarines and other emulsified spreads, especially stick-type products is disclosed.
This fat has a unique triglyceride composition. The important positional isomers are the SSS, SOS, SSO-and SOO/SLS triglycerides, wherein S = saturated fatty acid residue, O = oleic acid residue and L = linoleic acid residue. The weight ratios of palmitic to stearic acid and oleic to linoleic acid residues attached to the glycerides are important. The fat can be obtained from a solventless two-step thermal fractionation of palm oil.

Description

8~
,~i .

: STRUCTURAL FAT
; AND METHOD FOR MAKING SAME
.

Michael W. Tafuri Bernard Y. Tao , ~ .
Technical Field - The present application relates to a structural ~at suitable for margarines and other water-in-oil emulsified spreads, especially : stick-type products.
'~ s Back~round Art Emulsified fat spreads, in particular margarines, desirably provide certain consumer benefits, usually in terms of the taste properties. One important consumer benefit of a spread is its moJth texture. Factors which contribute to mouth texture are cooling impact, mouthmelt, and mouthfeel (cleanup). A preferred emulsified spread provides a significant cooling impact, a rapid, sharp melt sensation, and no coated or waxy feel on the tongue. Another important consumer benefit is the temperature cycling stability of the spread. During normal usage, spreads such as margarines are repeatedly taken in and out of the refrigerator and are thus exposed - to a frequent cycle of warmer and colder temperatures. Also, during storage and shiprnent, the spread can be subjected to warmer and colder temperatures. Such temperature cycling can affect the properties of the spread, especially mouth texture. Preferred -~ 20 emulsi~ied spreads have temperature cycling stability, i.e. the ability to be taken in and out of the refrigerator without significant adYerse effects.
The spread should also satisfy certain consumer requirements in terms of the handling properties. The spread should be su-fficiently plastic to be easily spread on soft foods such as bread or toast.
Another important consurner requirement is heat stability or resistance to slump. The spread should not lose its shape (slump) ,, ",~

upon exposure to room temperatures while the spread is used.
Preferred emulsified spreads will maximize the bene~its o~ mouth texture and temperature cycling stability while at the same time satisfying the consumer requirements for spreadability and heat stability.
The emulsified spread normally used as the yardstick for all others, especially with regard to mouth texture, is butter. Butter has a particularly pleasing mouth texture. The cooling impact on the tongue is significant and the mouthmelt is rapid and sharp with lo no coated or waxy mouthfeel. The heat stability of butter is also adequate. However, refrigerated butter can become quite hard, and - there~ore difficult to spread, especially after temperature cycling.
To improve the spreadability of the emulsified spread ~hile approximatizing the mouth texture of butter, workers in the art have developed various margarines in stick and tub-type forms. Perhaps most important to the spreadability and mouth texture of a margarine is the margarine fat used. These margarine fats usually contain a sufficient solids content to provide heat stability to the margarine at room temperature yet have sufficient plasticity to be spreadable when re~rigerated. Such fats often contain a soft oil high in polyunsaturated ~atty acids (linoleic and linolenic) such as saf~lower oil or sunflower oil. Blends o~ ~ats and oils are frequently used in formulating such margarine fats.
ûne category of margarine fat contains triglycerides high in lauric acid content, such as coconut oil, palm kernel oil and oabassu oil. These triglyceride compositions are brittle at re~riyerator temperatures and have such low melting points (coconut oil melts at 75F (24C) to 80F (26.6C)) such that the ~preadaboility and heat stability o~ the margarine formed there~rom 3~ can be af~ected. See ~ailey's Industrial Oil and Fat Products (3rd ed. 1954), p. 339. Improvements in the spreadability and heat stability c~ margarines made ~rom high lauric acid content fats are achieved by appropriate blendiny with other ~ats and oils and interesteri~ication. See U.S. Patent 2,874,056 to Drew, issued FebxlJary 17, 1959 (margarine ~at containin~ coconut-type oil, ,. ..

-glycerides of higher fatty acids of coconut oil and glycerides of caprylic-capric-caproic acids); U.S. Patent 3,006,771 to Babayan, issued October 31, 1961 (margarine fat containing coconut-type oil modified with one or more triglycerides having fatty acids of from 6 to 10 carbon atoms which can be further interesterified ~ith - triglycerides haYing fatty acids of from 16 to 18 carbon atoms);
U.S. Patent 3,949,105 to Wieske et al, issued April 6, 1976 - (margarine fat containing interesterified blend of coconut oil, palm oil and hydrogenated oil). See also U.S. Patent 3,592,661 to Seiden, issued July 13, 1971 (margarine fat containing - interesterified trilaurin and tripalmitin).
~; Margarine fats can also be made ~rom triglycerides which have predominantly long chain length fatty acids (e.g. palmitic, stearic, oleic and/or linoleic acid residues). These long chain fatty acid - 15 triglycerides can be interesterified to provide margarine fats : having different melting profiles. See for example7 U.S. Patent Re 30,086 to Carlisle et al, issued August 28, 1979 (margarine fat consisting essentially of randomized palm oil); U.S. Patent 3,889,011 to Read, issued June 10, 1975 (margarine fat containing ~ 20 palm oil or cottonseed oil co-randomized with soybean or sunflo~Jer s oil); U.S. Patent 3,63~,100 to Fondu et al, issued January 11, 1972 (margarine ~at containing liquid oil such as sunflower or safflower oil, and co-randomized blend of coconut oil, palm oil and palm stearine); U.~. Patent 3,559,447 to SreeniYasan, issued January 7, 25 lg75 ~Margarine fat containing oils high in linoleic acid content such as sun~lower oil and safflower oil ~,Jhich have been interesterified). More typically, the long chain fatty acid ttriglyceride is a hydrogenated (hardened) oil. See Bailev's Industrial Oil ana Fat Products, supra, at page 33g. Hydrogenation 30 increases the solids content of the oil ~hioh raises the meJting point of the margarine fat, thus increasing the heat stability of t~argarlne. Other methods for increasing the heat stability of the margarine ha~/e also been practiced. See U.S. Patent 3,956,522 to ~attenberg et al, issued May 11, 1976 (margarine fat high in 3s polyunsatlJrated ~atty acid content containing hydrogenated hardstock A
. '~

't fat from which higher melting triglycerides have been remo~led b~J
fractionaticn).
Most commercial margarines are sufficiently plastic when refrigerated to have satisfactory spreadability properties and have sufficient solids content to provide heat stability at normal room temperatures. HoweYer, commercial margarines, especially those formulated from margarine fats containing hydrogenated oils, have mouthmelting properties which are flat or "thick" in character with a waxy or coated mouthfeel. Also, the temperature impact on the tongue does not provide a cooling sensation close to that of butter. Thus, while commercial margarines satisfy consumer requirements for spreadability and heat stability, they lack the mouth texture of butter.
~ingle fractionated or "topped" palm oil fats have been used in formulating margarine products to improve mouth texture. U.S.
Patent 3,189,465 to Oakley et al, issued June 15, 1965 relates to a "cool tasting" margarine wherein at least a major proportion of the fat phase consists of one or more lower melting fractions. These lower melting fractions can be obtained from semi-soft fats by single thermal fractionation in which the higher melting fraction containing substantially all the trisaturated glycerides is reMoved. A representative example of such a fat phase consists of about 60 to 70~ topped palm oil, about 15 to 25% lard (whole or topped~ ith the remaining Fat being ground nut oil. Margarines forrmJlated with topped palrn oil~ such as the liquld fraction from a sin~le thermal fraction of palm oil, do not satisfy the consumer - requirern~nts for heat stability in a stick-type product. Also, margarines made frorn topped palm oil are extremely brittle and difficult to spread. See also U.S. Patent 4,055,679 to Kattenberg et al, issued October 25, 1977 (plastic fat suitable fo~ margarines c~ntainin~ a palm based -fat such as palm olein co-randomized with ~ats such a5 soybean oil or sa~flower oil); U.S. Patent 4,0~7,564 to ,~
Poot et al, issued May 2, 197~ (olein fraction obtained by single thermal fraction o~ co-randomized blend of palm oil and soybean oil).

J

Double fractionated palm oil fats are also kno~n in the art but are used as cocoa butter substitutes and extenders. One example is - disclosed in U.S. Patent 4~205~095 to Pike et al, issued May 27~
1980~ ~hich relates to a thermal fraction method for producing a 5 palm mid-fraction suitable as a cocoa butter substitute or extender. Refined, bleached palm oil is heated (70-75C) and then in~ediately cooled (28-33C) to form a first liquid fraction (iodine value 55-60) and a first solid fraction (iadine Yalue 38-44 and melting point 50-55C). The first liquid fraction is separated, heated (60-65C) and then immediately cooled (14-17C) to produce a second liquid fraction (iodine value 59-64) and the desired palm mid-fraction (iodine value 48-53 and melting point 32-36C) ~hich is disclosed as having about 83% by ~eight symmetrical mono-unsaturated triglycerides and asymmetrical di-unsaturated triglycerides combined. The palm mid-fraction is separated and then hydrogenated to an iodine value of 38-45 to - provide a hydrogenated palm mid-fraction having a melting point of 33 -36 C .
Another such example is disclosed in British Patent Specification 827~172 to Best et al, published February 3~ 1960~
~hich relates to a method for making a cocoa butter substitute by a t~o-step solvent ~ractionation of palm oll. The palm mid-fraction used as the cocoa butter substitute has an iodine value of up to about 4~ (preferably 30-36) and a softening point of 30-45C
~ 25 ~pre~erably 32~-37C). ~his desired palm mid-fraction can be obtained by removing 5 to 15% of a high melting glyceride fraction containing ~ully saturated triglycerides and at least 50%
(~referably 60Yo) by ~eight of a lo~/ melting glyceride fraction.
3ritis~ Patent Specifications 1~431~781 to Padley et al, published 3r~ ~pril 14~ 1976~ and 1,390,g36 to ~oetters et al, published ~pril 16 1975~ ~Jhich blend such solvent fractionated palm rnid-fractions ~ith other ~ats to Porm cocoa butter e~tenders disclose one such palm rnid-fractiun having 3.1% trlsaturated triglycerides, 76.5~
s1rnMetrical mono-unsaturated triglycerides, 7.1Yo asymmetrical 3S rnono-lJnsaturatad triglycerides and ~.3Yo asymmetrical di-unsaturated triglycerides, with an iodine value of about 34 and a melting point - of about 33C. See also British Patent Specification 893,337 to Dansk Sojakagefabrik), published April 4, 1962 ~bloom inhibiting fat mixtures (melting range 31-43C) containing at least 65%
mono-unsaturated triglycerides obtained from double solvent fractionated shea butter and palm oil); U.S. Patent 3,012,891 to Best et al, issued December 12, lg61 (cocoa butter substitute formed ~rom blend of double solvent fractionated palm mid-fraction and - double solvent fractionated shea butter mid-fraction); U S. Patent -~ 10 2,903,363 to Farr, issued September 8, 1959 (cocoa butter-like fat having at least 75% mono-unsaturated triglycerides obtained by double solvent fractionation o~ palm oil); U.S. Patent 3,686,240 to Kawada et al, issued August 22, 1972, (cocoa butter substitute having a melting point of 33-38C formed from a hydrogenated palm 15 mid-fraction (iodine value of 38-47 and melting point of 27-31C~
obtained from double solvent fractionated palm oil).
It is an object o~ the present invention to provide a fat suitable as a structural fat for margarines or other emulsified spreads ~hich imparts a desirable mouth texture and temperature cycling stability.
It is another object of the present invention to provide a ~at suitable as a structural fat for margarines and other emulsified spreads ~hich lmparts satisfactory spreadability and heat stability, especially to stic~-type products.
It is another object o~ the present invention to provide a ~at suitable as a structural fat for margarines and other emulsified spreads ~Jhich imparts improved consumer benefits of mouth texture and ternperature cycling stabili'ry ~hile at the same tirne satisfying consurner requirernents ~or spreadability and heat stability.
It is yet a further ~bject of the present invention to provide a fat suitable as a structural ~at ~or rnargarines and othPr emulsified spreads ~hich can be obtained from double fractionated palm oil.
Tnese and further objects of the present application are hereina~ter disclosea.

Disclosure of the Invention This invention involves a novel fat which is particularly useful as a structural fat in margarines and other water-in-oil emulsified spreads, especially stick-type products. These emulsified spreads, can provide a desirable mouth texture in terms of cooling impact, mouthmelt and mouthfeel. These spreads can also have temperature cycling stability such that the spread can be taken in and out of the refrigerator repeatedly without significant adverse effects on the properties thereof, especially mouth texture. These spreads can also satisfy consumer requirements for spreadability, and heat stability (resistance to slump), especially in stick-type products.
In addition, these spreads can provide improved baking performance in the preparation of baked goods such as cakes.
The fat has aunique triglyceride composition in terms of positional isomers as measured by Argentation, Carbon Number Profile, and Fatty Acid Composition.
In terms of Argentation values, the fat has:
(a) from about 3 to about 9% by weight SSS triglycerides;
(b) from about 32 to about 50% by weight SOS triglycerides;
(c) from about 6 to about 12% by weight SSO triglycerides; and (d) from about 20 to about 32% by weight SOO/SLS triglycerides, wherein S = saturated C16 or C18 fatty acid residue, O =
oleic acid residue and L = linoleic acid residue.
In terms of Fatty Acid Composition, the by weight ration of P:St acid residues attached to the glycerides is about 8.5 or more while the by weight ratio of O;L acid residues is about 3.5 or more, wherein P = palmitic, St = stearic, O = oleic, and L = linoleic.
the fat has aunique melting profile, as measured by a Solid Fat Content of:
(a) from about 67 to about 80% at 50°F;
(b) from about 31 to about 58% at 70°F;
(c) from about 12 to about 39% at 80°F;
(d) from about 4 to about 18% at 92°F; and (e) about 7% or less at 105°F.

.~i, In terms of Carbon Number Profile, the fat has:
(a) from about 5 to about 1 æ by weight C48 triglycerides;
(b) from about 40 to about 55% by weight C50 triglycerides;
(c) from about 23 to about 35% by weight C52 triglycerides; and (d) from about 5 to about 10% by weight C54 triglycerides~
This fat can be obtained by a solventless, two-step thermal fractionation of palm oil. Whole palm oil (iodine value of from about 50 to about 55) is heated until essentially crystal free and then slowly cooled to a temperature of from about 75F to about 95F. After cooling, a first solid fraction (iodine value of from about 42 to about 47) forms or crystallizes and is separated from a first liquid fraction (iodine value of from about 56 to about 61).
This first liquid fraction is heated until essentially crystal free and then slowly cooled to a temperature of from about 50F to about 80F. After cooling, the desired second solid palm mid-fraction (iodine value of from about 39 to about 50) crystallizes (forms) ~nd is separated from a second liquid fraction.

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;', 8~39 -~ Definitions.
- The term "water-in-oil emulsion" refers to a composition characterized by dispersion of water as discrete droplets in a continuous oil phase.
The term "emulsified spread" refers to a solid or plastic water-in-oil emulsion. Such spreads can contain from about ~0% to about 90% margarine oil product.
The term "stick-type product" normally refers to an emulsified ; spread product in the form of a rectangular solid, usually having a length of about 5 inches and a cross-sectional thickness of 1-lJ4 inch square.
-~ The term "margarine" refers to an emulsified spread characterized by an oil phase of at least about 80~ by weight of the spread. Thus, margarines have an aqueous phase of up to about 2C~
by weight of the spread.
The term "low fat content spread" refers to an emulsified spread, other than a margarine. Low fat content spreads have an oil phase of less than about 80% by weight of the spread.
The term "fat" refers to a triglyceride composition charac-terized by a solid or plastic consistency at room temperatures, e.g.
at about 70F.
The term "oil" refers to a triglyceride composition characterized by a fluid or liquid consistency at room temperatures, -~ e.g. at about 70F.
The terms "margarine oil product" and "margarine fat" refer to the structural fat and soft oil blend used in the oil phase of an emulsified spread.
The term "structural fat" refers to the unique fat of this in~/ention which provides heat scability to the emulsified spread and stabilizes the emulsion.
The designations "SSS, 505 or SLS, SS0 and S00" refer to trisatura'ced, syrnmetrical mono-unsaturated, symmetrical ,~
diunsaturated, asyrnrnetrical mono-unsaturated and asymmetrical ~ di-unsaturated triylycerldes, respectively.
,,~ .

.~, 3, ~ 39 ;

The designations "C48, C50, C52 and C54" refer to the total number of carbon atoms of the combined fatty acid residues attached to the glyceride. Thus, a "C48 triglyceride" will yield on hydrolysis three fatty acid residues Nhich have a combined total of 48 carbon atoms.
- The designation-of fatty acids throughout the specifict~on are P = palmitic, St = stearic, 0 = oleic, L = linoleic, S = saturated fatty acid, U = unsaturated fatty acid, C16 ~atty aci~ is palmitic, C18 fatty acid is stearic. When S = C16 or C18, the - 10 triglyceride SSS can be tripalmitin, tristearin, 1,3-dipalmityl-stearin, 1,2-dipalmitylstearin, 1,3-distearylpalmitin or - 1,2-distearylpalmitin.
- Brief Description of the Drawinqs Figure 1 represents a flow diagram of a preferred method for making the structural fat of the present invention.
- Figure 2 represents a ~low diagram o~ methods for makingmargarines and other emulsified spreads of the present invention.
Figure 3 represents a sectional side view of the Hot Probe used : to measure the cooling impact o~ margarine products.
Figure 4 represents a typical Hot Probe curve of a margarine containing a structural fat of the present invention.
Figure 5 represents a sectional side view of the Instron and related apparatus used to measure the Shear Stress of margarine products.
Figure 6 represents a typical Shear Stress Force curve of a margarine containing a structural fat o~ the present invention.
Figures 7a throuqh 7i represent a Slurnp Chart used to evaluate the neat stability of maxgarlne products.
Structural Fat.
A. [~ o~ o '~
1~ Triql~/ceride Composition.
The structural fat of the present invention has a unique trigl~ceride coMpositi~n.
The triglyceride cornposition in terms of positlonal isomers can be determined b~J Ar~qentation thin la~er chrornatograph~J (hereafter ~ , :sj ;

~ Argentation). Argentation uses silver nitrate as a complexing ;l reagent in a chromatographic separation. The triglycerides separate according to the degree of unsaturation and the position of the fatty acid on the triglyceride molecule. However, chain length of the saturated fatty acids cannot be determined by this method. For example, Argentation can be used to distinguish SOS, SSO and SOS
- triglycerides, but cannot be used to distinguish POSt, POP, and -^~ StOSt triglycerides. The specific Argentation method used to determine the triglyceride composition of the structural fat of the present application is described under the section entitled "Analytical Methods for Determining Triglyceride Composition of Structural Fat".
From Argentation, it has been determined that the structural fat comprises:
(a) from about 3 to about 9% by weight SSS triglycerides;
(b) ~rom about 32 to about 50% by weight SOS triglycerides;
(c) from about 6 to about 12% by weight SSO triglycerides; and (d) from about 20 to about 32% by weight SOO/SLS triglycerides, - wherein S = saturated C16 or C18 fatty acid residue, O - oleic2~ acid residue and L = linoleic acid residue. Argentation also indicates that up to about 24% by weight other compounds mainly in the forrn of other positional isomer triglycerides (e.g. 000, OOL, SLL, SLO), plus mono- and di-glycerides, can be present in the struc'cural fat. Preferred structural fats for stick~type products have the following Aryentation values:

''I' Triql~/cerides % By Wei~ht SSS ~rom about 4 to about 7.0 SOS from about 35 to about ~6 SSO from about 7.7 to about 10.2 3~ SOO/SLS from about 23 to about 29~5 By ccmparison, cocoa butter and cocoa butter substitutes and e~tenders have higher levels (at least about 70-80% by weight) of SOS trl~lycerides.

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2. Fatty Acid Composition.
Anoth~r parameter used to define the triglyceride composition of the structural fat is the Fatty Acid Composition (hereafter FAC), especially the weight ratio of P:St acid residues attached to the glycerides and the weight ratio of O:L acid residues. The P:St ratio is about 8.5 or higher, and preferably ranges from about 9 to about 10. The O:L ratio is about 3.5 or higher, and preferably ranges from about 4 to about 5. By comparison, cocoa butter has an P:St ratio of at least about 1, and usually from 0 70 to 0.75.
The structural fat usually has an FAC of:
(a) from about 44 to about 55% by ~eight palmitic (P) acid residues;
- (b) from about 4.5 to about 5.5% by ~eight stearic (St) acid residues;
(c) from about 31 to about 40% by weight oleic (0) acid residues, (d) from about 6 to about 9.5% by weight linoleic (L) acid residues.
Up to about 3% by weight of other fatty acid residues (e.g.
myristic) can also be present. The FAC of preferred structural fats used for stick-type margarine products is as follo~s:

Fatty Acid % by ~Jeig~t palmitic (P) from about 47.5 to abouE 54 stearic (St) from about 4.5 to about 5.5 oleic (0) from about 34 to about 38 linoleic (L) from about 6.5 to about g.5 c The FAC for a particular triglyceride cornposition can be obtained by the method described under the section entitled "Methods for Determining Triglyceride Composition of Structural Fat."

3~ By combinin~ the results from Argentation, CNP and FAC the trigl~ceride composition of the structural fat can be obtained. It is belie~/ed that the predominant SOS and SSS triglycerides of the structural fat are 2 oleo-1,3-dipalmitan (POP) and tripalmitin , ,,~

(PPP), respectively. The unique triglyceride composition of this structural fat should be compared to that of typical cocoa t~utter and cocoa butter substitutes or extenders. The triglycerides of cocoa butter and cocoa butter substitutes or extenders are predominantly in the form of 2-oleo-1-stearin-3-palmitin (StCP) ' (about 40% by weight for cocoa butter) t~ith lesser amounts of- 2-oleo-1,3-distearin (St0St) and 2-oleo-1,3-dipalmitin (P0P) (cocoa butter has about 20% by weight of each).
- 3. Meltin~ Profile.
An important characteristic of the structural fat of the present application is its unique melting profile. The solids content of the fat at a particular temperature can be given in terms of a Solid Fat Content value (hereafter SFC value). An SFC value provides a reasonably accurate approximation of the percent by weight solids of the fat at a given temperature. By determining SFC values at a number of different temperatures, a melting profile of the fat ca~o be obtained. The fat of the present application can have an SFC of:
(a) from about 67 to about 80% at 50F (10C);
(b) from about 31 to about 58~ at 70F (21C);
(c) from about 12 to about 39% at 80F (26.6C);
(d) from about 4 to about 18% at 92F (33.3C); and , (e~ about 7% or less at 105F (40.5C).
Preferred structural fats for stick-type products have an SFC o~:
(a) from about 71 to about 77% at 50F (10C);
~5 (h) ~rom about 33 to about 48% at 70F (21C);
(c) from about 18 to about 28% at 80F (26.6C);
' (d) from about 6 to about 13% at 929F (33.3C); and (e) about 3% or less at 105F (40.5C).
~e~ore determininy SFC values, the fat sarnple is heated to a temperature o~ 158F or higher for at least 0.5 hours or until the sarrIple is completely melted. The melterJ sample is then terr~pered at a temperature of 40F for at least 72 hours. After tempering, the SFC value of the fat at a particular temperature can be determined pulsed nuclear magnetic resonance (PNMR). The method for determining SFC values of a fat b~ PNM~ is described in Madison and ,,~
'~'?

38~

~ill, J. Amer. Oil Chem. Soc., Vol. 55 (1978), pp. 328-31.

4. Carbon Nunber Profile.
Another parameter used to identify the triglyceride compositlon of the structural fat is its Carbon Number Profile (hereafter CNP).
The CNP indicates the percentage of triglycerides having a certain number of carbon atoms for the combined fatty acid residues attached to the glyceride. The structural fat has a CNP of:
(a) from about 5 to about 12% by weight C48 triglycerides;
(b) from about 40 to about 55% by weight C50 triglycerides;
(c) from about 23 to about 35% by weight C52 triglycerides; and (d) from about 5 to about 10% by weight C54 triglycèrides.
CNP also indicates that up to about 12% by weight other compounds mainly in the form of mono- and di-glycerides can be present in the structural fat. The CNP of preferred structural fats for stick-type products is as follows:

Caroon No. % bV Weiqht 48 from about 7.5 to about 9.5 5û from about 43 to about 50 52 from about 26 to about 33 ~0 54 from about 7 to about 9 rhe C~JP for a particular triglyceride compositlon can be obtained by the method described under the section entitled "Methods ~or Determining Triglyceride Cornposition of Structural Fat".

5~ Iodine Value.
rhe struckural ~at of the present invention has an lodine value Sherea~ter IY) in the range of from about 39 to about 50 and preferably from about 42 to about 4~. ~y comparison, cocoa butter and cocoa butter substitutes and extenders usually have an IV of abolJt 35 or less. The X`l of a fat or oil indicates the number of ; grams of iodine equivalent to halogen adsorbed by a 100 g. sample.
'J Because the halogen adsorbence is due to the double bonds present in -~ the fatty acid residues attached to the glycerides, the I\/ of a fat -~ or oil can give a general indication of solids content at a given temperature. As the fatty acid residues become more saturated, th2 . fat or oil increases in solids content. In general, the lower the IV of a given fat or oil, the greater will be the solids content at a given temperature. The IV of a fat or oil can be determined by A.O.C.S. Official Method Cd 1-25, known as the Wijs method.
lo 6. Methods for Determining Triglyceride Composition of Structural Fat.
a. Ar~entation - The positional isomer triglyceride composition of a fat can be determined by Argentation Thin Layer Chromatography. 20 cm. square, 15 250 micron layer thickness, silica gel H plates (Analtech, Newark, Del.) are sprayed with a 2.5% solution of silver nitrate until evenly wet. These plates are then activated in a forced-air oven for 60 minutes at 115~C and stored in a dark enclosure until cool.
Solutions of the individual fat samples are prepared at two - 20 concentrations (in chloroform): dilute (5.0 mg./ml.) to better quantitate the major glyceride components and concentrated (50 mg./ml.) to better quan'citate the trace components. Analytical standard solutions are prepared for spotting alongside the fat samples of interest. These standards contained equal amounts of 25 tristearin, oleo-distearin, dioleo palmitin, 2-oleo-l,~-distearin, - and 3-oleo-1,2-distearin, each at 1 mg./ml. concentration. Samples of each individual fat solution are then spotted at lO microg. and 100 microg. concentrations alongside analy-tical standards which are spotted at 1, 2, 4 and 8 microg~ for each component. A secondary 3~ standard of A~rican cocoa butter at concentrations the same as the f~t solution is also spotted. After the spotting solution solvent (chloroform) e~/aporates, the plates are ready for ~Jevelopment.
Each analyti~al plate is developed at room temperature in a dar~ened chamber with 85~ methylene chloride, 15% toluene, 0.1%
35 acetic acid developirlg solvent until the solvent reaches a i~

prescribed line (17 cm. from the origin). The developing solvent is allowed to evaporate in a forced nitrogen chamber for 10 rninut2s.
Each plate is then sprayed evenly with a 25% sulfuric acid solution and placed on a 21 cm. square by û.~ cm. thick aluminum 5 plate atop a hot plate. The plate is heated from 25~C to 2}DC over a period of 105 minutes.
After cooling to room temperature, the individual fat sam,ole is then quantitatively scanned versus the spotted standards in a Carnag " densitometer set at 6ûû nm. The individual scans are integrated by 0 a Spectraphysics SP-41ûû integrator and calibration curves are prepared from the spotted standards for quantitation purposes. At least 4 (usually 6) samples for each fat are used to determinc mean SSS, SOS, SS0 and S00/SLS triglyceride levels.
b. Carbon Number Profile.
The CNP of a particular triglyceride composition can be determined by programmed temperature-gas chromatngraphy using a short fused silica column coated with methyl silicone for analysis and characterization of the composition by molecular weight. The glycerides are separated according to their respective carbon numbers, wherein the carbon number defines the total number of carbon atorns on the combined fatty acid residues. The carbon atcms ' on the glycerol molecule are not counted. Glycerides with the same oarbon number will elute as the same peak. For exarrlple, a ;. triglyceride composed o~ three C16 (palmitic) fatty acid residues will co-elute with triglycerides made up of one C14 (myristic), one C16 and one Cl~ (stearic) fatty acid residue or with a triglyceride composed of two C14 fatty aci.d residues and one C2û (arachidic) fatty acid residue.
Preparation of the fat sample for analysis is as follows:
30 1.0 ml. o~ a tricaprin internal standard solution (2 mg./ml.) is pipetted into a vial. The methylene chloride solvent in the ~tandard solution is evaporated using a stearn hath under a nitrogen strearn. Two draps o~ the ~at sample (2û to 4û mg.) are pipetted into the vial. If the ~at sample is solid, it is melted on a stearn oath arld stirred well to insure a representatlYe sarnple~ 1.0 ml. of ~"~
,....

. . , , bis (trimethylsilyltrifluoroacetamide) (85TFA~ is pipetted into the vial which is then capped. The contents of the vial are shaken vigorously and then placed in a heating block (temperature of 100C) for about 5 minutes.
For determining the CNP of the prepared fat sample, a Hewlett-Packard 5880A series gas chromatograph equipped with temperature programming and a hydrogen flame ionization detector is used together with a He~lett-Packard 3351B data system, A 2 m.
- long, 0.22 mm. diameter fused silica capillary column coated with a 'chin layer of methyl silicone (Chrompak CP-SIL 5) is also used. The column is heated in an oven ~here temperature can be controlled and increased ~ccording to a specified pattern by the temperature prograr,uner. The hydrogen flame ionization detector is attached to - the outlet port of the colurnn. The signal generated by the detector is arnplified by an electrometer into a working input signal ~or the data system and recorder. The recorder prints out the gas i chromatograph curve and the data system electronically integrates the area under the curve. The following instrument conditions are used with the gas chromatograph:
Septum purge 1 ml./min.
Inlet pressure 5 psi Yent ~low 75 ml./min.
Makeup carrier 30 ml./min.
Hydrogen 30 ml~/min.
Air 400 ml./min.
1.0 microl, of the prepared ~at sample is taken by a gas-tight syringe and injected into the sample port of the gas chromatograph.
The coMponents in the sample port are warmed up to a temperature of 365C and swept by a helium carrier gas to push the components into 3~ the oolumn. The column temperature is initially set at 175C and held at this ternpera'cure ~or 0.5 minu'ces. The column is then heated up to a final temperature o~ 355C at a rate o~ 25C/min. The 'i column is malntained at the final temperature o~ 355C ~or an~ addltional 2 minutes.
.,, ,,~

8~9 . ~ .

., The chromatographic peaks generated are then identified and the peak areas measured. Peak identification is accomplished by -¦comparison to known pure glycerides previously programmed into the data system. The peak area as determined by the data system is used to calculate the percentage of glycerides having a particular Carbon Number (CN) according to the following equation:

I
%CN ~ (Area o~ CN/S) x 100 -1~herein S = sum of Area of CN for all peaks generated ;.:
.
-,The Area of CN is based upon the actual response generated by ',lo the chromatograph multiplied by a response factor for glycerides ~f -the particular Carbon Number. These response factors are determined by comparing the actual responses of a mixture of pure glycerides of various Carbon Numbers to the known amounts o~ each glyceride in the MiXture. A glyceride generating an actual response greater than its actual amount has a response factor less than 1.0; likewise, a glyceride generating a response less than that of its actual amount has a response factor o~ greater than 1Ø The mixture of glycer~des used ~in a methylene chloride solution) is as follows:

, . . .
Component Carbon No. Amount (mg./ml.
palmi'cic acid 16 0.5 , monopalmitin 16 0 5 monostearin 18 0 5 dipalmitin 32 0.5 palmitostearin 34 0.5 2~ distearin 36 0.5 tripalmitin 48 1.5 dipalmi'costearin 50 1.5 d~stearopalmitin 52 1.5 ~r~stearin 54 1~5 3~ c. ~ LYIaa ~ 9:
~ Thæ FP~ o~ a partlcular triglyceride composition can be "~

determined by gas chromatography performed on the corresponding methyl esters. The fatty acid residues attached to the glycerides are converted to the respective methyl esters and injected directly into the gas chromatograph where the components are separated by carbon atom chain length and degree o~ unsaturation. The peak areas for each methyl ester can be determined either graphically or electronically.
Prior to gas chromatographic analysis of the fat sample, the fatty acid residues attached to the glyceride are converted to the respective methyl esters. Fifty ml. of sodium methoxide reagent (3 g. of sodium per 1. of methanol) is added to 10-15 9. of the fat sample. This mixture is boiled with stirring for 3-5 minutes.
After boiling, 25 ml. of saturated NaCl-0.5% HCl solution is added to the mixture. After addition of the NaCl-HCl solution, 50 ml. of hexane is added. The mixture is then mixed and the hexane layer decanted through filter paper containing about 5 g. of anhydrous sodium sulfate. The filtered hexane is evaporated to obtain the methyl esters.
To determine the fAC o~ the prepared fat sample, a Hewlett-Packard 5712A series gas chromatograph equipped ~ith temperature programming and a thermal conductivity detector ls used together with a Hewlett-Packard 7123A recorder and a Hewlett-Packard 3351B
data system. A 10 ~t. long, 1/4 inch diameter stalnless steel column packed wlt ~ a preconditioned packing of 10% DEGS-PS on 100/120 Chrornosorb ~HP is also used. The column ls heated in an oven wnere temperature can be controlled. The thermal conductivity detector is attached to the outlet port o~ the column. The signal ger~rated by the detector is amplified by an electrometer into a "orking input signal ~or the data system and recorder. The recorder prin~s out the gas chromatograph curve and the data system electronically lntegrates the area under the curve.
The ~cllo~/ing instrument conditlons are used with the gas chromatograph:
De'ceotor 300C
~arrier gas Ylo~/ 60 ml./min.

~ - i 8~9 ...1 :.

One microl. of the prepared fat sample is taken by a gas-tight syringe and injected into the sample port of the gas chromatograph.
; The components in the sarnple port are warmed up to a temperature o~
300C and swept by a helium c æ rier gas to push the components into s the column. The column temperature is held at 215C.
-The chromatographic peaks generated are then identified and the peak areas measured. Peak identification is accomplished by comparison to known pure methyl esters previously programmed into th~ data system. The peak area as determined by the data system is used to determine the percentage of the particular fatty acid (CN) according to the following equation:
;.

% CN = (Area of CN) ( ~Molecular Weight of CN
S
wherein S = sum of (Area of CN) ( ~holecular Weight of CN) of all peaks generated B. Method for Makin~ Stru t_ al Fat.
A preferred method for obtaining the structural fat is by a solventless, two-step thermal fractionation of palm oil. Figure 1 20 represents a ~low diagram of this preferred method. Basically, palm oil is melted and then slowly cooled to produce a first solid ~raction which is then separated from a first liquid fraction. This ~ l~quid ~raction ls heated and then cooled to ~orm or crystallize a J desired second solid, palm mid-fraction which is then separated from 25 the second liquid fraction.
Referring more specifically to Figure 1, whole (unfractionated) palm oil (iodine value of from about 50 to about 55) is used as the starting material. This whole palm oil has preferably been re~ined and bleached ~RB), or re~ined, bleached and deodorized (R~D). The 30 w~ole palm oil is heated or mel~ed to insure an essentially cr~stal~ree homogeneous oil mixture. Heating to a temperature of at least about 1~0F, and typically withln a temperature range o~

,~
,",~

~,J~
88~
.~

; ~rom about 150F to about 170Ft ~or at least about 0.5 hours, : provides such a crystal-free mixture. During heating, the palm oil is typically agitated to make the mixture homogeneous.
- The heated palm oil is then slowly cooled, pre~erably under 5 gentle agitation, to a temperature of ~rom about 75F to about 95F
and more preferably-a temperature of from about 80F to about 85F.
The rate of cooling depends upon several factors such as the amount of palm oil, the amount of agitation and the diglyceride concentration in the palm oil. The cooling rate is usually about 20F./hr. or less, and preferably about 10F./hr. or less. The palm oil is maintained at this cooler temperature for a period of time sufficient to permit crystallization (or solidification) of a ~irst solid ~raction (stearine fraction) having an iodine value of from about 42 to about 47. The amount o~ time necessary to complete this ~irst separation depends upon various factors, including the configuration of the crystalizer, the rate at which the palm oil is cooled, the quantity o~ palm oil (larger quantities increase crystallization time), and the amount o~ agitation (which decreases crystallization time). For example, this ~irst crystallization is usually complete a~ter a holding time of at least about lû hours for smaller quan'cities o~ about 20 lbs. or less7 and at least about 48 hours ~or lar~qer quantities of about 100 lbs. or more. The first solid ~raction is then separated, usually by ~iltration (e.g. using a ~acuum drum ~ilter), ~rom a first liquid fraction (first olein ~raction) having an iodine value o~ from about 56 to about 61.
The separated ~irst liquid ~raction is then heated to insure an -' essentially crystal-~ree, homogeneous mixture. Usually, this first liquid ~raction is heated to a temperature o~ at least about 140F
and more typicallv to a temperature within the range of ~rom about 3~ 150F to about 170F, ~or at least about 0.5 hours to provide the crystal-~ree fnixture. Durinq heating, this ~irst liquid fraction is typicall~ agitated to make the mixture homogeneous.
The heated ~lrst llquid ~raction is then slowly cooled, pre~erably with gentle aqitation, to a temperature of from about ~OqF to about 80~F, and more pre~erably to a temperature Q~ ~rom "'Jl about 60°F to about 75°F. The rate of cooling of hte first liquid fraction is dependent upon the amount of agitation. The cooling rate is usually about 20°F/hr. or less, and more preferably about 10°F/hr. or less. The second solid fraction crystallizes or precipitates from the liquid phase.
In one embodiment of this second crystallization, the first liquid fraction is maintained at the cooler temperature for at least about 12 hours (preferably at least about 24 hours, more preferably at least about 48 hours for larger quantities of 100 lbs, or more) to permit complete crystallization or formation of the desired second solid fraction (palm mid-fraction) having an iodine value of from about 39 to about 50, and preferably from about 42 to about 48. This second solid fractionis then separated, usually by filtration (e.g. using a vacuum drum filter) and then centrifugation, from a second liquid fraction (second olein fraction) which has an iodine value of from about 58 to about 63.
It is particularly desirable to separate as much as possible of the second liquid fraction from the second solid fraction to provide preferred structural fats, especially for use in stick-type margarine products. This second solid fraction can be used (preferably after being deodorized) as the structural fat, or else can be blended with a minor amount of the second liquid fraction to vary the melting profile and triglyceride composition of the structural fat.
A second emboediment of this second crystallization involves temperature cycling wherein the first liquid fraction is held at the cooler temperature to crystallize out the second solid fraction with subsequent heating to enable better separation and yield of this solid fraction from the second liquid fraction. The particular conditions of temperature cycling can depend upon various factors, including the configuration and heat transfer characteristics of the crystallizer. For example, the first liquid fraction can be held at a temperature of from about 70°F to 80°F for at least about 5 hours )preferably at least about 24 hours for larger quantities of about 100 lbs. or more), cooled at a temperature of from about 55°F to 8~
. . , .

about 65F (preferably from about 55F to about 60F) for at least ~1 about 5 hours (preferably at least about 24 hours for larger quantities of about 100 lbs. or more) and then fairly slowly heated to and held at the original temperature range of from about 70~F to about 80F for at least about 5 hours (preferably at least about 24 hours for larger quantities of about 100 lbs. or more). A~ter this temperature cycling, the second solid fraction which crystallizes out is separated from the second liquid fraction as in the first embodiment.
-~ 10 Other methods can also be used to form the structural fat. One ~; such method involves blending a fat containing a high proportion of POP triglycerides with an oil containing a low proportion of such triglycerides. Examples of fats having high leYels of POP
triglycerides include Stillingia tallow, fats prepared according to - 15 Example II of U.S. Patent 3,808,245 to O'Connor et al, issued - April 30, 1974, and fats prepared according to Exanple II of U.S
Patent 3,809,711 to Yetter, issued May 7, 1974. Examples of oils low in POP triglycerides include the second liquid ~raction ~rom thermal fraction of palm oil. The fats and oils are blended so as to provide a structural ~at having the SFC, Argentation, C~P and FAC
-~ values previously defined in the section entitled "Composition of Structural Fat".
Margarines and Other Emulsified Spreads.
A. Composl'cion o~ Maruarine or Other Emulsified Spread.
1 Oil phase ingredients.
1 a. Marqarine_Oil Product.
- The main component o~ the oil phase is the margarine fat. In addition to the structural ~at7 the maryarine fat contains one or more soft oils. Suitable so~t oils have SFC values of:
(a) about 1% or less at 50F; and ~b) 0% at 70F.
The SFC ~/alues are determined by heating the soft oil to 14ûF for at least ZO minutes, temperlng the heated oil at 32F ~or at least 5 minutes~ ~urther tempering the so~t oil at 80F ~or at leas-t 30 3s minutes7 and measuring the sollds content o~ the tempered oil by , ,,,~ , 9~ 39 PNMR as in the case of the structural fat. Suitable soft oils can be derived from animal, vegetable or marine sourczs, including naturally occurring oils such as cottonseed oil, soybean oil, sunflower oil, corn oil, peanut oil, safflower oil, and the like.
Soft oils preferablv used are saf~lower oil, sun~lower oil, soybean s ~ oil and blends thereof. Soft oils high in solids content such as palm oil or hydrogenated soft oils usually need to be winterized to -~ provide suitable soft oils having the above de~ined SFC values.
Natural soybean oil has an IV which can vary from about 110 and about 150 with an average value of about 130. Soybean oil can be .'a' partially hydrogenated to prevent flavor deterioration caused by the ~ more highly unsaturated components such as the triglycerides having -' linolenic acid residues. The partial hydrogenation of soybean oil - can be achieved by any of a number of art recognized techniques, all of which involve contacting the oil with gaseous hydrogen in the presence of a catalyst such as nickel and/or copper. See, e.g.
Bailey's Industrial Oil and Fat Products, supra, pp. 793 et seqO
This partially hydrogenated soybean oil is winterized to remove solids to provide a so~t oil having an IV of from about 110 to about 115. See, e.g., ~ailey's Industrial Oil and Fat Products, supra, pp. 1007 et seq. ~or wlnterization techniques. It is also desirable that the so~t oil, e.g. partially hydrogenated and winterized soybean oil, be refined, bleached and deodorized in accordance with conventional practice. See, e.g., Baile~'s Industrial ûi]. and Fat Products, supra, pp. 719 et seq. and 897 et seq.
The structural ~at in an amount o~ ~rom about 35~ to about 70%
of the oil phase is blended with the so~t oil in an amount of ~rom a~out 3û% to about 65% by weight of the oil phase. The amount of structural ~at and soft oil used a~eots the physieal properties in t~e spread. Increased levels o~ so~t oil impart better cooling impact and spreadability to the spread. Increased levels of structural ~ak impart better heat stability to the spread. Tub-type spreads typically have hlgher levels o~ soft oil while stick-type spreads typically have higher levels o~ structlJral fat.

,...

.
81~9 For stick-type spreads, the structural fat in an amount of from about 35% to about 70% by weight of the oil phase is blended with the soft oil in an amount of from about 30 to about 65% by weight of the oil phase. More typically, the amount of structural fat ranges from about ~0 to about 55% by weight while the amount of soft oil ~ ranges from about 45 to about 60% by weight. Margarine oil products for stick-type spreads have SFC values of:
(a) from about 17% to about 54% at 50F;
(b) ~rom about 6% to about 33% at 70F;
(c) ~rom about 4% to about 16% at 8ûF;
-~ (d) from about 2% to about 7.5% at 92F; and . ...
- (e) less than 2% at 105F.
Margarine oil products having much lo~er SFC values normally have insufficient heat stability. By contrast, margarine oil products having much higher SFC values normally have too little mouth cooling impact, especially upon temperature cycling.
The palmitic to s-tearic acid weight ratio o~ the margarine fat ranges from about 3.4 to about 7.5. The oleic to linoleic acid weight ratio ranges ~rom about 0.4 to about 2.2 The exact value is dependent on the particular soft oil used.
- eesides the structural ~at and soft oil, the margarine oil product can include minor amounts of other fats and oils. Soft oils ; which have high solids content are included within the term "other fats and oils". Examples of such fats and oils include palm oil and lnteresteri~ied oils or blends of various oils, either by random or directed interesteri~ication. Examples of oils which can be interesterified either alone or by appropriate blending are palm oil, sunflowsr oil and saf~lower oil. Fats or oils high in lauric acid, such as hydrogenated or unhydroyenated coconut oil, palm kernel oil and babassu oil, are usually lncluded only in tub-type ,~

,"~ , products due to the decreased heat stability of the spread;
hydrogenated hardstocks such as blends of rapeseed and soybean hardstocks are usually not included due to the decreased mouth cooling impact of the spread. These other fats and oils, either s alone or by appropriate blending, can be included in the nargarine fat in various amounts depending upon the properties desired in the spread. Normally, these other fats and oils are included in amounts of about 15% by weight or less and more typically in amounts of about 6% by weight or less.
b. Other oil phase inqredients.
Other ingredients can be presented in the oil phase. One particularly important ingredient is the emulsifier. Emulsifiers which can ~e used include mono- and d~-glycerides twater-in-oil stabilizers and baking aids), lecithin (oil in-water stabilizer, as well as anti-stick and anti-spatt~ agent), an~ polyoxyethylene sorbitan monoesters such as ~WEEN 60 and T~EEN~û (oil-in-water stabilizers). Other conventional emulsifiers can also be used. The emulsi~iers are added in amounts of from about 0.01 to about 10% by weight o~ the spread, and preferably in an amsunt of from about 0.1 ~0 to about 0.5% by weight. Coloring agents such as beta-carotene and oil soluble ~lavors can be in the oil phase. The amount of colors and ~la~/ors depends upon the color and flavor characteristics desired and is within the skill of 'che art.
2 ~queous phase in~redients Th~ aqueous phase u~ually contains milk or milk solids. The mllk ccmponen'c can be derived Yrom whole milk, low-fat milk (about 2~ butterfat content), sk~m milk or non~at dry milk solids. Tne amount of milk and/or milk solids (in terms o~ % by weight solids) usuaily ranges from about û.5 to about 5% by weight o~ the emulsified spread, and more typically from about l to about 3% by wei~h~. Particularly where milk solids are used, water, typically in the ~orm o~ distllled or deionlzed water, is included as part of the aque4us phase~ For a non-browning sp~ead, the milk solids or reCuclng sugars in them are eliminated.

.~ 9az88~

--0-ther ingredients included within the aqueous phase are ~, flavorants such as salt and other water-soluble fla~/ors. Usually, salt is included in an amount of from about 0.5 to about ~.5~ by weight of the emulsified spread, and more typically in an amount of ~rom about 1 to about 2.5% by weight. The amount of the other ~d, water-soluble flavors depends upon the particular ~lavor characteristics desired.
-, Another important component of the aqueous phase are the preservatives, for example, citric acid, potassium sorbate and -~ lo sodium benzoate. The preservatives are added in amounts effective -~g to prevent oxidation, bacterial and mold growth.
a B. Methods for making margarines and other emulsified spreads.
~- Methods for making margarines and other emulsified spreads according to the present invention are shown in the flow diagram lS presented in Figure 2. These methods involve blending the aqueous ' and oil phase ingredients and then chilling this mixture in a scraped-wall heat exchanger known as an A unit. After chilling, the emulsion is further crystallized in what is known as a B unit. The ~ crystallized emulsion, with or without ~urther chilling and - 20 crystallization in other A and B units, is packed and then tempered to provide a margarine, or other emulsified spread, having the desired properties. ~Ihile the flow diagram in Figure 2 shows several methods for ~orming rnargarines and other ernulsified spreads according to the present application, other variations of A and B
~ 25 units and processing conditions can be employed depending upon the -,; properties desired.
Re~erring rnore speci~ically to Figure 2, the aqueous and oil phase ingredients can be ~ormulated in separate mix tanks. The ~ormulations Frorn these mix tanks are rnetered out and the aqueous 3~ phase disperser~ in the melter~ oil phase. X~ desired, the aqueous phase containing milk/milk solids can be dispersed in the oil phase 'A, ar,d then the color, ~lavors and emulsifiers subsequently dispersed in this emlJlsion. This melted dispersion is t.hen sent through one or more scraped-wall heat exchangers kno~/n as A units. rhese A
units usually corlsist o~ a steel sha~t rotating in a tube which is ~, 8~
, ., cooled externally by liquid ammonia or brine or other refriserant.
-- The rotating shaft is fitted with scraper blades which at high rotation speeds are pressed against the cooled inner sur~ace. The - high internal pressures and chilling action induce nucleation and crystallization of the emulsion in the A unit.
~ The rotator speed of the A unit usually ranges from about 100 to about 500 rpm. The emulsion is discharged from the A unit at a temperature of from about 15F to about 6ûF. The hardness of the ultimately formed spread normally decreases as the emulsion is chilled to lower temperaturess~ The particular temperature to which , the emulsion is chilled also depends upon the form of product. For the stick-type products of this invention, the trmperature is from about 15F to about 45F, and preferably from about 20F to about 35F. Total residence time ~ithin the A unit or units is at least about 0.5 minutes and usually ranges from about 0.5 to about 2 minutes. Residence time ~ithin the A unit can be calculated by dividing the volume o~ the unit by the flo~ rate of the emulsion through the unit. Up to three A units are typically used to chill the ennulsion.
2~ The chilled ernulsion from the A unit or units is then sent to a ~!~ cryst~llizer kno~n as a B unit. As shown in Figure 2, the B unit can be either a s~atic B unit or a ~orking B unit. In the case of a static e unit, the crystallizer is usually in the form of` a hollo~J
pipe or resting tube, or else in the f'orm of a motionless mixer.
2$ For a ~/orking B unit, t~e crystallizer is usually in the form of a ''~ picker box. A picker box typically consists of a large diameter tube ha~lng stator p~ns on the inner cylinder ~lall and a rotating sha~t fitted ~Jith rotor pins. The combination of stator and rotor pins tnechanically ~/ork the fat as it passes throush the B unit so as 3~ to break up the ~at crystals. The rotor usually rotates at speeds of 7rom about lûO to about 1500 rpm.
'~ For either a ~lorkin~ or static a unit, the residence time of` the emulslon (calculated as in the A units) is at least about 3 minutes f'or stick-type prorJucts. More typically, the residence time is from '~S abolJ~ 3 to a~out 5 rninutes. For a working B unit, crystallization .~
~'1 ~; l : and work adds from about 10F to about 25F to the temperature of -` the emulsion. For a static B unit, crystallization adds from about - lûF to about 20F to the temperature of the emulsion.
- The crystallized emulsion is then either packed or else sent through an additional A unit or units to further chill the crystallized emulsion. When sent through this additional A unit or units, the crystallized emulsion is discharged at a temperature o~
-~ from about 15F to about 40F. For stick-type products, the temperature is from about 15F to about 40~F, and more preferably from about 20F to about 25F. Total residence time within this additional A unit or units is at least about 0.2 minutes and usually ranges from about û.2 to about 1 minutes. The chilled crystallized emulsion discharged from the additional A unit or units can either be packed or else sent through a static B unit (when previously ~ crystallized in a working B unit) to provide additional - crystallization time.
A~ter crystallization, with or without further chilling7 the margarine (or other emulsified spread) is then packed in either stick or tub ~orm. The ~orm in which the margarine is packed will frequently depend on how much the emulsion has previously been ~lorked in the B units. For stick-type products, the margarine either can be extruded or molded into bars by techniques well known in the Margarine art. The packed margarine is usually tempered at a temperat~Jre o~ from about 3ûF to about 50~F for at least about 24 hours.
;~ t~ethods for ~easurin~ Properties of Margarine Products.
A. Mouth Texture.
....
rhe mouth texture o~ a margarine in terms of cooling impact can be measured by use o~ a Hot Probe (HP) te~st. The instrument used to conduct the ~P tes~ ls knot~n as a Hot Probe and is sho~tln as 10 in Figure 3. Probe 10 conslsts baslcally of a sensing head 14, a ~ r,on-thermally conducting body in the form of 1 in. diameter plastic ",~
cylindrical tube 1~ and a thermocouple 22. The tip of thermocouple 22 is imbedded in the sensing head 14 which conslsts of' a 3/4 in.
diatnfter copper ring 26 ~illed t/ith lead solder 30. The thickness .~
, ~948B9 --~o-of solder 30 inside ring 26 is 5/32 in. The tip of thermocouple 22 is buried within solder 26 to a depth of 3/32 in.
To fabricate probe 10, thermocouple 22 is held in place by cork 34 while the reservoir created by the end of plastic tu~e 18 and ring 26 is filled with molten solder 30. When the solder solidifies, the tip of the thermocouple is permanently imbedded within it. The exposed surface of the solidified solder ls filed smooth. Teflon~tape (not shown) is wrapped over ring 26 and tube 18 to offer additional support. A weight 38 is added to the top of probe 10 to provide a total weight for the probe of 600 9. This particular weight was chosen so as to insure adequate contact between the probe and the margarine sample. The probe is supported by a brass pipe collar 42 of sufficient inside diameter to permit free movement of tube 18 while preventing lateral shifting. This collar 42 is held vertically in place by a ring stand (not shown) "hen probe 10 is ready for testing a margarine sample.
The HP test indicates the cooling effect in the mouth that occurs ~hen a cool ma2garine (40F~ is placed in contact with the tongue. Sensing head 14 of the probe is warmed to a temperature to approximate that o~ the mouth (95f~ and then placed in contact with cool sarnple pad o~ the margarine. The cool pad causes the tempera'cure of sensing head 14 to decrease over time. This terrperature dzcrease is sensed by thermocouple 22 and then recorded on chart paper o~ a recorder as a Hot Probe curve. This curve in~lcates the rate of heat lsss from probe 10 to the sample pad.
Tn carrying out the HP test, sample pads fram the margarine are form~d. Sample preparation is done in a 40F constant temperature roan so tha'c the margarine does not melt. Samples ~or HP testing are in the form o~ 1-1/4 in. square by 1/4 in. thick pads. The pads are cut wlth a stlck cutter or a thin wire "cheese cutter". The cut pads are put in a sguare plastic petri dish and submerged in a 40F
~laterbath to lnsure therMal equillibrium.
~ e~sre ~he s~nplf oad~ are tested, probe 10 is calibrated.
T~ermocouple 22 ls connected to a chart recorder (Sargent-Welch 35 ll,odel ~o. ~KR or equi-~alent). Probe 10 is then submerged in a ~ waterbath which is at a temperature of 7ûF as determined by a -:~ thermometer. ~hile stirring -the bath, the pen of the recorder is zeroed to the proper position on the chart paper. This procedure is repeated in a waterbath having a temperature of lû~F, as determined ~ 5 by a thermometer. The variable span control is used to adjust the ^~ pen of the recorder to the proper position on the chart paper. This procedure is repeated until the recorder indicates the proper - position on the chart paper of both the 70F and 100F baths with no further adjusting.
- 10 The HP test is performed by first removing the sample pad from the 40F bath and drying the pad off using a paper towel. The dry pad is then placed on the ring stand base below probe 10. The probe is submerged in a 12ûF waterbath until its temperature is approximately 100F as indicated by the recorder. The probe is t'nen dried and inserted within collar 42 directly above the sample patl.
~hen the recorder indicates 95F (chosen to approximate mouth temperature), the sensing head 14 of the probe is gently placed in - contact ~ith the pad to initiate the HP test. The entire HP test is conducted in a 70F constant temperature room. The temperature decrease over time of the sensing head is measured on the chart - paper of the recorder as a Hot Probe curve.
A typical Hot Probe curve 50 for a margarine made with a structural ~at of the present application is shown in Figure 4.
Point 54 on curve 50 represents the time at which the sensing head 14 of the probe ~as brought into contact ~ith the pad. The distance from point 54 to point 58 along line 62 (95F) represents a 6 second tlme inter~/al. Line 66, perpendicular from line 62 to curve 50, represents the teMperature drop during the 6 second interval, in this case 14F. Such Hot Probe values for 4 pads of each margarine 3~ are averaged to give a more representative indication of cooling impact A Hot Probe value of greater than 11.3F/6 sec. normally indicates a signi~icant benefit in terms of cooling impact, preferably the value is 13 to 17.
~rhe probe lrJ can be calibrated by determining Hot Probe values for distilled ~t/ater (~later standard~ and refined, bleached, deodorized and winterized soybean oil (oil standard). The probe is heated to 95F as previously described and then immersed about 1/8 of an inch deep into a 40F bath o~ the particular standard. The Hot Probe values for the water an~ oil standards should be 19.4F/6 sec. and 9.8F/6 szc., respectively.
B. Spreadabilitv.
The spreadability of margarine products in terms of hardness can be measured by a s~ear stress (SS) test. The device used in the SS
test is an Instron Universal Testing Machine tModel No. TMS) shown generally in Figure 5 as 70. Instron 70 consists basically of a vertically movable cross head 78 and a 200 lb. compression load cell 82 (for measuring the force generated) mounted on base 84 of the Instron. Cross head 78 drives unconnected cylindrical punch 74 whlch is received by rectangular fixture 88. This fixture 88 has a cylindrical bore in the form of punch guide 92 for slidable movement of punch 74. A test chamber 96 is also formed in fixture a8 for receiving the sample pad S to be tested. Fixture 88 also has a cylindrical bore in the ~orm of die 100 over which sample S sits.
The entire ~ixture 88 sits on load plate 104 of' load cell 82.
The SS test measures the hardness of the margarine and thus is an indication 3~ ~ts spreadability. The downward movement of crosshead 78 pushes punch 74 against sample pad S. Pad S is put under shear jointly by the action of the tip of punch 74, and dl~ l~r~ o~ ure 8~. Load cell 82 measures the ~orce required to Z5 purch throu~h pad S and records it as a force curve on chart paper o~ a recorder, The Shear Stress value o~ pad S is then calculated ~rom thi.s force curYe.
In carrylng out the SS test, sample pads from the margarine are forrned. For stick-type products, sample pads 1/4 in. thick by 1-1/4 in, square are cut using a thin wire cutter. The cut pads are then equilibrated at ~0F by submergence in a constant temperature waterbath ~or at least 1 hour. For tub type products, the product is gen~ly removed ~rom the tub and then cut into sticks having a 1-1/~ in. sq. cross sectlon ~ith a wire eutter. These sticks are 3~ then cut into sarnple pads in the same mannPr as the stick-type products.

8~39 , .

The SS test is conducted by placing sample pad S in test chamber 't 96 of fixture 88. Sample pad S is centered over die 100 of fixture 88. Fixture 88 with pad S is then placed on load plat? 104 of load cell 82 and the load cell is then tarred. The full force scale of the Instron is then calibrated by placing a known weight on load plate 104 of load cell 82 along with fixture 88 and pad S. The scale is set to provide maximum resolution for a given sample pad, - usually 5 lbs. full scale. The Instron is then set at a cross head speed of 10 ipm and a chart speed of 10 ipm. The upper and lower lû limits of cross head 78 are set to determine the penetration depth -~ and the return height, respectively. The SS test is initiated by bringing cross head 78 into its downward motion which pushes punch 74 through sample pad S. The chart paper of the recorder moves in concert with cross head 78 ~lith the pen recording the Shear Stre,s force curve of the penetration.
- A typical Shear Stress force curve 108 for a margarine made with the structural fat of the present application is shown in Figure 6.
The height of curve 108 from the base thereof to the tip 112 indicates the amount of force (F) applied to the sample pad during the SS test, in this case about 1.~ lbs. The F values for 4 sample pads of the margarine are averaged for a representative indication of the amount of hardness. The shear stress value, S5, is calculated by using the following formula:
"~
~', j. S5 = F/(7r DT) wherein D = diameter of punch 74 and T = thickness cf the sample pad ~ecause D - 0.5 in. and T = û.25 in., the above formula reduces j~ to the follo~f/ing: Ss = 2.55 F
-- An Ss value of about 12 psi or less at 40F (based on the ,s ~ 30 hardness of butter) lndicates a rnargarine having acceptable hardness.

,~
" , 48~
.

. C. Heat Stability.
- The heat stability of a margarine, in particular a stick-type product, can be determined by a Slump Grade ~SG) test. The SG test measures, by visual inspection, the deformation of a sample due to ~ 5 melting when exposed to a warm environment (80F). At a speci~ied -~ time, the sample is compared to a Slump Chart (Figures 7a through 7i) to determine the Slump Grade.
_ The SG cest is conducted by first preparing samples in the form - of l-l/4 in. cubes from margarines which have been stored in a 40F
constant temperature room for at least 1 day. These samples are cut from the margarine by using a thin wire cutting device. The sample cubes are equilibrated to 4ûF.
The sample cube is then placed in an 80F constant temperature room. Visual deformation measurements are taken at 30 minutes, 45 15 minutes and l hour. Deformation of the sample cube is determined by comparison to the Slump Chart shown in Figures 7a through 7i. A
grade of lO is the highest and represents no melting. A grade of 9 (Figure 7a) represents the first indication of melting, while a grade of O (Figure 7i) represents a completely melted sample cube.
s 20 The S1UMP Grades of 3 sample cubes are averaged For each margarine to give a more representative measure of heat stability. A Slump Grade of about 8 or better (based on consumer testing) at 8ûF for l hour indicates a rnargarine having acceptable heat stability for a stick-type product.
25 D Temperature C~/cling Stability~
;~; Temperature cycling is the exposure of a margarine to a tempera Wre higher than the norma]. storage temperature for a speci~ied period one or more consecutive times. The temperature cycling stability of the margarine can be measured by evaluating the 30 mouth texture, spreadability and heat stability thereof after cyclin~. Stick-type margarine products are initially stored at a ;~ temperature of 4ûF. On three consecutive days, the margarine is placed in an environment of 70f for 2 hours and then returned to the /~O~F environmerlt. ~hese conditlons ~ere selected to approximate 35 temperature cyclin~ by the consurner. After this teMperature ~"tJ
, cycling, sample pads or cubes of the margarine are evaluated by the preceding HP, SS and SG tests. Hot Probe, Shear Stress and Slump Grade (for stick-type products) values satisfying the previously mentioned criteria after cycling of the margarine indicate a significant benefit in terms of temperature cycling stability.
Effects of Different Structural Fats, Different Levels of Structural Fat, Different Soft Oils, and Addition of Minor Amounts of Other Fats and Oils on Prperties of Margarine Products.
A. Structural Fats The effects of different structural fats on the properties of margarine products were evaluated. The characteristics of three palm mid-fractions (PMF-1 to PMF-3) used as the structural fats in terms of SFC, Argentation, CNP and FAC values are as follows:
(continued) L ;~

-~ Linoleic 7.2 8.1 8.9 Other 2.7 1.6 1.6 ''' The margarine fat basically consisted of the Palm Mid-Fractions - and soybean oil. The margarines were formulated under similar processing conditions. The properties of these margarines (age of 10 to 17 days) are presented in the following Table:

,, Uncycled Structural Hot Probe 40 Shear Stress 80 Slump Fat* (F/6 sec.)(psi)Grade (at 1 hr.) 46% PMF-l 17.4 5.5 7.8 42.5% PMF-2 14.6 4.8 9.5 42.5% PMF-3 18.1 4.0 9.5 Cvcled 46% PMF-l 13.4 6.2 9.7 42.5% PMF-2 12.5 4.1 10**
42.5% PMF-3 16.1 3.6 8.5 *Percentages are by weight of oil phase.
**Age o~ 24 days.

As can be seen from the above Table, margarines formulated frorn all o~ the palm mid-fractions had signi~icant cooling impact (Hot Probe), an acceptable hardness (Shear Stress), and sufficient heat s'cability (Slump Grade) ~or stick-type products, even after temperature cycling.
B. Structural Fat Levels.
The e~fects of different levels of structural ~at on the properties of margarine products were evalua'ced. The margarine fat - basically consisted of a structural ~at o~ the present application (P~F-l) at various levels with the remainder of the margarine fat consisting o~ soybean oil. The margarines were formulated under ~ 30 similar processing conditions. The properties of these margarines -~ (age o~ 10 days) are presented in the ~ollowing Table:
.~

',''~

, 7 ~ ~. : . J

38~

Uncycled PMF Hot Probe 40~ Shear Stress 80 Slump Level (%)* (F/6 sec.) (psi) Grade (at 1 hr.) 19 - 18.7** 1.3 0 , i, 31 16.7 3.8 4.0 - 46 17.4 5.5 7.8 -~ 75 13 . 8 11 . O 10 CYcled 19 14.4** 1.3 0 31 15.3 3.7 5.0 46 13.4 6.2 9.7 10.2 16.rJ 10 *Percentages are by weight of oil phase.
: **HP test performed without weight.
. .
- 15 As shoYIn by the above Table~ margarines formulated with PMF-l at ~` levels of 31~o by weight or lower had insufficient heat stability (Slump Grade) ~or stick-type products. As also shown by the above ~ Table, the marrJarine formulated with PMF-l at a level of 75~ by '~ weight had insu~ficient cooling impact (Hot Probe) and unacceptable hardness (Shear Stress) a~ter temperature cycling. It is to be understood that the amounts of structural ~at and soft oil which can be blended together to formulate margarines having significant cooling irnpact, acceptable hardness and suf~icient heat stability, everl after cycling, can depend upon the melting profile (SFC) and triglyceride csmposition (Argentation, CNP and FAC) of the particular struc'cural ~at as ~lell as the particular margarine ;~ processing conditions.
'''7 C. So~t O~ls.
The effects of di~erent 50ft oils and hydrogenation thereof on the praperties of margarine products were also evaluated. The ,....

: -38-margarine fats basically consisted of PMF-l at 46% by weight of the -; oil phase, the remainder consisting of the various soft oils. The margarines were formulated under similar processing conditions. The properties of these margarines (age of 10 to 14 days) are presented in the following Table:
. ,~
Uncycled_ Hot Probe 40 Shear Stress 80 Slump 5~ Soft Oilst~F/6 sec.) (psi) Grade (at 1 hr.) Soybean17.4 5.5 7.8 lo Sunflower 14.6 4.5 8.3 Hydrogenated 13.3 6.9 10 Sunflower Hydrogenated 11.3 15.9 10 - Cottonseed Cvcled Soybean 13.4 6.2 9.7 ,5 Sunflower11.3 4.9 10 Hydrogenated 10.0 8.9 9.3 Sunflower Hydrogenated 10.0 13.8 10 Cottonseed "-;, As can be seen from the above Table, rnargarines formulated with Soybean and SunYlower oil as the soft oil had significant cooling irnpact ~Hot Probe), acceptable hardness (Shear Stress), and suf~icient heat stability (51ump Grade) for stick-type products, en after temperature cycli.ng. By contrast, the margarines forrnulated ~ith the hydrogenated soft oils had unacceptable hardness ~Hydrcgenated Cottonseed), and insufficient cooling impact after c~clin~ (Hydrogenated Cottonseed and Hydrogenated Sunflower).

',',~
, .. .

i.
8~3~
:`;1 D. _her Fats and Oils.
- The effects of the addition of minor amounts of other fats and - oils on the properties of margarine products were also evaluated.
The margarine fats basically consisted of PMF-l at 46% by weight of the oil phase, the remainder consisting of a major proportion of soybean oil, plus a minor amount sf the various other fats or oils.
The margarines ~ere formulated under similar processing conditions.
The properties o~ these margarines (age of 10 to 14 days) are presented in the following Table:

.
.d 10 Uncycled - Added Hot Probe 40 Shear Stress 80 Slump Fat or Oil* (F/6 sec.) (psi) Grade (at 1 hr.) Control** 17.4 5.5 7.8

- 6% Palm Oil 14.7 5.1 9.7 15 12 5% 16.1 6.0 6.3 Hydrogenated Coconut Oil 4% Fix-X 8.9 3.7 10 Cvcled 20 Control 13.4 6.2 9.7 - 6% Palrn Oil 12.1 5.6 9.0 12.5% 13.9 7.4 6.7 Hyd-rogenated Coconut Oil 25 4~ Fix-X*** 9.0 1.3 10 *Percerltages are by weight of~ oil phase.
**Soybean Oil only.
***rnixture o~ 96% rapeseed and 4% soybean hardstocks.
,~
As sho~Jn by the above 1able, the margarines Forrnulated ~ith 6%
3() Palm Oil had signiflcarlt cooling irnpact (Hot P-robe), acceptable ':~

,.

s hardness (Shear Stress), and sufficient heat stability (Slump Grade) ~, for stick-type products, even after temperature cycling. By ; contrast, the margarine formulated with 12.5% Hydrogenated Coconut : Oil had insufficient heat stability for a stick-type product. Also, the margarine formulated with 4% Fix-X (rapeseed/soybean hardstock) had insufficient cooling impact.
: Effects of Processing Conditions on Properties of Margarine Products.
- The effect of processing conditions on the properties of ` 10 margarine products were evaluated. The first system involved -~ chilling the emulsion in an A unit, followed by crystalli7ation of the chilled emulsion in a static B unit. The flow rate (hence residence time) and outlet temperature of the A unit were varied.
The margarine fats used basically consisted of PMF-l at 46% by weight of the oil phase, the remainder consisting of soybean oil.
- The properties of these margarines (age of 10 to 14 days) are presented in the following Table:

_Uncyoled ,~ Processinq Conditions 80 Slump Flow Rate Outlet Hot Probe40 Shear Grade (Lbs/min.) ~ (F/6 sec.) Stress (psi) (at 1 hr.) 1 0 20 13.210.9 1.0 40 11.911.5 10 , is 0.6 20 13.711.6 9 0.6 40 13.~12.1 10 CYcled _ _ 1.0 2~ 13.0 4.1 ~,~
1.0 49 11.3 7.6 10 3~ 0.6 20 12.0 6.1 10 0.~ 4~ 7.1 9.5 ."

.,.i, 88~
, ~41-; As shown by the above Table, the margarines formulated under the various processing conditions of the first system had significant cooling impact (Hot Probe), acceptable hardness (Shear Stress), and sufficient heat stability (Slump Grade) for stick-type products, .~ 5 even a~ter temperature cycling.
The second system involved chilling the emulsion in an A unit, crystallizing the chilled emulsion in a working B unit, and then chilling the crystallized emulsion in an additional A unit. The flow rate (hence residence time) and the outlet temperature of the ~ 10 first A unit were varied. The outlet temperature of the second A
- k unit was kept constant at about 40F. The margarine fats consisted : basically of PMF-l at 46% by weight of the oil phase, the remainder consisting of soybean oil. The properties of these margarines (age of 10 days) are presented in the following Table:

Uncycled : Processing Conditions 80 Slump Flow Rate Outlet Hot Probe 40 Shear Grade -~ (Lbs/min.) Temp.(F) (F/6 sec.) Stress (psi) (at 1 hr.) 20 1.0 40 15.0 10.8 8.5 1.0 25 15.0 11.9 9.0 .6 25 14.0 11.4 10 0.6 40 16.0 10.~ 8.7 ~ycled 2S 1.0 40 12.2 2.~ 9.0 1.~ 25 12.~ 5~8 9.0 .6 25 12.1 5.4 9.5 , ,~
.6 40 12.7 7.0 9.0 , ,~

L ~i_~48~39 : As shown by the above Table, the margarines formulated under the various processing conditions of the second system had significant -` cooling impact (Hot Probe), acceptable hardness (Shear Stress), and sufficient heat stability (Slump Grade) for stick-type products, even after temperature cycling.
-~ Comparison of Margarine Products of the Present Application to Butter, Commercial Margarines and Margarines Containing Different Margarine Fats.
A. Butter and Commercial Margarines.
The oroperties of a margarine product of the present application were compared to butter and commercial margarines. The properties - of this margarine product (46% PMF-l by weight of the oil phase, the remainder of the margarine fat consisting of soybean oil), butter ....
~ (B) and three commercial margarines (CM-l to CM-3) are presented ln ; 15 the following Table:

Uncycled 8û Slump ; Hot Probe 4û Shear Stress Grade Product(F/6 sec.) (psi) (at 1 hr.) "s ~ 20 PMF-l 17.4 5.5 7.8 ;, B 11.8 11.0 10 , CM-l 10.4 405 10 CM-2 10.5 3.0 10 CM-3 9.9 1.7 10 CYcled PMF-l 13.4 6.2 9.7 B 11.8 14.6 10 C~1 10.6 3.1 10 C~-2 9.7 1.1 10 CM-3 g.b, 1.0 10 ,""~

As shown by the above Table, the PMF-l margarine compared favorably to butter (B), especially in terms of cooling impact (Hot Probe). In particular, butter had unacceptable hardness (Shear Stress) after temperature cycling. As also shown by the above Table, commercial margarines CM-l to CM-3 had an insufficient ~ cooling impact.
:.~ B. ûther Marqarine Fats.
- The properties of a margarine product of the present application (46% PMF-l by weight of the oil phase, the remainder of the margarine fat consisting of soybean oil) were also compared to margarines formulated from different margarine fats. These other margarine fats consisted basically of different structural fats with . the remainder thereof consisting of soybean oil. The PMF-l and - other margarine fats were formulated into margarines under similar ~-~ 15 processing conditions. The properties of these margarines (age of 7 , to 14 days) are presented in the following Table:
;
_ Uncycled 80 Slump Hot Probe 40 Shear Stress Grade Product* (F/6 sec.) (psi) (at 1 hr.) 46% PMF-1 17.4 5.5 7.8 46~ Palrn Oil 15.7 4.7 6.0 ~, 75~ ls~ 17.7 4.6 0 Palm Olein**
46% Randomized 15.0 2.6 10 Palm Oil i 46% ~Ydro9enated 9.2 2.3 10 2d Palm Olein***
b6% Cocoa autter 14.4 3.0 9 n*~*
4~ Cocoa But~er 14~6 2.7 9.0***~
Suostitute ,, , ,j;
"~J.~

s~

46% Hydrogenated 16.8 5.9 8.0*****
Coconut Oil Cycled 46% PMF-l 13.4 6.2 9.7 ; 46% Palm Oil 15.~ 3.9 5.3 75% 1st 18.1 5.1 0 Palm Olein**
-t'~ 46% Randomized 10.9 1.1 10 Palm Oil 46% Hydrogenated 9.6 1.6 10 ~; 2d Palm Olein***
46% Cocoa Butter 12.7 5.4 46% Cocoa Butter 12.4 5.6 Substitute 46% Hydrogenated 14.2 1.5 7.0*****
Coconut Oil *Percentages are by weight of oil phase.
**lst liquid fraction from thermally fractionated palm oil.
***Hydrogenated 2d liquid fraction from thermally fractionated palm oil.
****Age o~ 1 day.
*****Age of 28 days.

As shown by the above Table, the PMF-l margarine compared favorably with the margarines made from Randomized Palm Oil, Cocoa 3utter and Oocoa Butter Substitute, especially in terms of cooling ~, impact (Hot Probe), even after temperature cycling. By contrast~
the rnargarines made from Palm Oil or 1st Palm Olein had insuf~icient heat stability (Slump Grade)for stick-type produc-ts. As also shown by the above Table, the maryarine made ~rom Hydrogenated 2d Palm Dlein had insu~ficient cooling impact while the margarine made from Hydrogenated Coconut Oil had insufficient heat stability for stick-type products after cycling.

,~
, ",~

8~
--~ Specific Embodiments of Methods for Ma~ing Structural Fat and - Margarine Products According to the Present Application.
-~ The following are specific embodiments ~hich illustrate methods for making structural fats and margarine products according to the present application:
A. Structural fat.
Embodiment 1 ûne method for making a structural fat is as follows:
Sixty-eight hundred 9. of whole RBD palm oil (IV of 53.8) was placed in a glass ~ractionation column having a length of about 30 inches and an inside diameter of about 6 inches. This column had a jacket ' for circulation of a mixture of water-propylene glycol to heat and cool the palm oil. The palm oil was heated to a temperature of 170F under agitation by an impeller rotating at 11 rpm for about 0.5 hours. The heated oil was slowly cooled to 80F at a rate of 12.6F/hr. under agitation of the impeller rotating at 11 rpm. Tlle temperature of the cooled oil was maintained at 80F for 16 hours with no agitation. The solid crystals forming the stearine fraction were filtered out with a 8uchner funnel. A vacuum of 28 to 29 ~0 inches of mercury was applied to the funnel.
,~ The yield of the stearine fraction was about 20% by weight.This stearine fraction had an IV of 43.7. The triglyceride composltion of this stearine fraction is presented in the folluwing Table:

fatt~/ Acid Composition Carbon No. Profile Fatt~/ Acid % Carbon No. %
palmitic51.4 48 1~.0 stearic 5.2 50 36.0 oleic 33.4 52 27.7 linoleic ~.0 54 8.7 Other 2.0 Other 9.6 ,~
. "~
A first olein Yraction was flltered off from the stearine fraction. ~he yield of this olein fraction was about 80~ by "~

-. -46-i weight. This olein fraction had an IV of 57.~. The triglyceride composition of this olein fraction is presented in the following table:
:
Fatty Acid Composition Carbon No. Pro~ile ,~
s Fattv Acid % Carbon No. %
palmitic 39.3 48 3.9 -~ stearic 4.5 50 36.4 oleic 42.9 52 36.5 linoleic 10.8 54 11.2 o Other 2.5 Other 12.0 , ~
After filtering, -the first olein fraction was again placed in the fractionation column, and heated to a temperature of 150F under - agitation by the impeller rotating at 11 rpm for about 0.5 hours.
The heated olein fraction was then slowly cooled to a temperature~ of 15 60F at a rate of 14.2F/hr. under agitation of the impeller rotating at 11 rpm. The tempera'cure of the cooled first liquid fraction was maintained at 60F for 16 hours with no agitation. The solid crystals ~orming the desired palm mid-fraction ~/ere Filtered out as in the first filtration.
The yield of the palm mid-fraction (based on whole palm oil) was about 13~ bY weight. This palm mid-fraction had an IV of 44.9. The triglyceride composition of this palm mid-fraction is presented in the ~ollowing Table:

,t Fatty Acid Corn~osition Carbon No. Profile 2, Fatty Acid % Carbon No. %
palmitic 50.7 48 5.9 stearic 5.5 50 52.7 olelc 35.2 52 27.3 linoleic 6.9 54 6.5 Other 1.7 Other 7.6 ,~
i.,~
A seconcJ olein ~raction was ~iltered o~f from the palm rnid-fraction. The ~ield o~ this olein fraction (~ased on whole palm ,~
,~
, ...

oil) was about 65% by weight, This olein fraction had an IV of 60.4. THe triglyceride composition of this olein fraction is presented in the following Table:
Embodiment 2 Another method for making a structural fat is as follows: Ten separate 360 to 390 lb. quantities of whole RBD palm oil are heated to a temperature of about 150°F until melted. The melted quantities of palm oil are slowly cooled (without agitation) by holding at ambient temperatures for about 12 hours. The cooled quantities of oil are then held (without agitation) at about 80°F for about 48 hours to crystallize out the stearine fraction. The stearine fraction is then separated from the first olein fraction for each quantity of oil by using a rotary drum filter.
The first olein fraction in separate 375 to 410 lb. quantities is heated to a temperature of about 150°F until essentially crystal free. The heated quantities of olein fraction are slowly cooled (without agitation) by holding at ambient temperatures for about 12 hours. The cooled quantities of olein fraction are held (without agitation) at about 70°F for about 24 hours, are then held (without agitation) at about 60°F for about 24 hours, and are further held (without agitation) at about 70°F for about 24 hours to crystallize out the palm mid-fraction. The palm mid-fraction is then separated from the second olein fraction using a rotary drum filter and centrifuge. This palm mid-fraction can be used after deodorization as a structural fat.

:
8~3~

--- B. Marqarine Oil Products.
A margarine oil product was made by blending a structural fat prepared by double thermal fraction of palm oil with soybean oil.
The blend is heated to about 150F to melt the structural fat.
The fat designated PMF-l was used. A 46% mixture of PMF-l with 54~ soybean oil has the following Solids Fat Content:

Temperature % Solids Bv Weight 50F 29.9 7ûF 15.0 ; ] 80F 7.0 92F 3.2 105F 0.8 The P:St ratio is 6.6.
The O:L ratio is 0.94.

15 C. Marqarine products.
Embodiment 1.
A margarine ~as formulated from standard margarine aqueous phase ingredients (water, milk solids, salt, preservatives) dispersed in an oil phase containing the margarine fat of the present application (46% by weight palm mid-fraction, remainder soybean oil), plus other oil phase ingredients (mono-, di-glyceride and soybean lecithin eroulsifiers, beta-carotene, flavors). The aqueous phase formed about 20~ by weight of the total emulsion; the oil phase formed about ao~ by weight.
. 25 The melted dispersion (temperature of about 120F) of aqueous and oil phase ingredients was sent throuyh an A unit of the Votator-type. The flow rate was such as to provide about i minute residence time in the A unit. The mutator speed of the A unit was 150 rpm.
The water-in-oil emlJlsion was discharged from the A unit at a temperature of frorn 16 to Y6F.
The chilled emulsion from the A unit was sent through a ~ mot10nless mixer B unit. The residence time within the B unit was "~

"

~., about 3 to 5 minutes. The crystallized emulsion picked up lû to 15F of heat during crystallization. The crystallized emulsion was discharged from the static B unit and then stored at 40F. This product after cycling has a Hot Probe value of 12F/6 sec. and a slump grade of 10.
E_bodiment 2.
A margarine was formulated from aqueous an~ oil phase ingredients the same as those of Embodiment 1. The melted dispersion (temperature of about 120F) of aqueous and oil phase ingredients was sent through two A units in series of the Votator-type. The A units provided a combined residence time of about 1.6 minutes. The mutator speeds of the A units were 25û rpm and 180 rpm, respectively. The water-in-oil emulsion was discharged from the second A unit at a temperature of from 17 to 27F.
The chilled emulsion fro ~ the second A unit was sent through a working B unit of the Votator type. This working B unit pro~/ided a residence time for the chilled emulsion of about 3.8 minutes. The shaft speed of the working B unit was 260 rpm. The crystallized emulsion in the working B unit picked up crystallization heat such that the margarine was discharged at a temperature o~ from 44 to 48gF.
The crystallized emulsion from the working B unit was then sent through an additional A unit of the Votator type. The residence time of the crystallized emulsion in this-additional A unit was ab w t 0.7 minutes. The mutator speed of this additional A unit was 150 rpm. The crystallized emulsion was discharged from thls additional A unit at a temperature of from 22 to 28F. The chilled crystallized emulsion from this add,itional A unit was eY~truded into a stlck-type nargarine product and then stored at 40F.
'~hen thls margarine is used to prepare a cake, the cake has no g~n llnes and ~s higher than cakes prepared from commercially a~/allable mar~arlnes.

~,~
l~i

Claims (22)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A structural fat consisting essentially of:
(i) from about 3 to about 9% by weight SSS triglycerides;
(ii) from about 35 to about 46% by weight SOS
triglycerides;
(iii) from about 6 to about 12% by weight SSO
triglycerides; and (iv) from about 23 to about 29.5% by weight SOO/SLS
triglycerides;
wherein S = saturated C16 or C18 fatty acid residue, O = oleic acid residue and L = linoleic acid residue;
said fat having a weight ratio of P:St acid residues attached to the glycerides of about 8.5 or more and a weight ratio of O:L acid residues of about 3.5 or more, wherein P = palmitic, St = stearic, O = oleic and L = linoleic;
said fat having;
(a) a Solid Fat Content of:
(i) from about 67 to about 80% at 50°F.;
(ii) from about 31 to about 58% at 70°F.;
(iii) from about 12 to about 39% at 80°F.;
(iv) from about 4 to about 18% at 92°F.; and (v) about 7% or less at 105°F.; and (b) a Carbon Number Profile of:
(i) from about 5 to about 12% by weight C48 triglycerides;
(ii) from about 40 to about 55% by weight C50 triglycerides;
(iii) from about 23 to about 35% by weight C52 triglycerides; and (iv) from about 5 to about 10% by weight C54 triglycerides;;.

2. A fat according to claim 1 having a Carbon Number Profile of:
(i) from about 7.5 to about 9.5% by weight of C48 triglycerides;
(ii) from about 43 to about 50% by weight C50 triglycerides;
(iii) from about 26 to about 33% by weight C52 triglycerides;
(iv) from about 7 to about 9% by weight C54 triglycerides.

3. A fat according to claim 1 having a Solid Fat Content of:
(i) from about 71 to about 77% at 50°F.;
(ii) from about 33 to about 48% at 70°F.;
(iii) from about 18 to about 28% at 80°F.;
(iv) from about 6 to about 13% at 92°F.; and (v) about 3% or less at 105°F.

4. A fat according to claim 3 having a positional isomer triglyceride composition of:
(i) from about 4 to about 7% by weight SSS triglycerides;
(ii) from about 35 to about 46% by weight SOS
triglycerides;
(iii) from about 7.7 to about 10.2% by weight SSO
triglycerides; and (iv) from about 23 to about 29.5% by weight SOO/SLS
triglycerides.

5. A fat according to claim 4 wherein the ratio of P:St is from about 9 to about 10 and the ratio of O:L is from about 4 to about 5.

6. A fat according to claim 5 having a Fatty Acid Content of:
(i) from about 47.5 to about 54% by weight palmitic acid residues;

(ii) from about 4.5 to about 5.5% by weight stearic acid residues;
(iii) from about 34 to about 38% by weight oleic acid residues; and (iv) from about 6.5 to about 9.5% by weight linoleic acid residues.

7. A fat according to claim 4 having an iodine value (IV) of from about 39 to about 47.

8. A fat according to claim 7 having an IV of from about 42 to about 47.

9. A fat according to claim 1 having a Fatty Acid Content of:
(i) from about 44 to about 55% by weight palmitic acid residues;
(ii) from about 4.5 to about 5.5% by weight stearic acid residues;
(iii) from about 31 to about 40% by weight oleic acid residues; and (iv) from about 6 to about 9.5% by weight linoleic acid residues.

10. A solventless method for fractionating palm oil to obtain a structural fat, which comprises the steps of:
(1) heating whole palm oil having an iodine value of from about 50 to about 55 to a temperature of from about 140°F. to about 170°F. until essentially crystal free;
(2) slowly cooling the heated palm oil to a temperature of from about 75° to about 95°F.;
(3) maintaining the palm oil at a temperature of from about 75° to about 95°F. for at least 10 hours to permit crystallization of a first solid fraction having an iodine value of from about 42 to about 47;
(4) separating the first solid fraction from a first liquid fraction having an iodine value of from about 56 to about 61;

(5) heating the first liquid fraction to a tempera-ture of from about 140°F. to about 170°F. until essentially crystal free;
(6) slowly cooling the heated first liquid fraction to a temperature of from about 60° to about 75°F.;
(7) maintaining the first liquid fraction at a temperature of from about 60° to about 75°F. for at least 12 hours to permit crystallization of a second solid fraction having an iodine value of from about 39 to about 47; and (8) separating the second solid fraction from a second liquid fraction to yield a separated second solid fraction as the structural fat.

11. A method according to claim 10 wherein the whole palm oil of step (1) and the first liquid fraction of step (5) are heated to a temperature of at least 140°F for at least about 0.5 hours.

12. A method according to claim 11 wherein the tempera-ture during steps (1) and (5) is from about 150° to about 170°F.

13. A method according to claim 11 wherein the heated palm oil of step (2) and the heated first liquid fraction of step (6) are cooled at a rate of about 20°F./hr. or less.

14. A method according to claim 13 wherein the cooling rate of steps (2) and (6) is about 10°F./hr. or less.

15. A method according to claim 11 wherein step (3) comprises maintaining the cooled palm oil at a temperature of from about 75° to about 95°F. for at least about 48 hours.

16. A method according to claim 15 wherein the temperature of step (2) is from about 80° to about 85°F.

17. A method according to claim 11 wherein step (7) comprises maintaining the cooled first liquid fraction at a temperature of from about 60° to about 75°F. for at least about 24 hours.

18. A method according to claim 17 wherein the mainten-ance time in step (7) is at least about 48 hours.

19. A method according to claim 11 wherein step (7) comprises:
(a) holding the cooled first liquid fraction at a temperature of from about 70° to about 75°F. for at least about 5 hours;
(b) cooling the held fraction to a temperature of from about 60° to about 65°F. for at least about 5 hours;
and (c) slowly heating the held and cooled fraction to a temperature of from about 70° to about 75°F. for at least about 5 hours.

20. A method according to claim 19 wherein step (3) comprises holding the cooled palm oil at a temperature of from about 75° to about 95°F. for at least about 48 hours and wherein the holding time for each of substeps (a) to (c) of step (7) is at least about 24 hours.

21. A method according to claim 10 wherein the second solid fraction has an iodine value of from about 39 to about 47.

22. A method according to claim 21 wherein the second liquid fraction has an iodine value of from about 58 to about 63.