IE881398L - Improved sucrose fatty acid ester compositions and¹shortenings and margarines made therefrom - Google Patents

Abstract

The present invention relates to intermediate melting sucrose fatty acid ester compositions that are capable of rapid crystallization from a melted state. The compositions comprise 60% to 97% by weight intermediate melting sucrose fatty acid esters and 3% to 40% hardstock triglycerides or hardstock polyol fatty acid esters. Preferably the average fatty acid chain length of the hardstock material fatty acids is not less than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids. The sucrose fatty acid esters are characterized by their rheology, liquid/ solid stability, iodine value, and solids at body temperature. Rapid crystallization of the esters is useful in preventing anal leakage, and it could also translate into a reduction of post-hardening in shortenings and margarines, and into improved high temperature stability and temperature cycling stability as may be encountered during distribution of these products to the end user. [CA1339555C]

Description

63605 g This invention relates to intermediate melting sucrose fatty acid esters. la particular, the invention describes sucrose fatty add ©ster compositions which are capetol© of rapidly crystallizing from tlx® melted state, and shortening's and margarines made therefrom. 10 Sucrose fatty acid esters are known to be useful as replacements for triglyceride fats. U.S. Patent 3,600,186 to Mattson et al. discloses low calorie» fat-containing, food compositions in which at least a portion of the triglyceride 15 content is replaced with a polyol fatty acid ester such as a sucrose ester, the polyol fatty acid ester having at least four fatty acid ester groups with each fatty add having from 8 to 22 carbon atoms™ U.S. Patent 4,005,196 to Jandacek et al. discloses the 20 polyol fatty add esters of the Mattson et al. patent, in combination with fat-soluble vitamins selected from Vitamin A, Vitamin D, Vitamin E and Vitamin K.

U.S. Patent 4„DOS,195 to Jandacek discloses anti-anal leakage agents added to the polyol fatty add esters to 2S prevent an undesirable laxative effect. The agents include -2- aolid fatty acids (melting point 37°C or higher) and their triglyceride source, and solid polyol fatty acid esters.

Bailey, Melting and Solidification of Fats, p. 36, InterscieBce Publishers (1950} discloses that rapid solid!-5 fication of triglycerides in a melt or solution can often be initiated by "seeding" the liquid with a small proportion of crystals from an extraneous source.

None of these references suggests a way to make particular intermediate melting sucrose fatty acid ester 10 compositions that are capable of rapid crystallization from the melted state.

Therefore, it is an object of the present invention to provide intermediate melting sucrose fatty acid ester compositions that crystellize rapidly from a melt. 13 it is a related object of the present invention to provide these rapidly crystallising compositions by the incorporation of particular kinds of hardstock materials.

It is another object of the present invention to provide shortenings and margarines that contain the sucrose fatty 20 acid ester compositions.

These and other objects of the invention will become evident from the disclosure herein,.

All parts, percentages and ratios used herein are by weight unless otherwise defined.

Summary of the Invention The invention relates to intermediate melting sucrose fatty acid ester compositions that are capable of rapid crystallization from a melted state. The compositions comprise: 30 (a) from 60% to 97% by weight intermediate melting sucrose fatty acid esters containing at least four fatty acid ester groups, each fatty acid group having from 8 to 22 carbon atoms, wherein the sucrose fatty acid esters have: (i) a 33 non-Newtonian plastic rheology at 100°F (37.3°C) in 10 15 -3- particular a yield stress of not less than 15 Pa (150 dynes/on2) and a viscosity of not less than 1.5 Pa.s (15 poise J at !00°F (37.8°C) after 10 minutes of steady shear at 10 sec. % (ii) a liquid/solid stability of not less than 90% at 100®F (37„8eC}» (iii) an iodine value between 25 and 55, preferably between 36 '■ and 55, and (iv) from 51 to 50% solids at 37°C (body temperature)r; and (to) from 3% to 40% by weight hardstock nieterial selected from the group consisting of hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof, wherein the hardstock has an iodine value not more than 12.

Preferably the average fatty acid chain length of the hardstock 'materiel fatty acids Is not less than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids.

Detailed Description of the Invention i n ii 11 ■! i**" ii i !■■■ i i ■ ni — 20 It has noM been discovered that it la possible to increase the rate at which certain intermediate melting sucrose fatty acid esters crystallize from a melted state. This development is especially useful for sucrose fatty acid ester-containing food products that are eaten warm, where the sucrose esters 23 have been melted. It is believed that rapid crystallization of the melted sucrose esters after ingestion decreases the undesirable possibility of the esters remaining melted as they pass through the gastrointestinal tract and resulting in an anal leakage event. 30 Because in vivo measurements of crystallization are impractical, it is assumed for the purpose of this invention that in vitro measurements of solids formation st body temperature (98.6°F, 37°C) is a useful simulation of the in vivo experience. Precedent for an in vitro analytical 35 measurement simulating in vivo experience has been set in the -4- shortening and oils industry with the us© of measuring solids content at 92°F (33®C) simulating in vivo solids at mouth temperature.

Rapid crystallization of the present sucrose fatty acid 5 esters could also translate imo a reduction of post-hardening in shortenings and mergarines, and into improved high temperature stability and temperature cycling stability as may be encountered during distribution of these products to the end user. 10 In a typical shortening and margarine at room temperature,, less than 181 of the fat is in the solid, i.e., crystalline, state. The remainders 82% or more, is liquid. In a shortening and margarine it is very important to keep the liquid oil effectively entrapped by the solids so it 15 will not be released upon temperature fluctuations or vibration such as those experienced in distribution of product into commercial trade. Small crystals are most effective in entrapping the liquid oil- When shortenings and margarines are crystallized in 20 scraped-wall heat exchangers, picker boxes, or other equipment under shear and/or fast agitation, smell crystals are formed with few primary and secondary bonds. After suitable tempering, the shortening or margarine remains soft, creamy, and spreadable. This consistency will prevail in 25 commercial trade distribution and in the homes of consumers even after aging and temperature cycling.

If, however, the fat crystallizes too slowly, such as with intermediate melting sucrose fatty acid esters, a large part of the crystallization will take place after the material has left 30 the processing equipment, i.e., the agitated processing conditions. This results in significant growth is the crystal size. This interlocking network of crystals formed in the static state is more rigid, less creamy and cannot as effectively entrap liquid oil. With time the product becomes 35 hard and brittle, resulting in unacceptable consistency and -5- the liquid oil will -weep- or separate from the bulk materiel, pooling1 at the surface of the product.

The addition of certain hardstocks to the present intermediate melting sucrose fatty acid esters Increases the s rate of crystallization, permitting crystallization to be more complete in the processing equipment under agitation. The addition of hardstocks also causes other hardstock materials to crystallize which otherwise would aot crystallize or would crystallize very slowly. This increased 10 crystallization rate leads to greatly reduced crystal size, significantly improving consistency and stability of the shortening or margarine.

In particular, the present invention is a sucrose fatty acid ©ster -soniposition comprising: IS (a) from 60% to 97% by weight intermediate melting sucrose fatty acid esters containing at least four fatty acid ester groups „ each fatty acid group having from 8 to 22 carbon atoms s wherein the sucrose fatty acid esters have: Ci) a 20 non-Newtonian plastic rheology at 100°F (S7.8®C) in particular a yield stress of not less than .15 Pa (150 dynes/art3) and a viscosity of not less than 1*5 Pa.s (15 poise) at 100°F (37.8°C) after 10 minutes of steady shear st 10 sec."*, CM) a liquid/solid stability of not less 25 than 90% at 100°F <37.8®CK (ifl) an iodine value between . 25 and 55, preferably between 36 and 55, and (iv) from 5% to 50% solids at 37°C (body temperature); and (b) from 3% to 40% by weight hardstock 30 material selected from the group consisting ©f hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof, wherein the hardstock has an iodine value not more than 12. 35 -6- As 'discussed in more detail below, It Is preferred that the average fatty acid chain length of the hardstock material fatty acids Is not less than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids. S The Sucrose Fatty Add Esters The intermediate melting sucrose fatty acid esters used herein have a specific viscosity and liquid/solid stability, as will be described below. The sucrose esters are also substantially nondigestible and nonabsorbable. Therefore, 10 the sucrose esters must have at least four fatty acid ester groups. Polyol fatty acid ester compounds that contain three or less fatty acid ester groups are digested in and the products of digestion are absorbed from the intestinal tract much in the manner of ordinary triglyceride fats, whereas 15 polyol fatty acid ester compounds that contain four or more fatty acid ester groups are substantially nondigestible and consequently nonabsorbable by the human body. It is not necessary that all of the hydroxyl groups of the sucrose be esterified with fatty acid, but It Is preferable that the 20 sucrose contain no more than two unesterifled hydroxyl groups. Preferably the sucrose fatty acid esters have: (a) a total content of ©eta-, hepta-, and hexa~esters of not less than 95% j (b) an octa-ester content of not less than 70%; and (e) a content of the penta- and lower esters of not more 25 than 3%.

The fatty acid groups esterified to the sucrose molecule •contain from 8 to ' 22 carbon atoms, and preferably from . 14 to 18 carbon atoms. Examples of such fatty acids include caprylic, capric, lauric, myristic, 30 myristoleic, palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, linolenic. eleostearic, arachidic, arachidonic, behenic, and erucic acid. The fatty acids can be derived from naturally occurring or synthetic fatty acids; they can be saturated or unsaturated, including positional and geometrical isomers. The fatty acids esterified to the sucrose molecule -7- are of mixed chain length to obtain the rheoiogy and stability properties required herein.

The sucrose fatty acid esters suitable for use herein can be prepared by a variety of methods known to those skilled 5 in the art- These methods include: trsnsesterification of the sucrose with methyls, ethyl or glycerol fatty acid esters using a variety of catalysts; acylation of the sucrose with fatty acid chlorides; acylation of the sucrose with fatty acid anhydrides; and acylation of the sucrose with fatty acids, per se„ 10 Mixtures of different fatty acids are used in the synthesis. The preparation of sucrose fatty acid esters is described in generel in U.S. Patents Nos. 2,831,854. 3,963,699 and 4,517,360.

A specific example of the preparation 15 of intermediate melting sucrose fatty add esters suitable for use herein is the esterification of sucrose with methyl esters of a fully hydrogenated soy oil {I.V. 8) and a partially hydrogenated soy oil (I.V. 107) blended in a 45:55 ratio.

Examples of the ;• present sucrose fatty acid SO esters are esters oiade by esterifying sucrose with a Mend of partially and nearly 'completely hardened soybean oil methyl esters, for example, esters having the following properties: (1) octaester content 84.5%; SFC at 50°F <10°C) of 71.8, at 70°F C2i®C> of 64.2, at SQeF (27eC) of 51.1, at 92®F (33°C) 25 of 33.2, and at 10S°F (41°C) of 9.5? fatty add composition of 11.5% C16, 54.2% C18, 17.9% Cl8jl, 14.2% C18.r 1% Cl8;3. 6-5% C9^, and 0.3% C,9; and I.V. of 42.6; or (2) octaester content* of 92.1%; SFC at 50°F (10°C) of 61.2, st 70«*F C21eC) of 48.4, at 8©°F (27°C) of 36.2, at 92°F (33°C) of 19.2, and 30 at 105°F C41°C) of 3.1; fatty acid composition of 9.8% C,g, 50.6% C18, 21.6% C18;1, 15.7% C18;2, 1% C18j3, 0.5% C^and 0.3% C-«; and I.V. of 48.6. £b The intermediate melting sucrose fatty acid esters of the present invention have a non-Newtonian plastic rheoiogy at 35 100®F (37.8°C), in particular a yield stress of not less than 15 Pa (150 dynes/cm2) and a viscosity of not less than 1 .,5 Pa.s (15 poise) at 130®? (37.8°C> after 10 minutes of steady shear at 10 sec.

The sucrose esters also have a liquid/solid stability of not less than 90% at 100°F (37.8°C). In general terms,, the S esters can be described as being very viscous and plastic.

The Mould portion of the esters does not readily separate from the solid portion.

The sucrose fatty acid esters can be a single type of ester or a mixture of esters. It is not critical that each type 10 of ester has the above-mentioned physical properties as long as the intermediate melting sucrose esters as a whole have these physical properties.

It was discovered that sucrose fatty acid esters having the above-mentioned rheoiogy and liquid/solid stability are 15 effective at avoiding anal leakage while containing surprisingly low levels of solids at body temperature (37°C). The low solids levels allow the production of non-waxy, excellent-tasting foods. For further details on esters having these rheoiogy characteristics, see European Patent Application 20 236,288 of Bernhardt, published September 9, 1987.

If the hardstock material of the present invention comprises sucrose fatty acid esters, it is preferred that the combination of intermediate melting sucrose fatty acid esters 2S end hardstock has the above-mentioned rheoiogy and liquid/solid stability.

Viscosity and yield stress are known rheological properties, and can be measured by use of an instrument such as a plate and cone viscometer (e.g., a Ferranti-Shirley 30 viscometer, manufactured by Ferrauli Electric, Inc., 87 Modular Ave., Commack, NY 11725). The basics of rheoiogy are discussed in Idson, "Rheoiogy: Fundamental Concepts", Cosmetics and Toiletries, Vol. 93„ pp. 23-30 (July 1978).

Viscosity is calculated from a point on the rheogram curve. _0_ «SF Additional details are provided below under the Analytical Methods section.

The Hardstock Materials The sucrose fatty acid ester compositions of the present 5 invention contain from 3% to 40% by weight of a hardstock materiel In addition to the sucrose esters. The hardstock is selected from hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof* and it has an Iodine value of not more than 12. The 10 hardstock contains between 80% and 100% solids at body temperature (37°C).

As discussed more fully below, it has been found that in order to achieve the most rapid crystallization of the intermediate melting sucrose fatty acid ester compositions from 15 the melted state, the average fatty acid chain length of the hardstock material fatty acids must be not less than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids. However* crystallization more rapid than that of the sucrose esters alone can be achieved 20 using hardstock materials with a shorter average fatty acid chain length as well.

The hardstock is a substantially completely hydrogenated triglyceride fat or polyol fatty acid ester having an iodine value not exceeding 12. The hardstock can be obtained 25 by hydrogenating naturally occurring triglyceride oils such as palm oil* cottonseed oil* soybean oil* sunflower oil, corn oil* peanut efil or mixtures thereof.

Hardened polyol fatty acid polyesters having an iodine value not more than 12 are also useful as the hard- 30 stock. The polyol fatty acid polyesters are those described generally above. However, the hardstock polyesters generally contain fatty acids that are more saturated than unsaturated* and more longer than shorter fatty acid chains. Typical examples of hardstock polyol polyesters Include 33 completely esterified sucrose polyester made from the esters of hardened palm or soybean oils, sucrose heptastearate, xylitol pentastearate, galactose pentapalmitate or mixtures thereof.

The present invention Is illustrated by the crystallization behavior of th® following compositions: .11. 15 HO 30 Intermediate Intermediate Intermediate n'l siting- Melting Melting Sucrose Ester Sucrose Ester Sucrose Ester A.

B ■is c w12 - _ - c *"14 C,» 16 C 17 gn 18 ,r^ "18; I 11.1 50.6 21.1 q © V m tir 0.2 30.0 91 '3 to hf 12.1 0.2 51.8 18.6 C18:2 C18:3 C20 Ml lU 15.8 1.0 0.1 16.3 1.1 0.4 CL3 15.8 0.8 0.5 0.2 Other IV 48.1 49,7 A ft A "SSI w "ffi Avg. f.

Btty 17.8 17.8 17.8 acid chain length Yield s tress 107.8 (1078) 84.3 (843) 140.0 (1400) (Pa(dynes/cm2)) vtseosi 31 /3.1 37.2 /3.7 60-1S0 /6-15 (p©is« y (Pa .s) Liquid/ > 95% 96.4% 92-100% solid stabiU ity Qcta ester 83% 89.4% 76-78% Octet, 1 iiepta , 98.6% 99-100% 91-100% hex® Penta i lower Solids k < 0.1* <§.1% <,0.2% at 8.8 6.3 18.3 body temp (37°C) -11 ?_ 12 *** "J d .1*8 '18:2 i Palm Soybean Eapeseed Triglyceride Triglyceride Triglyceride Hardstock Hardstock Hardstock A B C 0.2 1.1 - C,„ 43.2 10.3 3.9 C1? - 0»2 Cn 54.5 87„8 35.1 10 C~8;1 - 0-4 0.3 r* 18:3 C;o* 0.6 0.8 10.0 C99 - 0.4 49.1 1S Other 0.5 0.3 1.5 IV 0,1 0.5 0.5 Avg. fatty 17.1 17.& 20.1 length -13- Soybeen Sucrose Ester Hardstock 20 acid chairs length Soybean Sucrose Ester Hardstock S Palm Sucrose Ester Hardstock F 5 r "8 - - O.S C12 - - C!4 - - 1.0 cm 10.0 10.3 50.1 C17 - - — 10 C18 87.2 88.1 47.9 P 18:1 1.6 0.9 - C18:2 0.3 C18:3 - - - C20 0.6 0.6 - 15 C22 0.3 - - Other - _ - IV 1.9 0.8 0.0 Avg. fatty 17.8 17.8 16.9 as Average fatty acid chain length is calculated from the fatty acid composition determined by GCFAC. x = CGCFAC*' x chain length) GCFAC* *not including "other".

Example: Intermediate Melting Sucrose Ester A = ICO.Ill x 16) 4- (0.506 x 18) + (0.211 x 18) * (0.158 x 18) 4- (0.01 x 18) + (0.004 x 20)1/(0.111 + 0.506 * 0.211 + 0.158 4- o.oi + 0.004) 30 x ~ 17*8 -14- Samples are made conteining th© intermediate melting sucrose fatty acid esters by themselves, and in combination with the different hardstocks, using a hardstock level of 14% by weight of the total sample. Hardstocks A, B and C are 3 triglyceride hardstocks, hardstocks B and S are sucrose fatty acid ester hardstocks made by esterifying sucrose with hardened soybean oil fatty acids, and hardstock F is a sucrose fatty acid ester hardstock made by esterifying sucrose with hardened palm oil fatty adds. The compositions 10 are completely melted by heating at 158°F (70°C) for 30 minutes, and then held at 98.6°F (37°C) to observe the crystallization behavior. The table of results below illustrates the crystallization behavior of the samples made with intermediate melting sucrose ester A.

Rate of Solids Formation at 98.6°F C37°C) S8 SFC at .8°F (37 °C) 198 d. 252 308 s. 300 s. 414 s. 4SO i Intermedial© melting sucrose ester A 8.8 i .0 0.6 1A 1.0 1.2 1.0 Sucrose ester A/hardstock A 26.3 0.8 0.4 1.2 0,8 1.2 1.9 Sucrose ester A/hardstock B 34.5 2.4 2.S 2.7 3,4 7.1 8.4 Sucrose ester A/hardstock C 30.8 0.7 7.4 11.8 13.7 15.3 10.2 Sucrose ester A/hardstock D 31.? 0.0 0.1 7.3 11.8 13.8 14.9 Suer-ose ester A/hardstock E 30.1 0.0 1.8 7.8 12.2 14.4 18.8 Sucrose ester A /hardstock F 27.8 1.8 1.4 1.5 1.9 3.1 4.5 -16- Surprisingly, it has been found that the addition of hardstocks to an intermediate melting sucrose fatty acid ester results in a higher level of solids at body temperature (37 °c) (SABT) than expected. For example, when the SABT of s sucrose ester A is measured by SFC» it is found to be 8.8%. Assuming that the level of SABT in the hardstock is 100%, it is calculated that adding 14% hardstock to the sucrose ester would result in SABT of: (0.88 x 8.8} + (0.14 x 100) = 21.6% SABT 10 Actual measurement by' SFC results in an increased level of solids ranging from about 26% to about 35% SABT depending on the type of hardstock es shown In the table above. Given their higher SABT, it would be expected that the rate of crystallization of these hardstock/ sucrose ester mixtures 15 would be greater than the rate of crystallization of the sucrose ester alone. This is the case as seen In the table.

It would be expected that th© sucrose ester/hardstock mixture having the highest SABT would also have the highest rate of crystallisation at 98„6°F (37°C)» Surprisingly, this is 20 not the case. For example, the hardstock producing the highest rate of crystallization for the sucrose ester mixture shown above had 30.8% SABT. It appears that the hardstocks having the highest rates of crystallization at body tenperature (37°C) are those wherein the average fatty acid chain 25 length is not less than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids.

The following tables illustrate the crystallization behavior of the samples made with intermediate melting sucrose esters B and C and the different hardstocks: Rale of Solids Formation at 90,6°F (37°C) 98 SFC at e8°F (37°€) 198 Be 252 s. 308 s. 380 s3 414 450 s Intermediate melting sucrose ester 6 6.3 1.3 1.4 1.2 1.1 1.1 1.8 Sucrose ester- B/hardstock B 2 7.7 0.1 0.9 1.3 1.4 3.6 4.7 Sucrose ester B/hardsloek € 31.1 0.0 i.s 6.5 9.2 10.8 12.1 Sucrose ester B/hardgtock D 2Bsl 0.0 CL0 5.1 8.9 12.0 13.2 Sucrose ester B/hardstock E 29.1 0.0 0,0 3,0 U 10.9 12.1 Sucrose ester B/hardstock F 30 A 1.7 1.5 1.4 2,0 3.3 4.9 Rale of Solids Formation at SS,8°F (37°C) SFC at ■e3sS®P (37 ®C) 198 s. 252 s. 308 s. 380 s. 414 s, 450 , Intermediate melting sucrose ester- C 18,3 0.0 0,2 0,2 0,4 0,7 as? Sucrose ester C/hardstock A 34.8 0,0' 0.0 0.0 1.8 4,8 6.8 Sucrose ester- C/hardstock B 40,8 0.5 1.2 4.0 9,0 '12,0 13,0 Sucrose ester C/hardstock C 35.0 2.9 8.1 12.8 15.6 17 .6 18.0 Sucrose ester C/hardstock D 35.4 0.0 1.7 3.6 12. 8 15.2 18.S Sucrose ester C/hardstock E 35.7 0.0 1.3 f.O 11.6 14.3 18,2 Sucrose ester- C/hardstock F 37.0 0.0 §,0 0.0 2.2 8,0 8,2 -19- The results demonstrate that th© most rapid crystallization of the intermediate melting sucrose esters from a melt is achieved by adding a hardstock having an average fatty acid chain length not less than that of th® sucrose S ester fatty acids. Hardstocks B* C, D and E have an average fatty acid chain length not less than that of the intermediate melting sucrose ester fatty acids™ The significant increase in percent solids over time for these compositions indicates that the compositions undergo rapid 10 crystallisation at 98„SaP (37°C) from the melted state. By contrast, hardstocks A and F have an average fatty acid chain length shorter than that of the sucrose ester fatty acids, and the compositions undergo slower crystallization over time. In fact ii is suspected thai the intermediate 15 melting sucrose ester fatty acids have an inhibiting effect on the crystallization of these hardstocks having an average fatty acid chain length shorter than that of the sucrose ester fatty acids.

Integrated Rheogram Area 20 While the above data indicates that each of the added hardstocks form more solids at body temperature (37°C) than expected, it has been discovered that there are significant differences in the types of solid systems formed. This can be measured as the integrated rheogram area of the sucrose 23 fatty ester/hardstock mixtures at 100°F (37.8°C), at 100 seconds " using a Ferranti-Shirley viscometer. Additional details are provided below under -the Analytical Methods section. Measurements for mixtures of intermediate melting sucrose fatty acid ester A, B and C and 14% of hardstocks A, 30 3, C, D, E, and F are given below: Integrated 35 Sucrose ester A Sucrose ester A/hardstock A Rheogram Area '— (mm ) 1225 2305 -20- C 1604 D 7982 E 0272 P 1,394 S Sucrose ester B 0 Sucrose ©ster B/hardstock A 612 B 2343 C 6353 D 7057 10 E 5914 F 3898 Sucrose ester C 1079 Sucrose ester C/hardstock A 2238 B 4S22 15 C 8746 D 10220 E 9136 F 5174 These differences are important in th© formulation of products. Those sucrose fatty ©ster/hardstock mixtures which are more fluid (smaller rheogram area) ar® expected to be useful in formulating products such as fluid.» or pourable, shortenings but not useful in products such as solid shortenings or other products not intended to be pourable. Those sucrose fatty ester / hardstock mixtures which are more viscous (larger rheogram area) are expected to be useful in formulating products such as solid shortenings or margarines. Those mixtures which are particularly useful in formulating semi-solid or solid products such as solid shortenings and margarines are believed to be those mixtures of intermediate melting sucrose fatty acid esters and hardstocks wherein the: (i) average fatty acid chain length of the hardstock material fatty acids is greater than the average -21- fatty acid chain length of the intermediate melting sucrose ester fatty acids,, or (ii) the average fatty acid chain length of the hardstock material fatty acids is not less than the average fatty . acid chain length of the intermediate melting sucrose ester fatty acids and the hardstock material comprises sucrose fatty acid esters.

Crystallisation of Other Hardstocks As discussed above, the most rapid crystallization of the present intermediate melting sucrose fatty acid esters is caused by the addition of hardstocks having an average fatty acid chain length not less than that of the sucrose ester fatty acids. In the following discussion, these will be termed the "longer chain length hardstocks'-.

Another embodiment of the present invention relates to the effect of the addition of these longer chain length hardstocks on other hardstock materials present in the sucrose ester compositions. Surprisingly, it has been discovered that not only do the present sucrose ester compositions rapidly crystallize, but that these longer chain length hardstocks cause other hardstock materials to crystallise in the compositions as well.

These compositions comprise from .■ . SOI to 98% intermediate melting sucrose fatty acid esters as described above, from 1% to 39% hardstock materials as described above having an average • fatty acid chain length not less than that of the intermediate melting sucrose ester fatty adds (the "longer chain length hardstocks"), and from 1% to .39% of a second hardstock material selected from the group consisting of hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof, wherein the second hardstock has an iodine value not more than 12 and from 80% to 100% solids at body temperature (37°C)P and wherein the average fatty acid "chain length of the second hardstock material fatty acids Is less than -22- (*=> the average fatty acid chain length of the intermediate melting sucrose ester fatty acids. These latter hardstocks will be termed the -shorter chain length hardstocks" in the following discussion. 5 From 10% to 80% other materials such as soft oils, intermediate melting fat, water, milk solids, color, flavor,, emulsifiers may be used to dilute the above composition in formulating various finished foods ®s will be demonstrated hereinafter. 10 Differential Scanning Calorimetry (DSC) can be used to measure the amounts of energy given off by the formation of or the amounts of energy required to melt solids. The basics of DSC theory are discussed in Applewhite, Bejley'3 Industrial Oil and Fat Products, 4th Ed., Vol. 3, pp. 204-206 15 (1985), John Wiley & Sons, New York. Upon cooling a completely melted sample from ?0°C (I58QF) to -S0„Q°C (-78°F) using a DSC, it is possible to calculate the amount of energy given off as solids form. H is useful to the present invention to look at the level of solids formed above 80°F 20 (27°C). This temperature is slightly below the temperature representing onset of solids formation for the formulations given below. Solids formed above this temperature will largely be hardstock materials. -23- Cpoling from 10°C (158°F) 15 20 Formula Mould soybean (I.V. 107), Oil 35% intermediate me!ting sucrose ester,, 7% hardstock 10 triglyceride (I.V. < 1) 65% liquid soybean, oil (I.V. 107), 33% intermediate melting sucrose ester, 2% hardstock sucrose fatty acid ester (I.V. < 1) Calories/ gni (Joule /kilogram) 80°F (27°C) Onset Total Temperature 0.0«9 81.4°F (205.2 JAg) (27,5°C) 58% liquid sovbean oil (I.V. 107), 33% Intermediate melting sucrose ester, 7% hardstock triglyceride (I.V. < 1), 2% 'hardstock sucrose ester (I.V. < 1) 0.530 88.7°F (2219.0 J/kg) (31.5°C) 1.446 91.0°F (6054.1 JAg) (32.8°C) Upon cooling the formulae shown above it is seen that 25 the presence of 7% triglyceride hardstock with shorter average fatty acid chain length than the intermediate melting sucrose ester ("shorter chain length hardstock") results in 0.049 calories being given off. In the formula which contains no shorter chain length hardstock, but does contain 2% of a 30 hardstock with longer fatty acid chain length ("longer chain length hardstock"), 0.530 calories (2219 J) are given off. It would be expected that the presence of both hardstocks in the third formulation would result in giving off about the additive energy of when the two hardstocks are used by themselves 35 (0.040 + 0.530 = 0.570). Instead, surprisingly, snore than twice the additive energy (0.579 x 2 * 1.158) is given off (1.446). -24- This phenomenon Is also seen when the level of the longer chain length hardstock Ss varied. This has been demonstrated using DSC. The expected level of calories to be given off due to addition of the longer chain length S hardstock can be determined by adding th® hardstock to a liquid triglyceride (less than 1% solids above 70°F t21°CJ).

These samples are raised to 7©°C (158°F) and then are cooled to -60.0°C (-76°F) in a DSC instrument and the energies given off above 80°F (2"aC) are measured. Th® expected in level of energy given off above 80°F (27°C) for shortening formulations containing shorter chain length hardstock and varying -levels of longer chain length hardstock can be calculated. This is done by adding the expected level of calories (joules) obtained above for the longer chain length hardstock 'JS and adding It to the actus! calories .(joules) for a shortening containing shorter chain length hardstock and not containing longer hardstock. See below.

Cooling I Longer Chain Length Hardstocks SO 0.0 1.5 2.5 3„3 5.0 Expected calories/gm 0.00 0.29 0.54 0.79 1.16 (Joules/kg) (O.OJ/kg) (1214J/kg) (2261J/kg) (3308JAg) (4857J/kg) above 80°F (27°C) from added longer chain length hardstock ES Expected calories/gm (Joules Ag) above 80°F (27°C) of shortening with indicated levels of longer chein 30 length hardstock Actual eaIori.es/gtn 0.50 1.S7 2.02 2.31 2.60 (Joules Ag) (2093JAg) (S573JAg) (8457JAg) (9672JAg) (10,886JAg) above 80°F (2?&C) of shortening with indicated levels of longer chain 35 length hardstock 0.79 1.W4 1,28 1.68 (3308JAg) (4354JAg) (5401JAg) (695UAg) The levdi of energy given off above 80°F (27°C) Is surprisingly higher than expected.

Upon completely melting formulations to 70°C (158°F) and cooling back to -60.0°C (-76°F), then raising the temperature back to about 60°C (i40°F), it is possible to measure the amount of energy required to melt solids as a function of temperature. It Is useful in the present invention to look at the amount of energy required above 105°F (41°C). Energy required above this point will largely be the result of the presence of hardstock materials.

Upon heating the formula containing only the shorter chain length hardstock, 0.026 calories are required above 105°F (41°C). The formula containing only the longer chain length hardstock requires 0.367 calories above 105°F (41°C). It would be expected that the presence of both hardstocks in the third formulation would result in requiring the additive energies of when the two hardstocks ere used themselves (0.026 + 0,367 « 0,393). Instead, surprisingly, more than twice the additive energy (0.393 x 2 « 0,786) is given off (0.323). -26- Cooling from ?D°C (158°F) Formula Calories/gin (Joules /Kilogram) >80°F (27°C) Com p.

Total MP 50% liquid soybean oil (I.V. 107}, 35®o intermediate melting sucrose ester, 7% hardstock triglyceride (I.V. K 1) 0.026 (108.8J/kg) 107.6°? (42°C) 151 liquid soybean ail (I.V. 107)„ 331 intermediate melting sucrose ester. 2% hardstock sucrose fatty acid ester (I.V. < I) 0.367 (1536.6JAg) 58% liauid soybean oil (I.V. 107), 0.823 115.8°F (46.5°C) (3445„7J/kg) 33% intermediate melting sucrose ester, 71 hardstock triglyceride (I.V. <15, 2% hardstock sucrose ester (I.V. < 1) As with cooling, the same phenomenon in heating can be seen as the level of th© longer chain length hardstock is varied, the expected level of calories required, above 105°F (41°C) for the longer chain length hardstock can be determined by adding varying levels of the hardstock to a liquid triglyceride oil (same as used in cooling) and using DSC to measure the amount of energy required above X05°F C41°C},., The expected level of calories above 105®F (41°C) of a shortening with added longer chain length hardstock can be determined by measuring the actual level of energy required above 105°F (41°C> of a shortening without the longer chain length hardstock and adding to it the expected energy for the longer chain length hardstock. See below. 15 ao es 30 3S 0.0 0 J Heating Longer Chela Length Hegdstock 1.5 2„S 3.5 5 J 0.35 0.52 i a Expected calories/gta (Joules/kilogram) above 10S°F C41°C) (0„0JAg) (795.4J/kg) (1465„4JAg) (2177.1J/kg) (3223-8JAg) from added longer chain length hardstock 10 Expected calories/gin (JouJ.es/kilograiTis) above I05°F (41°C) of shortening with indicated levels of longer chain length hardstock Actual calories/gm (Joules Ailograms) above 105°F C4l°C) >.39 ,55 0/ 0.97 (1632.9JAg) (2302.7JAg) (3014„5JAg) (4061.2J/kg) Off shortening with radicated levels off. longer chain length hardstock ~ plastic! sed - recycle heating 0.20 1.08 # 1.53 1.89 2.25 (837.4JAg) (4521.2JAg) (6405.8JAg) (7913.1 JAg) (9420.3JAg) ®*2® §.42 0,941 1.26 • 1.74 (837.4JAg) (1758.5JAg) (3935»6J/kg) (5275.4JAg) (7285.OJAg) Again,, the level of energy requried above 105°F (4PC) is surprisingly higher than expected. This is the case both for a pl&stidzed shortening heated in she DSC fr'om about 2l°C C70°F) to about 60°C (M0°F), as well as for the plestidzed shortening which has been subjected to recycle heating by being completely melted (70°C, 158®F}, cooled to about ~SQ°C C-76°F), and heated to about 60®C Shortening Compositions Another embodiment of the present invention is shortenings that contain the sucrose fatty acid ester compositions described hereinabove. The shortenings comprise: from 101 to 80% by weight of a sucrose fatty add ester composition comprising: -28- (I) from 80% to §7% by weight intermediate melting sucrose fatty acid esters containing at least four fatty acid ester groups, each fatty acid group having from 8 to 22 carbon atoms, wherein th© intermediate melting sucrose fatty acid esters have an iodine value between 25 and 55, preferably between 38 and 55, from 5% to 50% solids at body tenperature (37°C)f a non-Newtonian plastic; rheoiogy at 100°F (37.8°C) and Ins particular a yield stress of not less than 15 Pa (150 dynes/cm2) and a viscosity of not less than 1.5 Pa.s (15 poise) at 190°F (37.8°C) after 10 minutes of steady shear at 10 sec. and a liquid/solid stability of not less than 90% at 100°F (37.8°C)s and (ii) from about 3% to about 40% by weight first hardstock material selected from th© group consisting of hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof. wherein th© hardstock has an iodine value not more than 12 and from 80% to 100% solids at body temperature (37°C), and wherein the average fatty acid chain length of the hardstock materiel fatty acids is not less than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids; from . 20% to 90% by weight soft oil; from 0% to 50% by weight Intermediate melting triglyceride; from 0% to 2d% by weight second hardstock material selected from the group consisting of hardstock triglycerides and hardstock polyol fatty add esters, and mixtures thereof, wherein the second hardstock has an iodine value not more than 12 and from 80% to 100% solids at body temperature. (37°C), and Wherein the average fatty acid chein length of th® second .90.

St> W hardstock material fatty acids is less than the average fatty acid chain length of the intermediate melting sucrose ©ster fatty acids; and (e) tmm 0% to 15% other shortening Ingredients. 5 The soft oil of the present shortenings Is a liquid oil which acts to provide fluidity to the shortenings so that they ere creamy and can be easily scooped. Suitable soft oils have en iodine value CIV) between 70 end 130. If an intermediate melting fat is used in the present shortenings it 10 is preferred that the soft oil have an IV between 80 and 130, to adjust for the solids introduced by the intermediate melting fat. The soft oil can be derived from animals, vegetable or marine sources, including naturally occurring oils such as cottonseed oil, rapeseel oil. canola oil, 15 low erucic acid rapeseed oil, soybean ©iL sunflower oil, com oil, peanut oil, safflower oil or mixtures thereof.

Soft oils can be partially hydrogenated to prevent flavor deterioration caused by their more highly unsaturated 20 components such as linolenic acid residues. The partial hydrogens,tion of oils can be achieved by any of a number of art recognised techniques, all of which involve contacting1 the oil with gaseous hydrogen in th® presence of a catalyst such as nickel and /or capper. See. e.g., Bailey's Industrial Oil 2!a and Fat Products, supra, pp. 793 et seci- This partially hydrogenated soybean oil is winterized to remove solids to provide a soft oil having an IV of from 110 to 115. Sm,» e.g.. Bailey's Industrial Oil and Fat Products, supra, pp. 1007 et seq. for winterization techniques. It is 30 also desirable that the soft oil, e.g., partially hydrogenated soybean oil, be refined, bleached and deodorized in accordance with conventional practice. See. e.g.. Bailey's Industrial Oil and Fat Products, supra, pp. 7IS et seq. and 897 et seq. -30- Both the longer chain length, hardstock and the shorter chair, length hardstock provide plasticity to th® present shortenings in combination with the other fat materials,, and also provide high temperature to,eat stability. Additionally, S the hardstocks affect the crystal structure of the shorten* ings. The addition of more hardstock tends to flatten out the solid fat content profile of the shortenings. The hardstocks are derived from sources described hereinabove. For use in the present shortenings, preferred second hardstock materials 10 are those that are triglycerides containing palmitic- stearic-palmitic or palmitic-steaxic-stearic fatty acids in the 1, 2 and 3 positions. Certain vegetable oils or fractions thereof contain these predominantly beta-prime triglycerides, for example, hardened palm oil and hardened cottonseed oil. 15 The intermediate melting triglyceride used in the present shortenings contributes to the crystal structure and increases the shortenings8 oxidative stability. Further, the intermediate melting triglyceride can be beneficial in increasing the plastic range of the shortenings. Suitable intermediate melting triglycerides have an W between 25 and 60 and contain between 0% and 80% solids at body temperature (37°C). Triglyceride oils which can be hydrogenated to yield an intermediate melting fat are soybean oil, palm oil, cottonseed afil, peanut oil, coconut oil, 23 or mixtures thereof. Rearranged fats or oils prepared by interesterif&cation can also be used herein. Preferred intermediate melting triglycerides are hydrogenated to an 3V of 35-51.

The present shortenings also comprises from 0% to 30 15% by weight of other shortening ingredients. Various additives can be used herein provided that they are edible and aesthetically desirable and do not have any detrimental effects on the shortenings. The shortenings can normally contain Etimor amounts of optional flavorings, emulsifiers, 3S anti-spattering agents, anti-sticking agents. and anti-ostidants. -31- Hhese shortenings are preferably supplemented with vitamin S at a level of 1.0 sag d-alpha-tocopherol equivalents per gram of non-caloric fat-like material. As with standard shortenings, nitrogen can also be added to the shortenings 5 during processing to improve th® lightness of color of the product. The present shortenings can be processed with one ©r more of the following processes; hydrogenation, winterization, dewaxing, interesterification. Any standard processing method can be used to plasticize the 10 present shortenings.

The following data illustrate the more rapid crystallization of shortenings made according to the present invention.

A shortening composition as described above is made 15 with varying levels of hardstock made by esterifying sucrose with the fatty acid esters of hardened soybean oil. This hardstock material has an iodine value of less than I. The hardstock fatty acids have an average chain length about the same as that of the intermediate melting sucrose ester fatty 20 acids. The hardstock is added at levels of Q„Q0%» 0.50%, 1.00%, 5.00%, 10.00%, and 15.00% by weight of the shortening. The shortening samples are melted by heating to 158°F O'0°C) over a time of 30 minutes, and then allowed to crystallize at a temperature of 80°F (27°C). The percent solids is recorded 25 versus time of crystallization. -32- ' Solid Formation at 80°P (27°C) Seconds % Hardstock 90 108 126 144 0.00 1.45 9 9 a M n «U 1.46 1.94 5 0.50 2.01 2.11 1.60 1.75 1.00 1.52 1.66 1.73 1.94 5.00 2.02 1.82 1.97 2.06 10.00 '2.2? il! ^ w g. Ui'Ui 3.60 8 *77 15.00 2.14 3.0® 4.90 8.68 ID 180 216 270 380 450 0.96 1.26 1.05 1.26 3.06 1.18 1.04 1.19 a*28 4.57 0.71 1.15 1.92 3.43 5.38 3.76 7.38 9.04 9.08 9.72 15 10.52 12.32 13.65 13.94 14.74 13.74 16.30 17.71 17.64 18.21 The results demonstrate that the addition of hardstoclc to the shortening increases its rate of crystallization from a melt, and that higher levels of hardstock result in faster a 0 crystallization.

Margarine-Type Compositions Initial experience with hardstock addition for increased rates of crystallization of intermediate melting sucrose fatty acid esters was with shortenings. Although it was desirable 25 to investigate margarines containing intermediate melting sucrose fatty acid esters, the thought of using hardstocks for improved stability was resisted for two reasons: (i) it was unclear whether or not th© benefits would be seen in a product containing water? (ii) hardstocks are not normally 30 desirable for margarines as they tend to impart a waxy mouthfeel.

Surprisingly,, however. It has been determined that hardstocks can be included in margarine compositions containing intermediate melting sucrose fatty acid esters with 35 resultant improved stability and acceptable in-snouth texture. -33- Another (embodiment of the present invention is a margarine-type composition comprising: (a) from 10% to SQ% by weight of a sucrose fatty acid ester composition comprising: (i) from 80% to S 97% by weight intermediate melting sucrose fatty acid esters containing at least four fatty acid ester groups, each fatty acid group having from 8 to 22 carbon atoms, wherein the sucrose fatty add esters have an iodine value between 25 and 10 55, preferably between 36 and S3, and from 5% to 50% solids at body tenperature (37°C), and wherein the sucrose fatty aeid esters have: a non-Newtonian plastic rheoiogy' at 1§0°F (37.8°C), in particular a yield stress of not less than 15 Pa (150 dynes/cm3) 15 and a viscosity of not less than l.5Pa.s (15 poise) at 100°F (37.8°C) after 10 minutes of steady shear at 10 sec. , and a liquid/solid stability of not less than 90% of 100°F (37.8°C); and (II) from 3% to 40% by weight hardstock material selected from the group consisting of 80 hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof, wherein the hardstock has an iodine value not more than 12 and from 80% to 1001 solids st body temperature (37°C)e and wherein the average fatty acid chain length of the 25 hardstock material fatty acids is not less than the average fatty acid chain length of the intermediate naelting sucrose ester fatty acids; (b) from 20% to 70% by weight soft oil; (c) from 0% to 10% by weight intermediate 30 melting triglyceride; (d) from 0% to 15% other margarine ingredients; and (e) from 0.1% to 20% water.

The soft oil and intermediate melting triglyceride are the same as those described above for the shortening compositions. The other margarine ingredients include flavors, colors,,, emulsifiers, preservatives, milk solids, salt, and mixtures thereof. These margarines are preferably supplemented with Vitamin E at a level of 1.(3 mg 5 d-alpha-tocopherol equivalents per gram of non-caloric fat-like material.

Analytical 'Methods I —s- i_I i - 1. Solid Fat Content The method for determining Solid Fat Content (SFC) 10 values of a fat by PMR is described in Madison and Hill, J. Amer. Oil, Chem. Soc., Vol. 55 (1978), pp. 328-31 (herein incorporated by reference). Before determining SFC values, the shortening sample is heated to a temperature of 140°F (60°C5 for at least 0.5 hours or until the sample is completely 13 melted. 'The melted sample is then tempered at a temperature of 32°F C0°C) for 15 minutes, 80°F (2?°C) for 30 minutes, and 32°F (0®C) for 15 minutes. After tempering, the SFC value of the shortening at temperatures of 50°F (10°C), 70°F (21®C), 80°F (27°C), 92®F (33°C) end 105°F (41°C) is 20 determined by pulsed magnetic resonance (PMR) after equilibrating for 30 minutes at each temperature. 2. Rheoiogy Measurements: a. Sample Preparation The sucrose fatty acid ester sample or sucrose fatty acid 25 ester/hardstock sample is heated until It completely melts (about 195°F, 91°C) and is thoroughly mixed. Ten grams of the melted sample is weighed into a pre-heated 20 ml glass vial. The sample Is then allowad to recrystaliize at 100°F i 5°F (37.8°C ± 3°C) for 24 hours. After tfee 24 hour time 30 period has elapsed, the sample is taken to the viscometer and the viscosity and yield stress are measured. b. Ferranti-Shirley Viscometer Operation Procedure A Ferranti-Shirley viscometer equipped with a 600 gm torque spring is used for the viscosity and yield stress 35 measurements of the sucrose fatty acid ester sample or -35- sucrose fatty acid ester/hardstock sample™ A cone is put into place, sad the viscometer temperature is adjusted to 100°F (37.8°C). The chart recorder is calibrated,, and the gap between the cone and plate Is set. The con© speed is S checked,, and the cob® and plate temperatures are equilibrated to 100°F (37.8®C). The panel controls are set. Sufficient sample is placed between the plat® and the cone so that the gap is completely filled. The temperature is allowed to stabilize at 100°F (S7.8°C) for about 80 seconds, and then the 10 cone rotation and recording are started. A rheogram for the sample is recorded and analyzed to determine the viscosity and yield stress™ Viscosity is measured at 10 seconds after 10 minutes of steady shear. Yield stress is measured at zero time and is the stress required to achieve deformational flow. 15 c. Integrated Area Under Rheogram A twenty-gram sample is melted and mixed as described above, and then about one gram of the melted sample is placed into the Ferranti-Shirley viscometer which has equilibrated at 100°F (37.8°C). The sample's shear stress is 20 measured at WO see 1 for a period of 5 minutes. Recording paper is used such that scale for chart speed is 25 millimeters 9 per minute and the scale for shear stress is 145 dynes/cm'" (14.5 Pa) equals one millimeter. After the rheogram is generated, the area under the curve is integrated using hand calculations or 25 any of several computer assisted programs for such. The integrated area is then reported in millimeters squared. 3. Liquid/Solid Stability Measurement: The sucrose fatty acid ester sample or sucrose fatty acid ester/hardstock sample is heated until it completely melts and 30 is thoroughly mixed. The sample is then poured into Beckman #344062 4.4 ml. centrifuge tubes. The tubes are immediately transferred to a 100°F t 5°F (37.8°C t 3°C) constant temperature room and allowed to recrystallize undisturbed for 24 hours. The samples are then centrifuged 35 at 6Oe©0Q rpm for one hour at 100°F (37„8°G> (the centrifuge -36- and centrifuge head is previously equilibrated at 100®? [37.8®C5)* The force on the samples is 486,©00 G5s (4766 N). The liquid/solid stability is then calculated as follows: Liquid/Solid Stability = 100 x (total volume of sample - volume of liquid) totaFvoIume of sample 4. Fatty Acid Composition Principle The fatty acid composition of th® sucrose esters and 10 hardstocks of the present invention is measured by gas chromatography. First, fatty acid methyl esters of the sucrose esters or hardstocks are prepared by any standard method (e.g., by transestexiflcation using sodium methoxide), and then separated on a capillary column which is coated with 15 DB-WAX stationary phase. The fatty acid methyl esters are separated by chain length and degree of unsaturatlon. A split injection is made with flame ionization detection. Quantitation is performed toy an area normalization method. This method can separate fatty acid methyl esters from C6 to 20 C24.

Equipment Gas Chromatograph 5 Hewlett-Packard 5890, or equivalent, equipped with a split injector and flame ionization detector,, Hewlett-Packard C©°, Scientific Instruments Biv., 1L6Q1-T California Ave., Palo Alto, CA 04304 IS Autosampler Injector column Hewlett-Packard 7673A, or equivalent IS m x 0.25 mm I.D., fused silica capillary column coated with DB-WAX (0.25 micron film thickness}., Hewlett-Packard Co., Scientific Instruments Biv.

Data System Hewlett-Packard 3350, 3000-T Hanover St.. Palo Alto, CA 04304 ao Eecorder Kipp & Zonen, BD40, Kipp & Zonen Internal Standards A reference standard of a known triglyceride is used when determining the fatty acid composition of th® sucrose fatty acid esters or hardstocks herein. The triglyceride reference standard has-the following fatty acid, composition: 0.41 Cir 21.4% C1g9 9.2% C18» 40.3% Clg„r 23.0% Cw.2, 0.4$ C20. 1.3% C20.r 2.21 C,8>3, and 0.3% C2r k, Instrumental Set-up 1. Install the column in the gas chromatograph, and sat up the instrumental conditions as in Table 1. 2. Set up the data system with the appropriate method to acquire and analyze the data. The retention times may have to be adjusted in the method due to instrument variations. Consult the data system reference manual on how to do this — HP3350 User's Reference Manual. Unity response factors ar© used for each component. -ae- Table 1 INSTHOMENTAL CONDITIONS Instrument Hewlett-Packard 5890 Column 15 m x 0.25 mm I.B., coated with DB-WAX, 0.25 u film thickness 12.5 psi (86.185 Pa) Helium 210°C (410°F) 100 oiL/min 1.5 mLtrain Column head pressure Carrier gas Injector "Aw temperature Split vent flow Septum purge Oven temperature profile Initial temperature Initial time Rate 1 Final temp 1 Pinal time 1 Hate 2 Final temp 2 Final time t Hate 3 Final temp 3 Final time 3 Detector Detector temp Make-up gas Detector flow Detector air flow 110°C (230®F) 1 snin 15°C/snin 170°C (333®F) 0 min 6°C/min 200°C (392°F) 0 snin 10°C/ min 220°C (428°F) 8 min FID 230°G (446®F) 42 mL/min 30 mL/min 300 mL/nrin 3. Analysis of Samples - (The samples ara analysed 'with an area normalisation procedure.) 1. Prepare fatty acid methyl esters of the reference standard and sucrose ester or hardstock sample according to any standard method. -40- 2. Set up a sequence in the LAS data system to inject th® samples and reference standard. 3. Activate the autosampler to inject 1.0 uL of the samples end standard la the sequence. The gas 5 chromatograph will automatically begin its temperature program and the data system will collect and analyse th® data for the sequence.

Example 1 A preferred sucrose fatty acid ester composition is 10 prepared by combining 86% by weight intermediate melting sucrose fatty acid esters with the following properties: 98.6% octe-, hepta-, and hexa esters and less than 0.1% penta- and lower esters; fatty acid compositions of 11.1% C16" 50-6% C18" 21.1% C18:F 15-8% Ol8.r 1.0% C18.3„, 0.41 C20? eve rage "iS fatty acid chain length of 17.8; yield stress of. 107.8 Pa (1078. dynes/cm2)? viscosity of 3.1 Pa.s (31 poise)? liquid/solid stability of 95%? iodine velue ©f 48.1; 8.8% solids at body temperature with 14% of a triglyceride hardstock material with the following properties = fatty acid composition of 3.9% C,8, 20 35.1% C18« 0.3% C18.r 0.1% C18.r 10.0% C2Q, 49.1% C~2r 1.5% other; average fatty acM chain length of 20.1; iodine value of 0.5.

Example 2 A composition Is prepared as in Example 1 except that 25 the hardstock is s sucrose ester hardstock material with the following properties: fatty acid composition of 10.0% C1gt 87.2% C18, 1.6% Clg;1. 0.3% C18;2, 0.6% C2Qf 0.3% C^i average fatty acid chain length of 17.6; iodine value of 1.9. -41- Example 3 Shortenings are prepared by combining the following ingredients: Ingredient Soybean oiL I.V. 107 Intermediate melting' triglyceride, I.V. 43 Palm triglyceride hardstock, X.?. 4 Intermediate melting sucrose fatty acid esters Hardstock sucrose fatty acid esters Emul sifter Ingredient Soybean oil, I.V. 107 Intermediate melting triglyceride,, I.V. 43 Palm triglyceride hardstock, I.V. 4 Intermediate melting sucrose fatty acid esters Hardstock sucrose fatty acid esters Emulsifier Shortening Shortening Shortening 58.5 58.5 4.0 33.0 0© 4.5 4.0 28.0 3.0 Shortening Shortening © E 53.5 3.5 3.5 27.4 TaS 4.5 S8.S 0 4»

Claims (24)

1. A sucrose fatty acid ester composition comprising: (a) from 60% to 97% by weight intermediate melting sucrose fatty acid esters containing at least four fatty acid ester groups, each fatty acid group 5 having from 8 to 22 carbon atoms, wherein the sucrose fatty acid esters have: Ci) a non-Newtonian plastic rheoiogy at 100°F (37.8°C), in particidsir a yield stress of not less than 15 Pa (150 dynes/cm2) and a viscosity of not less than 1.5 Pa.s (15 poise) 10 at 1Q0®F C37„8®C) after 19 minutes of steady shear -1 at 10 sec. . (ii) a liquid/solid stability of not less than 90% at 100°F (37.8°C); (Hi) an Iodine value between 25 and 55, and (iv) from 5% to 501 solids at 37°C (body temperature); and 15 (b) from 3% to 101 by weight hardstock material selected from the group consisting of hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof, wherein the hardstock has an iodine value not more than HO X2.

2. A composition according to Claim 1 wherein the iodine value of the intermediate melting sucrose fatty acid esters is between 38 and 55.

3. A composition according to Claim 1 wherein the 25 average fatty acid chain length of the hardstock material fatty adds is not less than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids.

4. A composition according to Claim 3 wherefe the average fatty acid chain length of the hardstock material fatty 30 acids is at least one carbon unit longer than the - 44 - average fatty acid chain length of the intermediate melting sucrose ester fatty acids.

5. A composition according to Claim 3 wherein the hardstock material comprises sucrose fatty acid esters. 5 S. A composition according to Claim 5 wherein the combination of intermediate melting sucrose fatty acid esters and hardstock has a yield stress of not less than 13 Pa (150 dynes/cm2)P a viscosity of not less than 1^5 Pa.s (15 poise) at 100°P

6. -I (37. 8°C) after 10 minutes of steady shear at 10 seconds and 10 a liquid/solid stability of not less than 90% at 100°F (37.8°C).

7. A composition according to Claim 5 wherein, the average fatty acid chain length of the hardstock material fatty acids is at least one carbon unit longer than the average fatty acid chain length of the intermediate melting 15 sucrose ester fatty acids.

8. A composition according to Claim 7 wherein the combination of intermediate melting sucrose fatty acid esters and hardstock has a yield stress of not less than 15 Pa (150 dynes/cm2 ), a viscosity of not less than 1.5 Pa.s (15 poise) at 100 °F 20 (37.8°C) after 10 minutes of steady shear at 10 seconds 1 and a liquid/solid stability of not less than 90% at 100°F (37.8°C).

9. S. A composition according to Claim 1 comprising from 5% to 25% by weight hardstock Material.

10. A composition according to Claim 1 comprising from 25 10% to 25% by weight hardstock materiel.

11. A composition according to Claim 1 wherein the hardstock Is selected from the group consisting of hardstock - 45 - triglyceride® and hardstock sucrose fatty acid esters, sad mixtures thereof.,

12. A composition according to Claim 11 wherein th® average fatty add chain length of the hardstock material fatty 5 adds Is st least one carbon unit longer than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids.

13. A composition according to Claim I wherein the hardstock Is a triglyceride. 10

14. A composition according to Claim 13 wherein the average fatty add chain length of the hardstoclc material fatty acids is at least one -carbon unit longer than the average fatty add chain length of the intermediate melting sucrose ester fatty adds.

15. 15. A composition . comprising from 60% to 98% by weight intermediate saeltMg sucrose fatty add esters, from 1% to 39% by weight of the first hardstock material of Claim 3 and additionally comprising from 1% to 39% by weight of a second hardstock 20 materiel selected from the group consisting of hardstock triglycerides and hardstock polyol fatty add esters, and mixtures thereof, wherein the second hardstock has an iodine value not more than 12, and wherein the average fatty acid chain length ©f the second hardstock material fatty acids 25 is less than the average fatty add chain length of the intermediate melting sucrose ester fatty adds.

16. A shortening composition comprising: (a) from 10% to 801 by weight of a sucrose fatty acid ©ster composition comprising: (i> fro® 60% to 97% toy weight intermediate melting sucrose fatty acid esters containing at least four fatty acid ester groups, each fatty acid group has from " 8 to 22 carbon atoms,, wherein the intermediate melting sucrose fatty acid esters have an iodine value between 25 and 55, from 5% to 50% solids at 37 °C (body temperature), a non-Newtonian plastic rheoiogy at 100°F (37.8°C)» and in particular a yield stress of not less than 15 Pa (150 dynes/cm2) and a viscosity of not less than 1.5 Pa.s (15 poise) at 100°F (37.8°C) after 10 minutes ot steady shear at 10 sec. and a liquid/solid stability of not Hess than 90% at 100°F (37.8°C); (ii) from 3% to 40% by weight first hardstock material selected from the group consisting of hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof, wherein the hardstock has an iodine ^alue ss©t more than. 12, and wherein the average fatty acid chain length of the hardstock material fatty acids is not less than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids; from 20% to 90% by weight soft oil; tram 0% to 50% by weight intermediate melting triglyceride; from 0% to 20% by weight second hardstock material selected from the group consisting of hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof, wherein the second hardstock material has en iodine value not sore than 12, astd wherein the average fatty acid chain length of the second hardstock material fatty acids is less thai?, the average - 47 - fatty acid chain length of the intermediate melting sucrose ester fatty acids (e) from 0% to 15% other shortening ingredients.

17. A shortening according to Claim 16 wherein the 5 average fatty acid chain length of the first hardstock materiel fatty acids is greater than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids.

18. A shortening according to Claim 16 wherein the average fatty acid chain length of the first hardstock material 10 fatty adds is not less than th® average fatty add chain length of the intermediate melting sucrose ester fatty acids and the first hardstock material comprises sucrose fatty acid esters.

19. A margarine composition comprising: 15 (a) from 10% to 60% by weight of a sucrose fatty acid ester composition comprising: (I) from 60% to 97% by weight intermediate melting sucrose fatty acid esters containing at least four fatty acid ester groups, each fatty acid group 20 having from 8 to 22 carbon atoms,, wherein the stscrose fatty acid esters have an iodine value between 25 and 55, from 5% to 50% solids at 37°C (body tenperature)f and wherein the sucrose fatty acid esters have: a 25 non-Newtonian plastic rheoiogy at 100®F (37.8°C), in particular a yield stress of not less than 15 Pa (150 dynes /on2) and a viscosity of not less than 1.5 Pa.s (15 poise) at 100°? (37„8°C5 after 10 minutes of steady shear -7 at 10 sec. *, and a liquid/solid stability of not less 30 than 20% at 100°F (37.8°C); (ii) from 3% to 40% by weight hardstock material selected from the group consisting of - 48 - hardstock triglycerides and hardstock polyol fatty acid esters, and mixtures thereof, wherein the hardstock has an iodine value not more than 12, arid wherein the average fatty acid chain length 5 of the hardstock material fatty acids is not Hess than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids; (b) from 20% to 70% by weight soft oil; (c) from ©% to 10% by weight intermediate 10 melting triglyceride; (d) from 0% to 15% other margerine ingredients; C\ Ti r3 (e) from 0.1% to 20% water.

20. A margarine according to Claim 19 wherein the 15 average fatty acid chain length of the hardstock material fatty adds is greater than the average fatty add chain length of the intermediate melting sucrose ester fatty adds.

21. A margarine according to Claim 19 wherein the average fatty add chain length of the hardstock material fatty 20 adds is not less than the average fatty acid chain length of the intermediate melting sucrose ester fatty acids and the hardstock material comprises sucrose fatty add esters.

22. - A sucrose fatty.acid ester composition according to Claim I, substantially as hereinbefore described with particular reference to Examples 1 and 2 of the accompanying Examples..

23. - A shortening composition according to Claim 16, substantially as hereinbefore described with particular reference to Sxample 3 of the accompanying Examples. §

24. A margarine composition according t© Claim 19, substantially as hereinbefore described with particular reference to Example 4 of the accompanying Examples. F. R„ KELLY & CO., AGENTS FOR THE APPLICANTS.