US20020081366A1

US20020081366A1 - Triglycerides, rich in polyunsaturated fatty acids

Info

Publication number: US20020081366A1
Application number: US09/998,179
Authority: US
Inventors: Frederick Cain; Gerald Mcneill; Stephen Moore
Original assignee: Loders Croklaan BV
Current assignee: Loders Croklaan BV
Priority date: 1995-04-28
Filing date: 2001-12-03
Publication date: 2002-06-27
Anticipated expiration: 2016-04-29
Also published as: US6410078B1

Abstract

Triglycerides, that have at least two long chain polyunsaturated fatty acids L₁and L₂, from which at least one is present for more than 20 wt %, while the weight ratio L₁:L₂is at least 2 and which triglycerides also contain at least 2 wt % of saturated fatty acids with 2-12 and/or 20-24 C-atoms, but not more than 10 wt % of saturated fatty acids with 16-18 C-atoms, while at least 5 wt % of the saturated C₂-C₁₂or C₂₀- C₂₄fatty acid residues is bonded on a triglyceride molecule, wherein at least L₁and/or L₂is present, display a number of advantageous properties (e.g. higher oxidative stability, healthier, lower caloric, structuring properties, digestibility).

Description

According to EP 265 699 fats with a superior digestibility and absorptivity are obtained, when these fats are composed of triglycerides having a specific amount of C ₈to C₁₄fatty acid residues at the 2-position, while residues with C₁₈or higher fatty acids are bonded at the 1.3-positions. Typical examples of the C₁₈and higher fatty acids are polyunsaturated fatty acids, such as arachidonic acid, eicosapentenoic acid and dodecahexenoic acid. However nothing is disclosed about fat compositions that combine in the fat saturated fatty acid residues and at least two different long chain polyunsaturated fatty acid residues. In WO 90/04012 it is disclosed that triglycerides that contain saturated C₈/C₁₀fatty acid residues in 1.3 and simultaneously a polyunsaturated fatty acid residue (in particular DHA) in the 2-position, have beneficial nutritional properties, in particular for enteral or parenteral purposes. However again, nothing is disclosed about fat compositions that contain in the fat specific amounts of saturated and two different polyunsaturated fatty acid residues.

From WO 94/00044 it is known that fatblends that contain unhardened fish oil have significant health benefits. Fish oil often contains appreciable amounts of two different polyunsaturated fatty acids, e.g. DHA and EPA. However it is also known that fish oil has a number of draw backs, such as a low oxidative stability (e.g. noticed as off taste during storage at ambient temperature). Further fish oils do not have structuring properties, which makes it difficult to apply them in fat compositions wherein a structuring agent is required in order to give the fat composition a performance, that is desired to make the fat applicable in foodproducts.

From Endo c.s in Bioscience Biotechn. Biochem. 57 (12) 1993 pages 2202-2024 it is known, that incorporation of myristic acid groups into sardine oil leads to a product with a slightly improved oxidation rate, whereas incorporation of stearic acid in the sardine oil hardly had any effect on the oxidation rate. This incorporation of saturated fatty acid is performed by an enzymic process, applying Candida cylindracea or lypozyme as an enzyme. It is taught that starting from sardine oil with about 8% DHA and 12% EPA, products are obtained with a decreased amount of total long chain polyunsaturated fatty acids (about 11% if C _14:0was incorporated and about 17.5% if stearic acid was incorporated).

Therefore, above document does not disclose triglycerides that contain at least 20 wt % of a most abundant long chain polyunsaturated fatty acid in combination with at least 2% of saturated C ₂-C₁₂or C₂₀-C₂₄fatty acids.

U.S. Pat. No. 5,151,291 discloses triglycerides that are rich in EPA and that also contain “higher fatty acid residues”. The higher fatty acid residues are defined as saturated fatty acid with at least 14 C-atoms, but also DHA could be considered as such. The products obtained must combine a high EPA level with a high melting point in order to make them suitable as margarine fat. Because of above requirements the triglyceride products never will combine levels of a most abundant long chain polyunsaturated fatty acid of more than 20% with the presence of a second most abundant long chain polyunsaturated fatty acid in a ratio between these two LCPUFA's of more than 2, while also at least 2% saturated C ₂-C₁₂or C₂₀-C₂₄fatty acid will be present in these triglycerides.

We have performed a study to find out, whether fat compositions existed, that could overcome the draw backs of the known fat compositions, while they would retain the beneficial effects of the presence of relatively high amounts of polyunsaturated fatty acids. This study has resulted in the finding of novel fats, that combine the following beneficial product properties:

our novel fats display better oxidative stability than triglycerides with similar compositions, however not having our levels of saturated fatty acids present;

our novel fats are better for the development of the brain, in particular when consumed by infants. This effect is due to the relatively high levels of dodecahexenoic acid (DHA) in our fats;

our novel fats also can contain relatively high levels of eicosapentenoic acid (EPA), which makes our fats healthier, due to the effect of EPA on coronary diseases;

our novel fats display a lower calorific behaviour. This is due to the presence of the short chain saturated fatty acid, which will decrease the molecular weight of our fats and thereby will decrease simultaneously its caloric contents. Fats, that contain long chain saturated fatty acids, such as behenic acid, display a reduced fat absorption by the body and thus display a decreased digestibility;

our novel fats display better structuring properties than fats without the saturated fatty acids;

our novel fats can be obtained as a result of interesterification reactions, in particular enzymic interesterification, which results in fats with a better triglyceride-distribution than known fats. Simultaneously these fats will display an improved melting behaviour as our fats will hardly contain any trisaturated triglycerides.

our interesterified fats will also give better digestion of polyunsaturated fatty acids because, as a result of the interesterification with short or medium chain fatty acids tripolyunsaturated triglycerides will be hardly present in our fats.

So our inventions concerns with novel fats, that display one or more of above beneficial effects. Our novel fats can be described as a triglyceride-composition, comprising at least two long chain polyunsaturated fatty acids L ₁and L₂, both having at least 3 unsaturations and having at least 20 carbon atoms from which L₁is the most abundant and L₂is the second most abundant, wherein the triglyceride composition contains at least 20 wt % of L₁, while the weight ratio L₁:L₂is at least 2, and the triglyceride composition also contains at least 2 wt % preferably at least 5 wt %, more preferably at least 15 wt %, most preferably at least 30 wt % of saturated fatty acids with 2-12 and/or 20-24 carbon atoms, whereas the triglyceride composition does not contain more than 10 wt % of saturated fatty acids with 16-18 carbon atoms, while at least 5 wt % of the saturated C₂-C₁₂or C₂₀- C₂₄fatty acid residues is bonded on a triglyceride molecule, wherein at least L₁and/or L₂is present.

Preferred fats are triglyceride compositions according to claim 1, wherein the amount of L₁is more than 30 wt %, while the weight ratio L₁:L₂is at least 3, while triglyceride compositions according to claims 1 or 2, wherein the amount of L₁is at least 40 wt % and the weight ratio of L₁:L₂is at least 3.5 are even more preferred.

The most preferred C ₂-C₁₂saturated fatty acids are acetic acid, butyric acid, octanoic acid, and lauric acid. It was found, that fats with relatively low levels of C₁₆-C₁₈saturated fatty acids could be obtained. Advantageously the level of C₁₆-C₁₈saturated fatty acids is less than 8 wt %, in particular less than 5 wt %.

The most abundant polyunsaturated fatty acid L, is preferably DHA (=C _22:6). The second most abundant polyunsaturated fatty acid advantageously is EPA (C_20:5). Very useful triglycerides are obtained, when L₁=EPA and L₂=DHA.

We found that the best oxidative stability was obtained, if at least 5 wt %, preferably at least 10 wt %, most preferably at least 20 wt % of the saturated C ₂-C₁₂or C₂₀-C₂₄fatty acid residues is bonded on a triglyceride molecule, wherein at least L₁and/or L₂is present.

Our triglycerides can be applied as such in foodproducts, however it can also be very suitable to blend our novel fats first, before applying them. Therefore part of our invention is also a blend of triglycerides, comprising

0.3-95 wt % of triglycerides according to claims 1-7, and

99.7-5 wt % of a complementary fat, having a solid fat index at 10° C. (N ₁₀) that is either at least 5% more, or at least 5% less than the N₁₀of the triglycerides according to claims 1-7.

Above blends suitably can be composed of 5-80 wt %, in particular 20-70 wt % of the triglycerides according to claims 1-7, and 95-20 wt %, in particular 80-30 wt % of the complementary fat.

Many types of complementary fat could be applied. However we prefer to use complementary fats having a solid fat content (NMR-pulse; not stabilized) of more than 15 at 20° C., preferably more than 20. The N-values were measured on fats subjected to the following T-regime: 5 minutes at 60° C., 60 minutes at 0° C. and 30 minutes at the measuring temperature.

Very useful complementary fats for our blends can be selected from cocoa butter equivalents, cocoa butter, palm oil or fractions thereof, palmkernel oil or fractions thereof, interesterified mixtures of above fats or fractions or hardened components thereof, or from liquid oil, such as sunflower oil, high oleic sunflower oil, soyabean oil, rapeseed oil, cottonseed oil, safflower oil, high oleic safflower oil, maize oil, MCT oils or fish oils.

The blends so obtained display a solid fat content (NMR-pulse; not stabilized) of 0-85, preferably 10-70, most preferably 20-60 at 5° C. and less than 30, preferably <20, most preferably<5 at 35° C.

Although our fats already have an improved oxidative stability, we found that this stability can be further improved when our blends contain an effective amount of an oxidation stabilizer, selected from the group consisting of: natural or synthetic tocopherols, other natural anti-oxidants, BHT, BHA, free radical scavengers, enzymes with anti-oxidant properties. Effective amounts can range from 100 ppm to 5 wt % (on fat).

Part of our invention are also the foodproducts, comprising a fat phase, such as spreads, margarine, cream alternative, infant food, chocolate, confectionery, bakery products, sauces, ice-creams, ice-cream coatings, cheese, soups, mayonnaise, dressings, enteral or parental products, wherein the fat phase contains a fat according to claims 1-13.

Our fats can be obtained by preparing the pure triglycerides and blending these in the required ratios. However a very useful method for the preparation of our blends is an interesterification of a (non-hardened) fish oil with a saturated fatty acid. This interesterification can be performed by using an enzyme. In that case enzymes can be applied, that display a specificity for e.g. long chain polyunsaturated fatty acids over saturated fatty acids, or that display a preference for one long chain polyunsaturated fatty acid over another long chain polyunsaturated fatty acid.

In our example I we have set out another possible interesterification method for the preparation of our novel fats. According to this method a fish oil is first subjected to a glycerolysis in the presence of a lipase. The crude reaction product obtained is enriched in long chain polyunsaturated fatty acids. This crude product is reconverted to triglycerides by performing an interesterification, using a fat high in saturated fatty acids.

Other methods to prepare our novel fats are illustrated by our other examples.



wf (TUNA) f = TUNAf =	The olein fraction of semi refined tuna
	oil obtained by low temperature solvent
	fractionation, having at least 35% of
	DHA.
(BOO)s =	The stearin fraction of an enzymic
	interesterified blend of high oleic
	sunflower oil and behenic acid.
fhPO =	Fully hardened palm oil.
CCB =	Cocoa butter.
POf37 =	Partially hardened palm oil olein
	fraction melting point of 37° C.
CN =	Coconut oil.
CNs =	Coconut oil stearin fraction.
nPOm =	Wet fractionated palm oil mid fraction.
df (PO) f =	Dry fractionated palm oil olein
	fraction.
HS1 = Hardstock =	The stearin fraction of a chemical
	interesterrified blend of fully
	hardened palm oil and a fully hardened
	palm kernel olein fraction.
SF =	Sunflower oil.
PC =	Palm oil.
in =	Interesterified.

EXAMPLE I

A fish oil enriched in 20:5 and 22:6 is prepared by reacting menhaden oil (composition given in table 1.) with glycerol in the presence of Pseudomonas cepacia lipase at a temperature of 37° C. The ratio of oil to glycerol is 3 (wt/wt) and the quantity of lipase is 1% by weight on oil. 5% water by weight is present in the glycerol. After 48 hours the reaction is terminated by heating to 100° C. and the glycerol is separated from the reaction mixture. The triglycerides are separated from the glyceride fraction by adsorption of the partial glycerides and the free fatty acids (FFA) onto silica, to give the enriched oil of composition shown in table 1. This oil is interesterified with hardened high erucic acid rapeseed oil (composition in table 1.) using a lipase catalyst (Rhizomucor miehei), to give the final product oil with a composition given in table 1. All the above processes are carried out under nitrogen to prevent deterioration of the oil.

TABLE 1


Fatty acid composition (wt %).

	C14:0	C16:0	C16:1	C16:u	C18:0	C18:1	C18:2	C18:3	C18:4	C20:0

Original oil	8.3	19.6	11.9	6.5	3.4	12.4	1.3	1.5	2.5	0.8
Enriched oil	0.3	4.3	6.7	3.8	1.5	16.9	1.8	1.7	3.5	1.0
Hardened high	0.0	3.3	0.0	0.0	36.0	0.0	0.0	0.0	0.0	8.9
erucic acid
rapeseed oil
(HEAR oil)
88% enriched	0.3	4.2	5.9	3.3	5.6	14.9	1.6	1.5	3.1	1.9
fish oil +
12% hardened
HEAR oil

	C20:1	C20:5	C20:u	C22:0	C22:1	C22:5	C22:6	C22:u	C24:0

Original oil	0.3	14.5	3.6	0.0	0.3	2.5	6.5	1.3	0.0
Enriched oil	2.8	28.1	6.8	0.0	0.0	5.6	13.6	1.9	0.0
Hardened high	0.0	0.0	0.0	49.2	0.0	0.0	0.0	0.0	2.6
erucic acid
rapeseed oil
(HEAR oil)
88% enriched	2.5	24.7	6.0	5.9	0.0	4.9	12.0	1.7	0.3
fish oil +
12% hardened
HEAR oil

EXAMPLE II

A low temperature solvent fractionation at −70° C. was done on semi refined tuna oil with the composition, mentioned in table II, under the conditions as mentioned in “Progress in the chemistry of fats and other lipids” vol. 3 Holman R. T. et al 1995, using 4 L of acetone per Kg tuna oil to enrich the oil in DHA and EPA. After removal of the acetone the olein fraction of the tuna oil (=wf(tuna)f) with the composition, mentioned in table 2, was obtained. This fraction was stored in the freezer under nitrogen. [0032]
All the ingredients for the enzymic interesterification were stored at ambient for at least one hour. All oils were used as liquid oils. To the tuna oil olein fraction 400 ppm of anti-oxidant (BHT) was added. [0033]
The tuna oil olein fraction was divided in different portions. Then the liquid complementary fat was added to each of the tuna oil olein fractions and mixed in. A sample was taken for carbon number and FAME analyses. For the enzymic interesterification a 1,3 specific lipase ([0034] Rhizomucor Miehei) was used. The lipase was added to the mixed oils in a weight ratio of 40:1 oil:lipase. A nitrogen blanket was put over the mixture to prevent deterioration of the oil. The reaction mixture was put in a magnetic stirred heatblock and the temperature was adjusted to 60° C. After 96 hours the reaction was stopped.
The samples were cleaned through an alumina column to remove FFA, mono- and diglycerides. Carbon number and FAME analyses were done via GC on the samples before and after lipase treatment. [0035]
Two methods were used to prove that at least 5% of the total amount of C2-C12 and/or C20-C24 was bonded on a triglyceride molecule with L1 and/or L2. The first method involves a calculation and gives the maximum amount which is bonded on a triglyceride molecule with L1 and/or L2. The second method which involves an analytical method gives some information about the minimum amount which is bonded on the same triglyceride molecule with L1 and/or L2. [0036]
A statistical programm was used to calculate a carbon number based on the randomized distribution of the fatty acids in a triglyceride molecule. This programm was checked by using the FAME results of a (random) chemical interesterification for a standard interesterified fat mix from palm oil stearin/palm kernel stearin and comparing the calculated carbon number profile with the measured carbon number profile (see table 3). The differences were very small so that it was concluded that the programm gives the correct results. Then the enzymic interesterification according to the invention was tested. The FAME and carbon number of the enzymic interesterified product was measured. The measured carbon number was equated to the calculated carbon number and the differences were very small. Because of this we concluded that the enzymic interesterification resulted in a random distribution of the fatty acids in the triglyceride molecule. In a randomized interesterified product it is possible to calculate the amount of C2-C12 and/or C20-C24 bonded on a triglyceride molecule with L1 and/or L2. [0037]
The second method is an analytical method. Two parts of the sample (Band a and band b) with a certain amount of unsaturation were collected by using Silver-ion HPLC. Band A had about 6 till 9 unsaturations and Band B had 9 till 18 unsaturations. On the triglycerides of the two bands FAME and carbon number analyses were done. From these FAME analyses a carbon number was calculated by using the statistical programm. This carbon number was equated to the measured carbon number. From these analyses and calculations it was possible to calculate the minimum amount of C2-C12 and/or C20-C24 which was bonded on a triglyceride molecule with L1 and/or L2. The actual amount will be even higher because there was more sample than just the two analyzed bands. [0038]
Interesterification experiments were done on the following blends: [0039]
75/25 wf(tuna)f/tributyrin [0040]
75/25 wf(tuna)f/tricaprin [0041]
75/25 wf(tuna)f/(BOO)s [0042]
75/25 wf(tuna)f/fhPO (=comparative example) [0043]
The composition of tributyrin; tricaprin; (BOO)s and fhPO are given in table 2. [0044]
The experiments were done according to the method described above. The experiments were stopped after 96 hours. The carbon number and FAME of the blends and the interesterified blends were determined. The results of the FAME analyses are listed in table 4 and the results of the carbon number analyses are listed in table 5. [0045]
The results of the calculated amount of C2-C12 and/or C20-C24 which is bonded on a triglyceride molecule with L1 and/or L2 are listed in table 6, 7 and 8. The results of the analyzed amount of C2-C12 and/or C20-C24 which is bonded on a triglyceride molecule with L1 and/or L2 are listed in table 9. [0046]

EXAMPLE III

Interesterification experiments were done on the following blends: [0047]
A: 75/25 wf(tuna)f/tributyrin [0048]
B: 75/25 wf(tuna)f/tricaprin [0049]
C: 75/25 wf(tuna)f/(BOO)s [0050]
D: 75/25 wf(tuna)f/fhPO (comparative example) [0051]
The tributyrin, tricaprin, (BOO)s and fhPO are the same as in example II (see table 2). [0052]
The experiments were done according to the method described in example II. This tuna olein fraction was alumina treated to remove FFA, mono- and diglycerides, before lipase treatment. After 96 hours the experiments were stopped. The analyses of the reaction mixtures of tributyrin, tricaprin and (BOO)s were done. The results of all these analyses are listed in tables 10 and 11. Part of the reaction mixture was cleaned again by using an alumina column to remove the FFA, mono- and diglycerides and oxidised materials. This cleaned material was mixed in a ratio of 1/99 with a palm oil olein fraction with a bland smell. This was stored at ambient for three days and evaluated by the panel. The results from the panel using the different products obtained were as follows: The panel was asked to make a ranking of the samples on fish smell. [0053]

C B A D

C B A D

C A B D

B C A D
Least flavour-->Strongest flavour [0054]
Everyone in the panel agreed that the product from D was the worst and the others were far better. So the samples according to the invention (A, B and C) were all better than the comparative example (D). [0055]
The results of the calculated amount of C2-C12 and/or C20-C24 which is bonded on a triglyceride molecule with L1 and/or L2 are listed in table 12, 13 and 14. The results of the analyzed amount of C2-C12 and/or C20-C24 which is bonded on a triglyceride molecule with L1 and/or L2 are listed in table 15. [0056]

EXAMPLE IV

A fish oil concentrate was made according to the following procedure. [0057]
1. Chemical Hydrolysis of Tuna oil [0058]
Method adapted from Ratnayake et al (Fat Sci. Tech. 90 10 1988 page 381) [0059]
Tuna oil (200g) was refluxed for 1 hour in an atmosphere of nitrogen with a mixture of 47 g of potassium hydroxide pellets, 260 mls ethanol (96%), and 88 mls deionised water. The saponified mixture was diluted with 500 mls of water and the non-saponifiable matter was extracted with hexane (3×100 ml). The aqueous layer was neutralised with 500 mls of 1 M HCl. The free fatty acids were extracted into hexane (3×100 ml). The hexane was removed by evaporation. [0060]
2. Urea Fractionation of Tuna Acids [0061]
Method adapted from Robles Medina et al JAOCS vol 72 no 5 (1995) [0062]
The fatty acids (100 g) were added with stirring to a hot (60° C.) solution of 400 g of Urea and 800 mls of ethanol. The mixture was stirred for 1 hour before the temperature was reduced by 1° C./hour to 4° C. at which temperature the mixture was held for 16 hours. The mixture was fractionated to remove the stearin fraction. The ethanol was removed from the olein fraction by evaporation. The olein was mixed with 250 mls of hexane and 250 mls of 1 M HCl. The hexane layer was isolated and the aqueous layer washed with a further 100 ml hexane. The hexane was removed by evaporation. [0063]
3. Recombination to triglyceride [0064]
Batch 1 [0065]
47 g of Tuna acids were mixed with approximately 4 g of glycerol and 4 g of [0066] Rhizomucor miehei in a jacketed vessel at 55° C. with a magnetic stirrer. Nitrogen was allowed to blow over the surface to remove any water produced during the reaction. The reaction was allowed to continue for 10 days until the FFA had been substantially reduced. The product after removal of the enzyme by filtration was stirred at 60° C. with 50 g of basic alumina in 100 mls of hexane. The alumina was removed by filtration.
Batch 2 [0067]
The free fatty acids were divided into 4 samples which were recombined to triglyceride on 12 to 15 g scale in glass vials at 55° C. in a magnetic hot block. Typically 14 g of free fatty acid were mixed with 1.3 g glycerol and 0.7 g [0068] Rhizomucor miehei. Nitrogen was allowed to flow over the surface to remove water. The reactions were allowed to continue for 1 week. 50 g of product, after removal of the enzyme by filtration, was stirred at 60° C. with 270 g of basic alumina in 100 mls of hexane. The alumina was removed by filtration.
The oil from “Recombination to triglycerides” batch 1 was called D58. [0069]
Interesterification experiments were done on the following blends: [0070]
75/25 fish oil concentrate (=D58)/tricaprin [0071]
75/25 fish oil concentrate (=D58)/(BOO)s [0072]
The interesterification experiments were done according to the method of example II. [0073]
The interesterification experiments of the fish oil concentrate and the tricaprin and (BOO)s were stopped after 115 hours. The FAME and carbon number analysis were done, the results are listed in table 16 and 17. [0074]
The results of the calculated amount C2-C12 and/or C20-C24 which is bonded on a triglyceride molecule with L1 and/or L2 of these samples are listed in table 18 and 19. [0075]

EXAMPLE V

The interesterification experiments were done according to the method of example II. This time the interesterification reactions were stopped after 46 hours. [0076]
The two following interesterified blends were used: [0077]
70/30 wf(TUNA)f (=D40)/Tributyrin [0078]
70/30 wf(TUNA)f (=D40)/(BOO)s [0079]
The FAME and carbon numbers of these interesterified mixtures are listed in table 20 and 21. [0080]
D40 being a tuna oil olein fraction, obtained by low temperature solvent fractionation, having about 38 wt % of DHA. [0081]

EXAMPLE VI

Blends were made of the two interesterified mixtures (=in(FISH)) and a complementary fat/fat blend for the following applications:



		Blends inside
Application	Reference	the patent

Chocolate	Cocoa butter	Cocoa
		butter/in (FISH)
		99/1
Bakery	POf37/df(PO)f	POf37/df(PO)f/
	40/60	in (FISH)
		40/50/10
Ice cream	Coconut oil	CN/CNs/in(FISH)
coatings		90/5/5
Ice cream	PO	PO/in (FISH)
		90/10
Non dairy creams	nPOm/df(PO).f	nPOm/df(PO)f/in
	40/60	(FISH)
		40/40/20
Health margarines	HS1/SF 13/87	HS1/SF/in (FISH)
/Health spreads		13/77/10
Confectionery	nPOm/df (PO) f	nPOm/df (PO) f/in
fillings	60/40	(FISH)
		60/20/20
Mayonnaise/	SF	SF/in (FISH)
Sauces		90/10
Dressings	SF	SF/in(FISH)
		90/10

EXAMPLE VII

Range style dressings were made according to the following recipe: [0083]

wt %

Liquid oil 25.0

Maltodextrin 20.0

Dried egg yolk 0.8

Xanthum gum 0.4

Vinegar 5.0

Water 44.8
In above recipe three different liquid oils were applied. The liquid oil for the reference was Sunflower oil and the liquid oils according to the invention were as follows: [0084]
Sunflower oil/in(D40/tributyrin) 90/10 [0085]
Sunflower oil/in(D40/(BOO)s) 90/10 [0086]
The FAME results of the in(D40/tributyrin) and the in(D40/(BOO)s) are listed in table 20. Results of the NMR measurements of the two blends according to the invention are listed in table 22b. [0087]
A large batch of aqueous phase was manufactured and used for all the dressings. The water and maltodextrin were first blended using a Silverson mixer. The egg yolk, xanthum gum and vinegar were sequentially added whilst continuing to stir with the Silverson until complete mixing had occurred. At this stage the pH=3.25, therefore no further adjustment to the pH was made. [0088]
The oils were slowly added to the aqueous phase whilst mixing using the Silverson. Mixing was continued until all the oil had been dispersed. The dressings were transferred to 200 ml plastic sterile bottles. [0089]
The viscosities of the samples were determined using a Brookfield Viscometer fitted with a number 4 spindle rotating at 10 rpm. The samples were contained in identical 200 ml plastic bottles hence the viscosities are directly comparable with each other. For each sample the average of three measurements was taken with the sample being allowed to relax for 1 minute between each 1 minute of shear. The viscosity results of the dressings are listed in table 23. [0090]
The oil droplet size distribution was determined using a Malvern Mastersizer using a 45 mm filter. The results of these measurements, as Sauter-mean particle diameter are listed in table 23. [0091]

EXAMPLE VIII

Spreads were made according to the following recipe: [0092]

Fat Phase

Fat Blend 40%

Hymono 7804 0.3%

Colour (2% β-carotene) 0.02%

Total 40.32%
[0093]

Aqueous Phase (to pH 5.1)

Water 56.44%

Skimmed Milk Powder 1.5%

Gelatin (270 bloom) 1.5%

Potassium Sorbate 0.15%

Citric Acid Powder 0.07%

Total 59.66%
In above recipe three different fat blends were applied. The fat blend for the reference was HS1/Sunflower oil 13/87 and the fat blends according to the invention were as follows: [0094]
HS1/Sunflower oil/in(D40/tributyrin) 13/77/10 [0095]
HS1/Sunflower oil/in(D40/(BOO)s) 13/77/10 [0096]
The FAME results of the in(D40/tributyrin) and the in(D40/(BOO)s) are listed in table 20. Results of the NMR measurements of the two blends according to the invention are listed in table 22a. [0097]
The spreads were processed according to the following procedure: [0098]
2 kg of material was prepared and processed. [0099]

A micro-votator processing line was set up as follows:



	Premix conditions	Stirrer Speed 60 rpm
		Temperature 50° C.
	pump	Proportioning pump set at 60% (30
		g/min.).
	A₁conditions	Shaft speed 1000 rpm
		Temperature set at 8° C.
	C₁conditions	Shaft speed 1000 rpm
		Temperature set to 10° C.
	A₂conditions	Shaft Speed 1000 rpm
		Temperature set to 10° C.
	C₂conditions	Shaft speed 1000 rpm
		Temperature set to 13° C.

The aqueous phase was prepared by heating the required amount of water to approximately 80° C. and then, using a silverson mixer, slowly mixing in the ingredients. The pH of the system was adjusted to 5.1 by adding 20% Lactic acid solution as required. [0101]
A premix was prepared by stirring the fat phase in the premix tank and then slowly adding in the aqueous phase. When addition was complete, the mix was stirred for a further 5 minutes before pumping through the line. When the process had stabilised (around 20 minutes), product was collected for storage and evaluation. [0102]

The typical process conditions were as follows:



					Line
	A_{1 Exit}	C_{1 Exit}	A_{2 Exit}	C_{2 Exit}	Pressure
Sample	(° C.)	(° C.)	(° C.)	(° C.)	(bar)

Reference	13.2	18.7	13.6	15.6	0.5 to
					2
HS1/SF/	13.2	19.5	13.8	15.6	1 to
in (D40/					3.4
tributyrin)
13/77/10
HS1/SF/	12.3	19.1	13.8	15.5	1.2 to
in (D40/					3.5
(BOO)s)
13/77/10

For all three systems, very good oil continuous low fat spreads were produced using this system. [0104]
Evaluations were done on C-value and on conductivity. The C-value in g/cm[0105] ²of the spreads was measured by using a cone penetrometer. The conductivity in μ siemens/cm was measured by using a Wayne Kerr.

20° C.

Sample C-value Conductivity

Reference 190 10⁻⁵

HS1/SF/ 180 10⁻⁵

in (D40/tr

ibutyrin)

HS1/SF/ 180 10⁻⁵

in (D40/

(BOO)s)
All samples spread very easily on grease-proof paper, with no obvious signs of water loss. [0106]

EXAMPLE IX

Ice cream was made according to the following recipe: [0107]

wt %

Fat blend 10.0

Skimmed milk powder 10.0

Icing sugar 12.0

Corn syrup solids 4.0

Dextrose monohydrate 2.0

Sherex IC 9330 ® 0.6

Water 61.4

Total 100.0
Sherex IC 9330® is a product from Quest International and comprises mono- and diglycerides admixed with different stabilizers. [0108]
In above recipe three different fat blends were applied. The fat blend for the reference was PO/Sunflower oil 90/10 and the fat blends according to the invention were as follows: [0109]
PO/in(D40/tributyrin) 90/10 [0110]
PO/in(D40/(BOO)s) 90/10 [0111]
The FAME results of the in(D40/tributyrin) and the in(D40/(BOO)s) are listed in table 20. Results of the NMR measurements of the two blends according to the invention are listed in table 22a. [0112]
All ingredients except the water and the fat were mixed. Then the cold water was added to this mixture. This mixture was heated in a water bath till a temperature of 70° C. Then the fully liquid palm oil was added to the mixture while “stirred” in the ultra-turrax. This emulsion was cooled in a water bath at 20° C. until a temperature of 30° C. was reached. The emulsion was stirred in the ultra-turrax again. The batch ice cream machine was held for 24 hours at −28° C. prior to use. The emulsion was placed in the batch ice cream machine and stirred for 15 minutes. The resulting ice cream was stored at −20° C. for 24 hours and then evaluated. [0113]
The viscosity of the ice cream emulsion, prior to freezing was measured. The overrun and hardness were determined. The viscosity was measured by using the Haake viscometer. Hardness was measured by using a Stevens texture analyser with a 45° cone at a speed of 0.5 mm/second till a deepness of 2 mm. [0114]

Overrun Hardness

Sample (%) (gram)

Reference 31.5 142

PO/in (D40/tributyrin) 31.5 148

PO/in (D40/(BOO)s) 36.7 185

The viscosities of the emulsions were similar.

TABLE 2


FAME data for the components used

	Semi
	refined			Tri-
FAME	tuna oil	wf(TUNA)f	Tributyrin	caprin	(BOO)s	fhPO

C4:0	0.0	0.0	99.0	0.0	0.0	0.0
C10:0	0.0	0.0	0.0	99.7	0.0	0.0
C12:0	0.1	0.0	0.0	0.3	0.0	0.3
C12:othe	0.0	0.0	0.0	0.0	0.0	0.0
C14:0	3.5	1.7	0.0	0.0	0.1	1.0
C14:othe	1.6	0.3	0.0	0.0	0.0	0.0
C16:0	20.8	3.1	0.0	0.0	1.9	41.7
C16:1	5.4	7.6	0.0	0.0	0.0	0.0
C16:othe	4.7	3.2	0.0	0.0	0.0	0.0
C18:0	6.1	0.6	0.0	0.0	3.1	54.6
C18:1	14.8	16.1	0.0	0.0	29.0	1.5
C18:2	1.2	3.1	0.0	0.0	2.3	0.2
C18:3	0.7	0.9	0.0	0.0	0.0	0.0
C18:othe	1.9	1.7	0.0	0.0	0.0	0.0
C20:0	0.4	0.0	0.0	0.0	3.4	0.5
C20:1	1.1	1.1	0.0	0.0	0.1	0.0
C20:2	0.0	0.2	0.0	0.0	0.0	0.0
C20:3	0.0	0.0	0.0	0.0	0.0	0.0
C20:4	0.0	0.0	0.0	0.0	0.0	0.0
C20:5	5.1	12.0	0.0	0.0	0.0	0.0
C20:othe	3.1	4.0	0.0	0.0	0.0	0.0
C22:0	0.0	0.0	0.0	0.0	58.5	0.1
C22:1	0.3	0.0	0.0	0.0	0.1	0.0
C22:5	1.5	2.1	0.0	0.0	0.0	0.0
C22:6	24.8	39.6	0.0	0.0	0.0	0.0
C22:othe	2.9	2.8	0.0	0.0	0.0	0.0
C24:0	0.0	0.0	0.0	0.0	1.5	0.1
Others	0.0	0.0	1.0	0.0	0.0	0.0
Total	100.0	100.0	100.0	100.0	100.0	100.0

TABLE 3


Programm check on chemical interesterification.

		Calculated
wfPOs/PKs	in	by statistical
(blend)	(wfPOs/PKs)	programm

FAME
C8:0 (%)	0.6	0.6
C10:0 (%)	1.1	1.1
C12:0 (%)	22.5	22.5
C14:0 (%)	10.0	9.9
C16:0 (%)	50.2	50.5
C17:0 (%)	0.1	0.1
C18:0 (%)	40.3	4.3
C18:1 (%)	9.9	10.0
C18:2 (%)	0.6	0.7
C20:0 (%)	0.3	0.3
C22:0 (%)	0.1	0.0
Carbon number
C28	0.1	0.0	0.0
C30	0.2	0.0	0.0
C32	1.4	0.4	0.2
C34	2.7	0.7	0.4
C36	11.5	3.3	2.5
C38	10.4	4.2	3.4
C40	6.4	12.7	11.4
C42	4.1	12.3	11.7
C44	2.4	21.9	22.1
C46	3.7	17.0	17.8
C48	30.5	15.5	17.0
C50	21.7	9.0	10.2
C52	3.8	2.5	2.9
C54	1.1	0.4	0.3
C56	0.1	0.1	0.0
C58	0.1	0.0	0.0

TABLE 4


FAME results

	TUNAf/	in	TUNAf/	in	TUNAf/	in	TUNAf/	in
	butyrin	(TUNAf/	caprin	(TUNAf/	BOOs	(TUNAf/	fhPO	(TUNAf/
FAME	(blend)	butyrin)	(blend)	caprin)	(blend)	BOOs)	(blend)	fhPO)

C4:0	30.3	36.7	0.0	0.0	0.0	0.0	0.0	0.0
C10:0	0.0	0.0	37.0	34.5	0.0	0.0	0.0	0.0
C12:0	0.1	0.0	0.1	0.1	0.1	0.1	0.0	0.0
C12:othe	0.1	0.0	0.1	0.1	0.1	0.1	0.0	0.0
C14:0	1.6	1.6	1.3	1.4	1.4	1.4	1.8	1.8
C14:othe	0.6	0.6	0.4	0.6	0.6	0.5	0.5	0.5
C16:0	4.8	4.9	4.1	4.4	5.0	5.0	19.5	18.6
C16:1	5.1	5.2	4.5	4.6	4.4	4.5	4.5	4.7
C16:othe	2.7	2.8	2.4	2.6	2.4	2.5	2.4	2.5
C18:0	0.7	0.8	0.6	0.7	1.8	1.8	20.6	19.9
C18:1	11.4	11.7	10.1	10.5	21.2	21.0	10.5	10.9
C18:2	1.2	1.2	1.1	1.1	2.0	2.0	2.0	1.8
C18:3	0.7	0.6	0.6	0.7	0.6	0.6	0.5	0.6
C18:othe	1.8	1.5	1.6	2.0	1.6	1.6	0.9	0.9
C20:0	0.0	0.0	0.0	0.0	1.2	1.2	0.2	0.2
C20:1	0.8	0.8	0.7	0.8	0.7	0.8	0.8	1.0
C20:2	0.3	0.2	0.2	0.3	0.2	0.2	0.3	0.2
C20:3	0.2	0.2	0.2	0.3	0.3	0.2	0.2	0.1
	1.7	1.5	1.6	1.7	1.6	1.6	1.6	1.7
C20:5	7.0	5.8	6.4	6.2	6.3	6.2	6.5	6.4
C20:oth	0.7	0.5	0.6	0.7	0.6	0.6	0.7	0.7
C22:0	0.0	0.0	0.0	0.0	21.8	21.3	0.1	0.1
C22:1	0.3	0.3	0.3	0.3	0.0	0.0	0.3	0.3
C22:5	1.2	1.1	1.2	1.2	1.2	1.2	1.3	1.3
C22:6	25.1	20.3	23.2	23.2	23.0	23.6	23.1	23.7
C22:othe	1.9	1.8	1.5	2.2	1.8	1.9	1.9	2.1
C24:0	0.0	0.0	0.0	0.0	0.4	0.4	0.0	0.0
Total	100.3	100.1	99.8	100.2	100.3	100.3	100.2	100.0

TABLE 5


Carbon number results

	TUNAf/	in	TUNAf/	in	TUNAf/	in	TUNAf/	in
Carbon	butyrin	(TUNAf/	caprin	(TUNAf/	BOOs	(TUNAf/	fhPO	(TUNAf/
Number	(blend)	butyrin)	(blend)	caprin)	(blend)	BOOs)	(blend)	fhPO)

C12	19.9	11.0	0.0	0.0	0.0	0.0	0.0	0.0
C20	0.0	0.1	0.0	0.0	0.0	0.0	0.0	0.0
C22	0.0	2.7	0.0	0.0	0.0	0.0	0.0	0.0
C24	0.0	12.7	0.0	0.0	0.0	0.0	0.0	0.0
C26	0.0	11.2	0.0	0.0	0.0	0.0	0.0	0.0
C28	0.0	6.7	0.0	0.0	0.0	0.0	0.0	0.0
C30	0.0	6.0	37.6	9.5	0.0	0.0	0.0	0.0
C32	0.0	0.2	0.2	0.1	0.0	0.0	0.0	0.0
C34	0.2	0.7	0.1	1.2	0.0	0.0	0.0	0.0
C36	0.4	2.2	0.1	6.9	0.2	0.0	0.0	0.0
C38	0.7	3.8	0.3	8.5	0.4	0.1	0.0	0.0
C40	1.2	5.6	0.5	5.8	0.7	0.2	0.0	0.0
C42	1.4	7.1	0.7	11.0	1.1	0.5	0.0	0.0
C44	1.2	6.3	0.7	5.0	0.9	0.7	0.0	0.2
C46	1.4	4.7	0.9	6.4	0.7	0.6	0.2	0.6
C48	1.9	6.7	1.4	9.1	1.9	2.0	3.2	2.9
C50	4.0	1.6	3.1	8.5	3.7	3.7	14.9	10.2
C52	6.9	1.4	5.3	6.2	5.5	6.8	18.6	16.2
C54	11.0	1.9	8.7	9.5	9.3	10.9	13.5	18.7
C56	14.0	2.3	11.2	3.5	12.8	15.2	11.6	16.6
C58	14.5	2.2	11.1	3.2	19.1	17.7	12.4	14.3
C60	12.5	1.9	10.3	3.1	15.5	16.0	13.4	10.1
C62	7.1	1.0	6.2	1.9	25.2	15.7	12.1	10.2
C64	1.7	0.0	1.6	0.6	2.1	4.7	0.0	0.0
C66	0.0	0.0	0.0	0.0	0.9	4.7	0.0	0.0
C68	0.0	0.0	0.0	0.0	0.0	0.5	0.0	0.0
Total	100.0	100.0	100.0	100.0	100.0	100.0	99.9	100.0

TABLE 6


Calculated results of example II of the amount of
C4:0 which is bonded on a triglyceride molecule
with L1 and/or L2.
75/25 wf(tuna)f/tributyrin

						wt % of the total
						added amount Bu
						bonded on a
Carbon	Analyzed	Calculated	% Bu + x + L1/L2	% Bu + Bu + L1/L2	Bu	molecule with L1
number	(wt %)	(wt %)	(wt %)	(wt %)	wt %	and/or L2

C12	11.0	14.7	0.0	0.0	0.0	0.0
C20	0.1	0.0	0.0	0.0	0.0	0.0
C22	2.7	1.6	0.0	0.0	0.0	0.0
C24	12.7	9.1	0.0	0.0	0.0	0.0
C26	11.2	10.7	0.0	0.0	0.0	0.0
C28	6.7	5.9	0.0	3.9	1.1	3.0
C30	6.0	15.1	0.0	13.0	3.5	9.4
C32	0.2	0.1	0.0	0.0	0.0	0.0
C34	0.7	0.6	0.0	0.0	0.0	0.0
C36	2.2	2.3	0.0	0.0	0.0	0.0
C38	3.8	4.2	0.0	0.0	0.0	0.0
C40	5.6	5.3	2.4	0.0	0.2	0.7
C42	7.1	7.7	5.7	0.0	0.5	1.5
C44	6.3	6.7	5.4	0.0	0.5	1.3
C46	4.7	3.4	2.7	0.0	0.2	0.6
C48	6.7	4.4	4.0	0.0	0.3	0.9
C50	1.6	0.5	0.0	0.0	0.0	0.0
C52	1.4	0.8	0.0	0.0	0.0	0.0
C54	1.9	1.2	0.0	0.0	0.0	0.0
C56	2.3	1.4	0.0	0.0	0.0	0.0
C58	2.2	1.4	0.0	0.0	0.0	0.0
C60	1.9	1.3	0.0	0.0	0.0	0.0
C62	1.0	0.9	0.0	0.0	0.0	0.0
C64	0.0	0.4	0.0	0.0	0.0	0.0
C66	0.0	0.3	0.0	0.0	0.0	0.0
Total	100.0	100.0			6.4	17.5

TABLE 7


Calculated results of example II of the amount of
C10:0 which is bonded on a triglyceride molecule
with L1 and/or L2.
75/25 wf(tuna)f/tricaprin

						wt % of the total
						added amount Ca
						bonded on a
Carbon	Analyzed	Calculated	Ca + x + L1/L2	Ca + Ca + L1/L2	Ca	molecule with L1
number	(wt %)	(wt %)	(wt %)	(wt %)	wt %	and/or L2

C30	9.5	7.5	0.0	0.0	0.0	0.0
C32	0.1	0.1	0.0	0.0	0.0	0.0
C34	1.2	1.1	0.0	0.0	0.0	0.0
C36	6.9	6.0	0.0	0.0	0.0	0.0
C38	8.5	7.4	0.0	0.0	0.0	0.0
C40	5.8	5.3	0.0	2.9	1.5	4.2
C42	11.0	14.5	0.0	10.5	5.0	14.5
C44	5.0	4.4	0.3	0.0	0.1	0.2
C46	6.4	6.1	2.4	0.0	0.5	1.5
C48	9.1	9.7	6.9	0.0	1.4	4.2
C50	8.5	9.4	7.2	0.0	1.4	4.2
C52	6.2	6.3	4.2	0.0	0.8	2.3
C54	9.5	8.5	6.2	0.0	1.1	3.3
C56	3.5	2.9	0.0	0.0	0.0	0.0
C58	3.2	3.0	0.0	0.0	0.0	0.0
C60	3.1	3.2	0.0	0.0	0.0	0.0
C62	1.9	2.4	0.0	0.0	0.0	0.0
C64	0.6	1.2	0.0	0.0	0.0	0.0
C66	0.0	1.0	0.0	0.0	0.0	0.0
Total	100.0	100.0			11.9	34.4

TABLE 8


Calculated results of example II of the amount of
C22:0 which is bonded on a triglyceride molecule
with L1 and/or L2.
75/25 wf(tuna)f/(BOO)s

						wt % of the total
						added amount Be
						bonded on a
Carbon	Analyzed	Calculated	Be + x + L1/L2	Be + Be + L1/L2	Be	molecule with L1
number	(wt %)	(wt %)	(wt %)	(wt %)	wt %	and/or L2

C38	0.1	0.0	0.0	0.0	0.0	0.0
C40	0.2	0.0	0.0	0.0	0.0	0.0
C42	0.5	0.0	0.0	0.0	0.0	0.0
C44	0.7	0.0	0.0	0.0	0.0	0.0
C46	0.6	0.2	0.0	0.0	0.0	0.0
C48	2.0	0.8	0.0	0.0	0.0	0.0
C50	3.7	2.4	0.0	0.0	0.0	0.0
C52	6.8	5.1	0.0	0.0	0.0	0.0
C54	10.9	8.9	0.0	0.0	0.0	0.0
C56	15.2	14.0	0.0	0.0	0.0	0.0
C58	17.7	17.0	1.5	0.0	0.6	2.7
C60	16.0	16.5	5.1	0.0	1.9	8.8
C62	15.7	18.8	7.8	0.0	2.8	13.0
C64	4.7	6.8	2.4	0.7	1.3	6.1
C66	4.7	9.2	3.9	2.6	3.0	14.2
C68	0.5	0.0	0.0	0.0	0.0	0.0
Total	100.0	99.7	0.0	0.0	9.5	44.8

TABLE 9


Analyzed results of example II of the amount of
C2-C12 and or C20-C24 which is bonded on a
triglyceride molecule with L1 and/or L2.

		Sum of
		Cno's		Target
		containing	Sum of	acids in	Target	Therefore
		target	target	target	acids in	target acids
	Band as %	TAG in	acids in	TAGs in	total	in target
HPLC	TAGs	band	band	band	FAME on	TAGs (% wt on
band	(g/100 g)	(% wt)	(% wt)	(g/100 g)	TG (% wt)	total FAME)

in (TUNAf/	A	21.9	79.8	20.2	3.5	36.7	9.6
Butyrin)	B	19.5	62.8	5.9	0.7	36.7	2.0
						Total:	11.6
in (TUNAf/	A	28.3	92.0	28.9	7.5	34.5	21.8
Caprin)	B	26.5	56.6	21.1	1.8	34.5	5.3
						Total:	27.1
in (TUNAf/	A	34.2	15.3	21.5	1.1	21.3	4.9
BOOs)	B	32.0	10.0	8.4	0.3	21.3	1.2
						Total:	6.1

TABLE 10


FAME results example III

	TUNAf/	in	TUNAf/	in	TUNAf/	in	in
	butyrin	(TUNAf/	caprin	(TUNAf/	BOOs	(TUNAf/	(TUNAf/
FAME	(blend)	butyrin)	(blend)	caprin)	(blend)	BOOs)	fhPO)

C4:0	27.6	28.3	0.0	0.0	0.0	0.0	0.0
C10:0	0.0	0.0	29.7	28.5	0.0	0.0	0.0
C12:0	0.0	0.0	0.1	0.1	0.1	0.1	0.1
C12:other	0.4	0.3	0.1	0.1	0.1	0.1	0.1
C14:0	1.5	1.5	1.4	1.4	1.4	1.5	1.8
C14:other	0.5	0.4	0.5	0.5	0.5	0.5	0.6
C16:0	2.7	2.7	2.5	2.5	3.1	3.2	14.8
C16:1	5.2	5.2	5.1	5.0	5.0	5.1	5.2
C16:other	2.5	2.7	2.3	2.5	2.5	2.5	2.6
C18:0	0.3	0.4	0.3	0.3	1.2	1.2	17.3
C18:1	11.4	11.4	11.1	11.0	19.9	20.5	12.1
C18:2	1.3	1.3	1.3	1.3	2.0	2.0	1.4
C18:3	0.7	0.7	0.7	0.7	0.7	0.7	0.7
C18:other	2.1	2.0	1.9	2.0	1.9	1.9	1.8
C20:0	0.0	0.0	0.0	0.0	0.9	0.9	0.2
C20:1	0.7	0.7	0.7	0.7	0.8	0.8	0.8
C20:2	0.2	0.2	0.2	0.2	0.2	0.2	0.2
C20:3	0.2	0.2	0.2	0.2	0.3	0.3	0.2
C20:4	1.8	1.8	1.8	1.8	1.8	1.7	1.7
C20:5	8.2	7.9	8.0	8.0	8.1	7.6	7.5
C20:other	0.9	0.9	0.9	0.9	0.9	0.9	0.7
C22:0	0.0	0.0	0.0	0.0	16.4	17.5	0.0
C22:1	0.2	0.2	0.2	0.3	0.0	0.0	0.3
C22:5	1.4	1.3	1.3	1.3	1.5	1.4	1.3
C22:6	28.1	28.3	27.6	28.9	28.5	27.4	26.6
C22:other	1.9	1.9	1.9	1.9	1.9	1.9	1.8
C24:0	0.0	0.0	0.0	0.0	0.3	0.3	0.0
Total	99.8	100.3	99.8	100.1	100.0	100.2	99.8

TABLE 11


Carbon number results example III

	TUNAf/	in	TUNAf/	in	TUNAf/	in	in
Carbon	butyrin	(TUNAf/	caprin	(TUNAf/	BOOs	(TUNAf/	(TUNAf/
Number	(blend)	butyrin)	(blend)	caprin)	(blend)	BOOs)	fhPO)

C12	16.6	6.7	0.0	0.0	0.0	0.0	0.0
C20	0.0	0.1	0.0	0.0	0.0	0.0	0.0
C22	0.0	1.4	0.0	0.0	0.0	0.0	0.0
C24	0.0	6.3	0.0	0.0	0.0	0.0	0.0
C26	0.0	9.4	0.0	0.0	0.0	0.0	0.0
C28	0.0	6.1	0.0	0.0	0.0	0.0	0.0
C30	0.0	7.3	30.0	4.7	0.0	0.0	0.0
C32	0.0	0.2	0.2	0.1	0.0	0.0	0.0
C34	0.0	0.4	0.1	0.9	0.0	0.0	0.0
C36	0.0	1.7	0.2	4.2	0.0	0.0	0.1
C38	0.1	3.5	0.0	6.1	0.0	0.0	0.1
C40	0.2	5.9	0.0	5.0	0.2	0.1	0.2
C42	0.3	8.0	0.0	9.3	0.4	0.4	0.4
C44	0.4	8.1	0.1	4.3	0.4	0.5	0.6
C46	0.9	6.2	0.3	6.2	0.7	0.8	1.3
C48	1.1	11.0	0.6	9.3	1.0	1.6	3.9
C50	3.1	0.9	2.3	9.7	2.9	3.6	9.7
C52	5.8	1.2	4.7	7.6	5.3	7.2	14.9
C54	10.1	2.1	8.3	11.5	9.0	11.5	17.7
C56	14.3	3.0	12.4	4.9	13.6	16.4	17.5
C58	16.5	3.6	14.4	4.9	20.5	19.4	13.1
C60	14.9	3.6	13.8	5.2	16.1	17.3	10.7
C62	11.0	2.9	8.6	4.4	25.5	15.6	7.0
C64	3.4	0.4	3.5	1.7	3.5	3.9	2.3
C66	1.3	0.0	0.5	0.0	0.9	1.7	0.5
C68	0.0	0.0	0.0	0.0	0.0	0.0	0.0
Total	100.0	100.0	100.0	100.0	100.0	100.0	100.0

TABLE 12


Calculated results of example III of the amount
of C4 which is bonded on a triglyceride molecule
with L1 and/or L2.
75/25 wf(tuna)f/tributyrin

C12	6.7	8.4	0.0	0.0	0.0	0.0
C20	0.1	0.0	0.0	0.0	0.0	0.0
C22	1.4	1.0	0.0	0.0	0.0	0.0
C24	6.3	5.6	0.0	0.0	0.0	0.0
C26	9.4	8.0	0.0	0.0	0.0	0.0
C28	6.1	5.7	0.0	3.9	1.1	3.9
C30	7.3	15.1	0.0	13.5	3.6	12.7
C32	0.2	0.0	0.0	0.0	0.0	0.0
C34	0.4	0.4	0.0	0.0	0.0	0.0
C36	1.7	1.7	0.0	0.0	0.0	0.0
C38	3.5	3.4	0.3	0.0	0.1	0.4
C40	5.9	5.4	2.4	0.0	0.2	0.8
C42	8.0	8.7	6.6	0.0	0.6	2.2
C44	8.1	9.0	7.7	0.0	0.7	2.5
C46	6.2	5.7	5.1	0.0	0.4	1.6
C48	11.0	7.4	7.3	0.0	0.6	2.1
C50	0.9	0.4	0.0	0.0	0.0	0.0
C52	1.2	0.9	0.0	0.0	0.0	0.0
C54	2.1	1.5	0.0	0.0	0.0	0.0
C56	3.0	2.1	0.0	0.0	0.0	0.0
C58	3.6	2.4	0.0	0.0	0.0	0.0
C60	3.6	2.7	0.0	0.0	0.0	0.0
C62	2.9	2.2	0.0	0.0	0.0	0.0
C64	0.4	1.2	0.0	0.0	0.0	0.0
C66	0.0	1.1	0.0	0.0	0.0	0.0
Total	100.0	100.0			7.4	26.3

TABLE 13


Calculated results of example III of the amount
of C10:0 which is bonded on a triglyceride
molecule with L1 and/or L2.
75/25 wf(tuna)f/tricaprin

C30	4.7	4.6	0.0	0.0	0.0	0.0
C32	0.1	0.0	0.0	0.0	0.0	0.0
C34	0.9	0.8	0.0	0.0	0.0	0.0
C36	4.2	3.8	0.0	0.0	0.0	0.0
C38	6.1	5.6	0.0	0.0	0.0	0.0
C40	5.0	4.6	0.0	2.8	1.4	4.9
C42	9.3	12.5	0.0	9.6	4.6	16.0
C44	4.3	3.6	0.3	0.0	0.1	0.2
C46	6.2	5.7	2.7	0.0	0.6	2.1
C48	9.3	9.4	7.2	0.0	1.5	5.3
C50	9.7	10.4	8.1	0.0	1.6	5.7
C52	7.6	7.7	6.0	0.0	1.2	4.0
C54	11.5	10.7	8.0	0.0	1.5	5.2
C56	4.9	3.6	0.0	0.0	0.0	0.0
C58	4.9	4.2	0.0	0.0	0.0	0.0
C60	5.2	4.7	0.0	0.0	0.0	0.0
C62	4.4	4.0	0.0	0.0	0.0	0.0
C64	1.7	2.3	0.0	0.0	0.0	0.0
C66	0.0	2.0	0.0	0.0	0.0	0.0
Total	100.0	100.2			12.4	43.4

TABLE 14


Calculated results of example III of the amount
of C22:0 which is bonded on a triglyceride
molecule with L1 and/or L2.
75/25 wf(tuna)f/(BOO)s

C40	0.1	0.0	0.0	0.0	0.0	0.0
C42	0.4	0.0	0.0	0.0	0.0	0.0
C44	0.5	0.0	0.0	0.0	0.0	0.0
C46	0.8	0.2	0.0	0.0	0.0	0.0
C48	1.6	0.7	0.0	0.0	0.0	0.0
C50	3.6	2.1	0.0	0.0	0.0	0.0
C52	7.2	4.6	0.0	0.0	0.0	0.0
C54	11.5	8.5	0.0	0.0	0.0	0.0
C56	16.4	13.3	0.0	0.0	0.0	0.0
C58	19.4	17.1	1.8	0.0	0.7	3.9
C60	17.3	17.0	4.8	0.0	1.8	10.1
C62	15.6	19.1	7.5	0.0	2.7	15.2
C64	3.9	7.8	3.0	0.6	1.4	8.3
C66	1.7	9.4	4.2	2.1	2.8	16.0
Total	100.0	99.8			9.3	53.4

TABLE 15


Analyzed results of example III of the amount of C2-C12 and or C20-C24 which is bonded
on a triglyceride molecule with L1 and/or L2.

						Therefor
		Sum of		Target		target
		Cho's	Sum of	acids in	Target	acids in
		containing	target	target	acids in	target
	Band as	target TAG	acids in	TAGs in	total	TAGs (% wt
HPLC	% TAGs	in band	band	band	FAME on	on total
band	(g/100 g)	(% wt)	(% wt)	(g/100 g)	TG (% wt)	FAME)

in	A	29.8	78.2	15.7	3.7	28.3	12.9
(TUNAf/	B	32.0	62.3	4.6	0.9	28.3	3.2
Butyrin)						Total:	16.2
in	A	32.9	21.5	17.9	1.3	17.5	7.2
(TUNAf/	B	42.0	16.8	8.3	0.6	17.5	3.3
BOOs)						Total:	10.6

TABLE 16


FAME results example IV

		in (D58/	in (D58/
FAME	D58	caprin)	(BOO)s)

C10:0	0.0	29.1	0.0
C12:0	0.0	0.1	0.0
C12:other	0.0	0.1	0.0
C14:0	0.1	0.1	0.1
C14:other	0.5	0.3	0.3
C16:0	0.1	0.3	0.7
C16:1	1.0	0.9	0.7
C16:other	3.4	2.7	2.5
C18:0	0.2	0.4	1.1
C18:1	0.9	1.2	10.4
C18:2	1.8	1.7	2.2
C18:3	0.8	0.6	0.5
C18:other	3.5	2.4	2.2
C20:0	0.0	0.1	1.1
C20:1	0.1	0.1	0.1
C20:2	0.0	0.0	0.0
C20:3	0.4	0.4	0.4
C20:4	4.6	3.3	3.3
C20:5	16.1	10.8	10.4
C20:other	1.4	1.1	1.0
C22:0	0.0	0.1	19.7
C22:1	0.1	0.0	0.0
C22:5	2.0	1.3	1.4
C22:6	57.3	39.8	37.4
C22:other	5.6	3.5	4.1
C24:0	0.0	0.0	0.4
Total	99.9	100.4	100.0

TABLE 17


Carbon number results example IV

	D58/	in	D58/	in
Carbon	caprin	(D58/	(BOO)s	(D58/
number	(blend)	caprin)	(blend)	(BOO)s)

C30	43.0	10.4	0.0	0.0
C32	0.5	0.7	0.0	0.0
C34	0.5	1.6	0.0	0.0
C36	0.4	2.2	0.0	0.0
C38	0.1	2.9	0.0	0.8
C40	0.2	9.3	0.3	1.8
C42	0.2	19.4	1.0	3.5
C44	0.7	2.3	0.8	3.3
C46	0.7	2.9	1.1	3.8
C48	0.5	5.0	1.0	2.2
C50	1.3	7.5	1.7	2.2
C52	0.9	10.6	1.5	2.4
C54	2.3	14.0	2.6	4.2
C56	4.1	1.4	5.9	7.8
C58	7.3	1.8	17.0	11.7
C60	9.9	2.8	15.8	16.6
C62	12.2	3.1	39.0	19.0
C64	9.0	2.1	7.9	10.6
C66	6.2	0.0	4.4	10.1
C68	0.0	0.0	0.0	0.0
Total	100.0	100.0	100.0	100.0

TABLE 18


Calculated results of example IV of the amount of
C10:0 which is bonded on a triglyceride molecule
with Ll and/or L2.
75/25 D58/tricaprin

C30	10.4	5.0	0.0	0.0	0.0	0.0
C32	0.7	0.0	0.0	0.0	0.0	0.0
C34	1.6	0.2	0.0	0.0	0.0	0.0
C36	2.2	1.6	0.0	0.0	0.0	0.0
C38	2.9	2.5	0.0	0.0	0.0	0.0
C40	9.3	6.0	0.0	4.1	2.1	7.0
C42	19.4	16.4	0.0	14.4	6.9	23.6
C44	2.3	0.8	0.0	0.0	0.0	0.0
C46	2.9	2.0	1.2	0.0	0.3	0.9
C48	5.0	5.3	4.2	0.0	0.9	3.0
C50	7.5	7.4	6.5	0.0	1.3	4.5
C52	10.6	12.4	11.7	0.0	2.3	7.7
C54	14.0	17.0	16.4	0.0	3.0	10.4
C56	1.4	1.1	0.0	0.0	0.0	0.0
C58	1.8	2.2	0.0	0.0	0.0	0.0
C60	2.8	3.8	0.0	0.0	0.0	0.0
C62	3.1	4.8	0.0	0.0	0.0	0.0
C64	2.1	6.0	0.0	0.0	0.0	0.0
C66	0.0	5.4	0.0	0.0	0.0	0.0
Total	100.0	99.9			16.6	57.1

TABLE 19


Calculated results of example IV of the amount of
C22:0 which is bonded on a triglyceride molecule
with L1 and/or L2.
75/25 D58/(BOO)s

C38	0.8	0.0	0.0	0.0	0.0	0.0
C40	1.8	0.0	0.0	0.0	0.0	0.0
C42	3.5	0.0	0.0	0.0	0.0	0.0
C44	3.3	0.0	0.0	0.0	0.0	0.0
C46	3.8	0.0	0.0	0.0	0.0	0.0
C48	2.2	0.0	0.0	0.0	0.0	0.0
C50	2.2	0.2	0.0	0.0	0.0	0.0
C52	2.4	0.7	0.0	0.0	0.0	0.0
C54	4.2	2.1	0.0	0.0	0.0	0.0
C56	7.8	5.1	0.0	0.0	0.0	0.0
C58	11.7	10.4	0.6	0.0	0.2	1.3
C60	16.6	16.1	2.8	0.0	1.0	5.9
C62	19.0	24.4	6.2	0.0	2.2	12.6
C64	10.6	18.5	8.1	1.1	3.5	20.2
C66	10.1	22.2	9.6	3.8	5.7	32.8
C68	0.0	0.0	0.0	0.0	0.0	0.0
Total	100.0	99.7			12.7	64.6

TABLE 20


FAME results of the interesterified mixtures used for the blends.

Fatty Acid Composition (wt %)

	D40	tributyrin/D40	(BOO)s/D40

C4:0	0.0	30	0
C14:0	3.7	3	3
C14unsat/C15	1.1	0	1
C16:0	6.7	0	4
C16:1	4.3	5	3
C16unsat/C17	0.0	6	4
C18:0	2.4	2	3
C18:1	15.6	11	18
C18:2	1.2	1	2
C18:3	0.8	0	0
C18:4	1.4	1	1
Other C18	0.4	0	1
C20:0	0.1	0	1
C20:1	2.0	1	2
C20:2	0.0	0	0
C20:3	0.0	0	0
C20:4	0.0	1	1
C20:5	7.2	5	5
Other C20	1.8	1	0
C22:0	0.0	0	21
C22:1	2.7	2	1
C22:5	4.1	3	3
C22:6	38.4	27	24
Other C22	2.0	1	2

TABLE 21


Carbon number results of the interesterified mixtures used for the blends.

Carbon

tributyrin/D40

(BOO)s/D40

	Number	0-time	46 hours	0-time	46 hours

C12	30.0	7.7	0.0	0.0
C20	0.0	0.1	0.0	0.0
C22	0.0	2.0	0.0	0.0
C24	0.0	7.4	0.0	0.0
C26	0.0	8.0	0.0	0.0
C28	0.0	6.2	0.0	0.0
C30	0.0	13.1	0.0	0.0
C32	0.0	1.2	0.0	0.0
C34	0.0	1.2	0.0	0.0
C36	0.0	1.6	0.0	0.0
C38	0.0	3.3	0.0	0.0
C40	0.0	5.6	0.0	0.0
C42	0.3	6.5	0.3	0.4
C44	1.9	9.4	0.7	1.6
C46	2.0	5.9	2.6	2.0
C48	1.6	8.8	2.4	1.7
C50	2.8	1.7	3.4	3.5
C52	5.1	1.1	5.8	5.7
C54	9.3	1.6	8.8	10.3
C56	9.9	1.6	11.6	13.9
C58	11.8	2.0	17.6	17.7
C60	11.2	2.0	13.7	14.9
C62	9.2	1.6	27.0	18.2
C64	2.7	0.3	4.2	5.2
C66	2.2	0.0	1.9	4.5
C68	0.0	0.0	0.0	0.4

TABLE 22a


N-values of the blends.

		N-5 n.s.	N-10 n.s.	N-20 n.s.	N-35 n.s.
Application	Blend	(%)	(%)	(%)	(%)

Chocolate	Typical values	85-95	80-95	55-65	<1
	99/1 CCB/	88.2	85.6	59.0	0.1
	in (D40/butyrin)
	99/1 CCB/	89.3	85.9	59.5	0.0
	in(D40/(BOO) s)
Bakery	Typical values	40-80	30-75	20-45	<15
	40/50/10 POf37/dfPOf/	41.9	34.6	21.2	0.1
	in (D40/butyrin)
	40/50/10 POf37/dfPOf/	42.2	37.3	23.4	0.4
	in (D40/(BOO) s)
Ice cream	Typical values	65-90	>35	>15	<1
coatings	90/5/5 CN/CNs/	72.3	37.9	31.2	0.2
	in (D40/butyrin)
	90/5/5 CN/CNs/	74.7	61.7	34.2	0.0
	in(D40/(BOO) s)
Ice cream	Typical values	40-60		15-30	<5
	90/10 PO/in (D40/butyrin)	52.9		21.4	3.6
	90/10 PO/in (D40/(BOO) s)	52.0		20.8	3.9
Non dairy	Typical values	1-70		0-37	0-11
creams	40/40/20 nPOm/dfPOf/	50.1		12.5	0.2
	in (D40/butyrin)
	40/40/20 nPOm/dfPOf/	55.4		10.6	0.0
	in (D40/(BOO) s)
Health	Typical values	7-20		3-12	<2.5
margarines/	13/77/10 HS1/SF/	14.7		9.6	1.6
Health	in (D40/butyrin)
spreads	13/77/10 HS1/SF/	17.7		10.6	2.0
	in (D40/ (BOO) s)

TABLE 22b


N-values of the blends.

		N-5 n.s.	N-10 n.s.	N-20 n.s.	N-35 n.s.
Application	Blend	(%)	(%)	(%)	(%)

Confectionery	Typical values	>50	>40	>25	<1
filling	60/20/20 nPOm/dfPOf/	65.8	58.3	31.8	0.1
	in (D40/butyrin)
	60/20/20 nPOm/dfPOf/	69.5	61.7	31.3	0.4
	in (D40/(BOO) s)
Mayonnaise	Typical values	0-10	0-5	<1	<0.5
/Sauces	90/10 SF/in (D40/butyrin)	0.0	0.0	0.0	0.0
	90/10 SF/in (D40/(BOO) s)	0.0	0.7	0.7	0.3
Dressings	Typical values	0-10	0-5	<1	<0.5
	90/10 SF/in (D40/butyrin)	0.0	0.0	0.0	0.0
	90/10 SF/in (D40/(BOO) s)	0.0	0.7	0.7	0.3

TABLE 23


Evaluation results of example VII

		SAUTER MEAN
	VISCOSITY	PARTICLE
OIL	cP	DIAMETER μM

Reference	5940	19.30
Sunflower oil/	5633	16.79
in (D40/tributyrin)
90/10
Sunflower oil/	5600	24.53
in (D40/(BOO)s)
90/10

Claims

1. Triglyceride-composition, comprising at least two long chain poly-unsaturated fatty acids L₁and L₂, both having at least 3 unsaturations and having at least 20 carbon atoms from which L₁is the most abundant and L₂is the second most abundant, wherein the triglyceride composition contains at least 20 wt % of L₁, while the weight ratio L₁:L₂is at least 2, and the triglyceride composition also contains at least 2 wt % preferably at least 5 wt %, more preferably at least 15 wt %, most preferably at least 30 wt % of saturated fatty acids with 2-12 and/or 20-24 carbon atoms, whereas the triglyceride composition does not contain more than 10 wt % of saturated fatty acids with 16-18 carbon atoms, while at least 5 wt %, preferably at least 10 wt %, most preferably at least 20 wt % of the saturated C₂-C₁₂or C₂₀-C₂₄fatty acid residues is bonded on a triglyceride molecule, wherein at least L₁and/or L₂is present.

2. Triglyceride composition according to claim 1, wherein the amount of L₁is more than 30 wt %, while the weight ratio L₁:L₂is at least 3.

3. Triglyceride composition according to claims 1 or 2, wherein the amount of L₁is at least 40 wt % and the weight ratio of L₁:L₂is at least 3.5.

4. Triglyceride composition according to claims 1-3, wherein the amount of C₁₆-C₁₈saturated fatty acids is less than 8 wt %, in particular less than 5 wt %.

5. Triglyceride composition according to claims 1-4, wherein L₁=DHA (=C_22:6).

6. Triglyceride composition according to claims 1-5, wherein L₂=EPA (=C_20:5)

7. Triglyceride composition according to claims 1-6, wherein L₁=EPA and L₂=DHA.

8. Blends of triglycerides comprising:

0.3-95 wt % of triglycerides according to claims 1-7, and

99.7-5 wt % of a complementary fat, having a solid fat index at 10° C. (N₁₀) that is either at least 5% more, or at least 5% less than the N₁₀of the triglycerides according to claims 1-7.

9. Blends of triglycerides, according to claim 8, comprising 5-80 wt %, in particular 20-70 wt % of the triglycerides according to claims 1-7, and 95-20 wt %, in particular 80-30 wt % of the complementary fat.

10. Blends according to claims 8-9, wherein the complementary fat has a solid fat content (NMR-pulse; not stabilized) of more than 15 at 20° C., preferably more than 20.

11. Blends according to claims 8-10, wherein the complementary fat is selected from cocoa butter equivalents, cocoa butter, palm oil or fractions thereof, palmkernel oil or fractions thereof, interesterified mixtures of above fats or fractions or hardened components thereof, or from liquid oil, such as sunflower oil, high oleic sunflower oil, soyabean oil, rapeseed oil, cottonseed oil, safflower oil, high oleic safflower oil, maize oil or MCT oils.

12. Blends according to claims 8-11, wherein the blend displays a solid fat content (NMR-pulse; not stabilized) of 0-85, preferably 10-70, most preferably 20-60 at 5° C. and less than 30, preferably<20, most preferably <5 at 35° C.

13. Triglyceride compositions or blends containing them, according to claims 1-12, wherein the compositions or the blends contain an effective amount of an oxidation stabilizer, selected from the group consisting of: natural or synthetic tocopherols, BHT, BHA, free radical scavengers, enzymes with anti-oxidant properties.

14. Food products, comprising a fat phase, such as spreads, margarine, cream alternative, infant food, chocolate, confectionery, bakery products, sauces, ice-creams, ice-cream coatings, cheese, soups, mayonnaise, dressings, enteral or parental products, wherein the fat phase contains a fat according to claims 1-13.