JPH08311485A - Triglyceride rich in polyunsaturated fatty acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a triglyceride compsn. which is stable to oxidation and is good for health by selecting a specific triglyceride compsn. derived from at least two specific long-chain polyunsatd. fatty acids.

SOLUTION: This compsn. contains at least two 20C or higher long-chain polyunsatd. fatty acids L₁ and L₂, each having at least three unsatd. bonds. The content of L₁ is 20 wt.% or higher; that of L₂ is the next highest; and the wt. ratio of L₁/L₂ is 2 or higher. The compsn. also contains a 2-12C or a 20-24C satd. fatty acid in a content of 2 wt.% or higher, pref. 5 wt.% or higher, still pref. 15 wt.% or higher, esp. pref. 30 wt.% or higher while not more than 10 wt.% 16-18C satd. fatty acid, while 5 wt.% or higher, pref. 10 wt.% or higher, still pref. 20 wt.% or higher, of the 2-12C or 20-24C satd. fatty acid residues is bonded on a triglyceride molecule in which at least L₁ and/or L₂ is present. Pref., the content of L₁ is 30 wt.% or higher and the wt. ratio of L₁/L₂ is 3 or higher.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to triglycerides rich in polyunsaturated fatty acids.

[0002]

2. Description of the Prior Art According to EP 265 699,
Fat has a C ₈ -C ₁₄ fatty acid residues at a specified amount in the 2-position, and the residue of C ₁₈ or higher fatty acids 1,3
When composed of triglycerides linked in the-position, fats with excellent digestibility and absorbency are obtained. C
Typical examples of ₁₈ or higher fatty acids are arachidonic acid,
Polyunsaturated fatty acids such as eicosapentaenoic acid and dodecahexenoic acid. However, nothing is disclosed about a fat composition combining saturated fatty acid residues and at least two different long-chain polyunsaturated fatty acid residues in fat. International publication pamphlet WO 90
/ 04012 contains saturated C ₈ / C ₁₀ in the 1,3-position.
Triglycerides containing fatty acid residues and at the same time polyunsaturated fatty acid residues in the 2-position (especially DHA) are described as having favorable nutritional properties, especially for enteric or parenteral purposes. However, here too, no fat composition is disclosed which comprises a certain amount of saturated fatty acid residues and two different unsaturated fatty acid residues in the fat.

International publication pamphlet WO 94/000
From 44 it is known that fat blends containing uncured fish oil have considerable health benefits. Fish oils often contain significant amounts of two different polyunsaturated fatty acids, such as DHA and EPA. However, fish oil
It is also known to have many drawbacks such as low oxidative stability (e.g. perceived as a change in flavor during storage at ambient temperature). In addition, fish oil has a structured property (structu
use fish oil in a fat composition where structuring agents are required to give the fat composition the desired performance to allow the use of fat in food products. Hard to do.

Bioscience Biotechn. Biochem. 57 (12)
From Endo cs, 1993, 2202-2024, incorporation of myristic acid groups into sardine oil results in a product with slightly improved oxidation rate, but incorporation of stearic acid into sardine oil has little effect on oxidation rate. Is known not to give. This incorporation of saturated fatty acids
It is carried out by an enzymatic process using Candida cylindracea or lypozyme as the enzyme. About 8% DHA and 12% EPA
Starting with a sardine oil having a total amount of long chain polyunsaturated fatty acids reduced (about 11% when C _{14: 0} is incorporated, about 17.5 when stearic acid is incorporated).
%) Is obtained.

The above-referenced documents therefore disclose triglycerides containing at least 20% by weight of the most abundant long-chain polyunsaturated fatty acids combined with at least 2% of saturated C ₂ -C ₁₂ or C ₂₀ -C ₂₄ fatty acids. I haven't.

US Pat. No. 5,151,291 describes EPA-rich, higher fatty acid residues.
Triglycerides including "s" are disclosed. Higher fatty acid residues are defined as saturated fatty acids having at least 14 carbon atoms, but were considered as such in DHA. The resulting product must combine a high EPA concentration with a high melting point to be suitable as a margarine fat. For the above requirement, the triglyceride product, while at least 2% of the saturated C ₂ -C ₁₂ or C ₂₀ -C ₂₄ fatty acid is present in the triglycerides, many of the most abundant long chain polyunsaturated than 20% The concentration of fatty acids is the second most abundant presence of long-chain polyunsaturated fatty acids and the presence of these two longer-chain polyunsaturated fatty acids (LC
It is never a combination of PUFA).

[0007]

SUMMARY OF THE INVENTION We have a fat composition that can overcome the drawbacks of known fat compositions while retaining the beneficial effects of the presence of relatively large amounts of polyunsaturated fatty acids. I did some research to find out if. This study has led to the discovery of new fats. This novel fat combines the following favorable product properties: The novel fat of the invention has the same composition but exhibits better oxidative stability than triglycerides without the saturated fatty acids present of the present invention; The novel fats of the invention are good for brain development, especially when consumed by young children. This effect is due to the relatively high concentration of dodecahexenoic acid (DHA) in the fats of the invention; the novel fats of the invention have a relatively high concentration of eicosapentaenoic acid (EP).
Due to the effect of EPA on heart disease, which also comprises A), the fats of the invention are healthier; the novel fats of the invention show a lower thermogenic behavior. This is due to the presence of short chain saturated fatty acids, which reduce the molecular weight of the fats of the present invention and thereby their caloric content at the same time. Fats containing long-chain saturated fatty acids such as behenic acid have less absorption of fats by the human body and therefore exhibit reduced digestibility; the novel fats of the invention have a better structure than fats without saturated fatty acids. It exhibits oxidising properties; the novel fats according to the invention can be obtained as a result of transesterification reactions, in particular enzymatic transesterifications, which result in fats having a better triglyceride distribution than known fats. At the same time, the fats according to the invention show an improved melting behavior, since they contain few trisaturated triglycerides; the transesterified fats according to the invention give a better digestion of polyunsaturated fatty acids. because,
This is because tripolyunsaturated triglycerides are scarcely present in the fats of the invention as a result of transesterification with short or medium length fatty acids.

[0008]

The present invention therefore relates to novel fats which exhibit one or more of the advantageous effects mentioned above. The novel fats of the present invention can be represented by the triglyceride composition comprises at least two long chain polyunsaturated fatty acids L ₁ and L _2, L ₁ and L both ₂ at least 3
Has two unsaturations and has at least 20 carbon atoms, then L ₁ is the most abundant and L ₂ is the second most abundant,
The triglyceride composition comprises at least 20% by weight L ₁
And the L ₁ : L ₂ weight ratio is at least 2, and the triglyceride composition is at least 2% by weight, preferably at least 5% by weight, more preferably at least 15% by weight, most preferably at least 30% by weight. %
Of saturated fatty acids having 2 to 12 and / or 20 to 24 carbon atoms, while the triglyceride composition does not contain more than 10% by weight of saturated fatty acids having 16 to 18 carbon atoms, at least 5 wt% of saturated C ₂ -C ₁₂ or C ₂₀ -C ₂₄ fatty acid residues is bonded on a triglyceride molecule at least L ₁ and / or L ₂ is present.

[0009]

DETAILED DESCRIPTION OF THE INVENTION Preferred fatty often and weight than the amount of 30 wt% of L ₁ L _1: L ₂ is at least 3 in which the second aspect triglycerides, or amount of at least 40 weight L ₁ % And the weight ratio L ₁ : L ₂ is at least
The composition of claim 3 which is 3.5.

[0010] The most preferred C ₂ -C ₁₂ saturated fatty acids, acetic acid, butyric acid, octanoic acid, and lauric acid. The fat with a relatively low concentration C ₁₆ -C ₁₈ saturated fatty acids is obtained has been found. C ₁₆ -C ₁₈ saturated fatty acid concentration of 8 wt%
Lowers are preferred, and lower than 5% by weight are particularly preferred.

The most abundant polyunsaturated fatty acid L is DHA
(= C _{22: 6} ) is preferable. The second most abundant polyunsaturated fatty acid is advantageously EPA (C _{20: 5} ). When L ₁ = EPA and L ₂ = DHA, very useful triglycerides are obtained.

At least 5% by weight, preferably at least 10% by weight and most preferably at least 20% by weight of at least L ₁ of saturated C _{2 to} C ₁₂ or C _{20 to} C ₂₄ fatty acid residues.
It has been found that the best oxidative stability is obtained when and / or L ₂ is attached on the triglyceride molecule present.

The triglyceride of the present invention can be used as it is in foods. However, it is also very suitable to blend the novel fats according to the invention before use. Therefore,
Part of the invention is 0.3 to 95% by weight of the triglyceride of claims 1 to 7 and 99.7 to 5% by weight of complementary fat, the solid fat index of the triglycerides of claims 1 to 7 at 10 ° C. At least 5% more than (solid fat index) (N ₁₀ ).
Fat with a N ₁₀ that is large or at least 5% smaller,
Is a blend of triglycerides containing.

The abovementioned blends comprise from 5 to 80% by weight, in particular 20
-70% by weight of triglycerides according to claims 1 to 7, and 95
It can optionally consist of ˜20% by weight, especially 80 to 30% by weight of complementary fat.

Many types of complementary fats could be used. However, it is preferred to use complementary fats having a solid fat content (NMR-pulse method; unstabilized (abbreviated as ns)) of greater than 15 at 20 ° C.
It is more preferred to use complementary fats having a solid fat content of greater than 20 at ° C. N-value is 5 at 60 ℃
Min, 60 minutes at 0 ° C., 30 minutes at the measuring temperature.

Very useful complementary fats for the blends of the present invention are cocoa butter equivalents, cocoa butter, palm oil or fractions thereof, palm kernel oil or fractions thereof, transesterification mixtures of said fats or fractions. , Or their hardened ingredients, or sunflower oil, high oleic sunflower oil, soybean oil, rapeseed oil,
It can be chosen from liquid oils such as cottonseed oil, safflower oil, high oleic safflower oil, corn oil, MCT oil, or fish oil.

The blend thus obtained has a temperature of 5 ° C.
At 0-85, preferably 10-70, most preferably 20
A solid fat content (NMR-pulse method; unstabilized) of ~ 60, less than 30, preferably less than 20, at 35 ° C,
Most preferably it has a solid fat content of less than 5.

Although the fats of the present invention already have improved oxidative stability, the blends of the present invention provide an effective amount of natural or synthetic tocopherols, other natural antioxidants, B.
When containing an oxidative stabilizer selected from the group consisting of HT, BHA, radical scavengers, enzymes with antioxidant properties,
It has been found that the oxidative stability can be further improved. Effective amounts may range from 100 ppm (based on fat) to 5% by weight.

Part of the present invention is also a spread, margarine, cream substitute, infant food, chocolate, confectionery, bakery product, sauce, ice cream, ice cream coating, cheese, soup, mayonnaise,
A food product comprising a fat phase, such as a dressing, enteric-coated or parenteral product, the fat phase comprising the fat of claims 1-13.

The fats of the present invention are obtained by preparing pure triglycerides and blending them in the required ratios. However, a very useful method of preparing the blends of the present invention is transesterification of (uncured) fish oil with saturated fatty acids. This transesterification can be carried out enzymatically. In such cases, an enzyme that exhibits specificity for long-chain polyunsaturated fatty acids over saturated fatty acids, or one long-chain polyunsaturated fatty acid over another long-chain polyunsaturated fatty acid Enzymes that show preference can be applied.

In Example I of the present invention another possible transesterification process for the preparation of the novel fats of the present invention was described. According to this method, fish oil is first exposed to glycerolysis in the presence of lipase. The crude reaction product obtained is rich in long-chain polyunsaturated fatty acids. The crude product is reconverted to triglycerides by transesterification with a fat rich in saturated fatty acids.

Other methods for producing the novel fats of the present invention are illustrated by the other examples.

List of abbreviations used and their description wf (tuna) f = tuna f = semi-purified tuna obtained by cryogenic solvent fractionation with DHA of at least 35%.
Oil olein fraction. (BOO) s = stearin fraction of enzymatically transesterified blend of high oleic sunflower oil and behenic acid. fhPO = fully hardened palm oil. CCB = cacao butter POf37 = partially hardened palm oil olein fraction with a melting point of 37 ° C. CN = coconut oil. CNs = coconut oil stearin slurries. nPOm = Wet fractionated palm oil intermediate fraction. df (PO) f = dry fractionated palm oil olein fraction. HS1 = Hardstock = Stearin fraction of a chemically transesterified blend of fully hardened palm oil and fully hardened palm kernel olein fraction. SF = sunflower oil. PO = palm oil. in = transesterified.

[0024]

EXAMPLES Example I Menhaden oil (composition given in Table 1) was mixed with glycerol and Pseudomonas cepacia (Pse).
Fish oils rich in C20: 5 and C22: 6 were prepared by reacting at 37 ° C. in the presence of udomonas cepacia ) lipase. The ratio of oil to glycerol is 3 (weight / weight) and the amount of lipase is 1% by weight based on oil
Met. 5% by weight of water was present in the glycerol.
After 48 hours, the reaction was stopped by heating to 100 ° C. and the glycerol was separated from the reaction mixture. Triglycerides were separated from the glyceride fraction by adsorbing partial glycerides and free fatty acids (FFA) on silica to obtain an enriched oil with the composition shown in Table 1. This oil was hardened with high erucic acid rapeseed oil (composition in Table 1) and lipase catalyst (Rhizomu
trans miehei ) to give a final product oil having the composition given in Table 1. All the above processes were carried out in a nitrogen atmosphere to prevent oil degradation.

[0025]

[Table 1]

Example II For semi-refined tuna oil having the composition shown in Table 2, Holman RT et al., "Progress in the chemistry of"
Under conditions described in "Fats and other lipids," Vol. 3, 1995, low-temperature solvent fractionation was performed at -70 ° C using 4 liters of acetone per kg of tuna oil to convert the oil into DHA. Enriched with EPA After removal of acetone, an olein fraction of tuna oil (= wf (tuna) f) was obtained having the composition shown in Table 2. This fraction was stored in a freezer under a nitrogen atmosphere.

All components for enzymatic transesterification were stored at ambient temperature for at least 1 hour. All oils were used as liquid oils. 400 ppm of antioxidant (BHT) was added to the tuna oil olein fraction.

The tuna oil olein fraction was divided into several parts. The liquid complementary fat was then added to each tuna oil olein fraction and mixed. A sample was taken for carbon number and FAME (Fatty Acid Methyl Ester) analysis (a method of converting a fatty acid residue into a methyl ester and then performing gas chromatography analysis). A 1,3-specific lipase (Rhizomucor miehei) was used for the enzymatic transesterification. Lipase was added to the mixed oil at an oil: lipase weight ratio of 40: 1. A nitrogen blanket was placed over the mixture to prevent oil degradation. Heat block where the reaction mixture is magnetically stirred
The temperature was adjusted to 60 ° C. The reaction was stopped after 96 hours.

The sample was cleaned through an alumina column to remove FFA, mono and diglycerides. The samples before and after the lipase treatment were analyzed for carbon number and FAME by GC (gas chromatography).

Using two methods, at least 5% of C2 to C12 and / or C20 to C24 are L1 and / or L2.
On the triglyceride molecule with The first method involves the calculation and gives the maximum amount bound to L1 and / or L2 on the triglyceride molecule. The second method, including the analytical method, provides some information about the minimum amount bound to L1 and / or L2 on the same triglyceride molecule.

A statistical program was used to calculate carbon numbers based on the randomized distribution of fatty acids in the triglyceride molecule. This program uses FAME results of (random) chemical transesterification on a standard transesterified fat mixture from palm oil stearin / palm kernel stearin, using calculated carbon number profiles and measured carbon number profiles. It was checked by comparing the profiles (see Table 3). The difference was so small that we concluded that the program gave the correct results. Thereafter, transesterification with the enzyme according to the invention was also tested. The FAME and carbon number of the product transesterified by the enzyme were measured. The measured carbon number was equal to the calculated carbon number and the difference was very small. For this reason, we conclude that enzymatic transesterification results in a random distribution of fatty acids in the triglyceride molecule. In the randomized transesterification product, C2 -C bound to L1 and / or L2 on the triglyceride molecule.
It is possible to calculate the amount of 12 and / or C20 to C24.

The second method is an analytical method. Two parts of the sample with a certain amount of unsaturation (band a and band b) were collected using Silver-ion HPLC. Band A had about 6-9 unsaturation and band B had 9-18 unsaturation. Two bands of triglycerides were analyzed for FAME and carbon number. From these FAME analyses, carbon numbers were calculated using a statistical program. This carbon number was equal to the calculated carbon number. From these analyzes and calculations, C bound to L1 and / or L2 on the triglyceride molecule
It is possible to calculate a minimum amount of 2 to C12 and / or C20 to C24. The actual amount will be higher, since there are more samples than just two analyzed bands.

Transesterification experiments were conducted on the following blends: 75/25 wf (tuna) f / tributyrin 75/25 wf (tuna) f / tricaprin 75/25 wf (tuna) f / (BOO) s 75/25 wf (tuna) f / fhPO (= comparative example).

Tributyrin, tricaprin, (BOO)
The composition of s and fhPO are given in Table 2.

Experiments were conducted according to the method described above. The experiment
It stopped after 96 hours. The carbon number and FAME of the blend and the transesterified blend were determined. The results of FAME analysis are shown in Table 4. The results of carbon number analysis are shown in Table 5.

L1 and / or L on the triglyceride molecule
The results of the calculated amounts of C2 to C12 and / or C20 to C24 combined with 2 are shown in Tables 6, 7, and 8. C2-C12 and / or bound to L1 and / or L2 on the triglyceride molecule
Alternatively, Table 9 shows the results of the analytical amounts of C20 to C24.

Example III Transesterification experiments were conducted on the following blends: A: 75/25 wf (tuna) f / tributyrin B: 75/25 wf (tuna) f / tricaprine C: 75/25 wf (tuna) ) F / (BOO) s D: 75/25 wf (tuna) f / fhPO (comparative example).

Tributyrin, tricaprin, (BOO)
s and fhPO are the same as in Example II (see Table 2).

Experiments were conducted according to the method described in Example II. Prior to lipase treatment, the tuna olein fraction was treated with alumina to remove FFAs, mono and diglycerides. The experiment was stopped after 96 hours. Analysis of the reaction mixture of tributyrin, tricaprin, and (BOO) s was performed. The results of all these analyzes are shown in Tables 10 and 11. A portion of the reaction mixture was again cleaned using an alumina column to remove FFA, mono and diglycerides, and oxidised material. This cleaned material was mixed in a ratio of 1/99 with a palm oil olein fraction having a bland smell. It was stored at ambient temperature for 3 days and evaluated by the panel. The panel results for the different products obtained are as follows:

The panel was asked to rank the samples for fish odor.

[0041]

All panels were in agreement that the product from D was the worst and the others were much better. Therefore, the inventive samples (A, B, and C) were all better than the comparative example (D).

L1 and / or L on the triglyceride molecule
The results of the calculated amounts of C2 to C12 and / or C20 to C24 combined with 2 are shown in Tables 12, 13, and 14. C2-C12 and / or bound to L1 and / or L2 on the triglyceride molecule
Alternatively, the results of the analytical amounts of C20 to C24 are shown in Table 15.

Example IV A fish oil concentrate was prepared according to the following method.

1. Chemical hydrolysis of tuna oil Ratnayake et al. (Fat Sci. Tech. 90 10 1988 page 381)
The method adopted from.

A mixture of 47 g of potassium hydroxide pellets, 260 ml of ethanol (96%), and 88 ml of deionized water and tuna oil (200 g) were refluxed under a nitrogen atmosphere for 1 hour. The saponified mixture was diluted with 500 ml of water and the unsaponifiable material was extracted with hexane (100 ml x 3 times). Aqueous layer 1M
Neutralized with 500 ml of HCl. Free fatty acids were extracted into hexane (100 ml x 3 times). Hexane was removed by evaporation.

2. Urea Fractionation of Tuna Acids A method adopted from JAOCS Vol. 72, No. 5 (1995) by Robles Medina et al.

Fatty acid (100 g), 400 g of urea and 800
It was added with stirring to a hot (60 ° C.) solution of ethanol in ml. After stirring the mixture for 1 hour, the temperature was reduced at a rate of 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. Ethanol was removed from the olein fraction by evaporation. Add olein to 250 ml hexane and 250 ml
Of 1 M HCl. The hexane layer was separated and the aqueous layer was washed with an additional 100 ml of hexane. Hexane was removed by evaporation.

3. Reincorporation into triglycerides Batch 1 47 g of tunaic acid were mixed with about 4 g of glycerol and 4 g of Rhizomucor miehei in a 55 ° C. jacketed vessel equipped with a magnetic stirrer. Nitrogen was blown over the surface to remove water formed during the reaction. The reaction was continued for 10 days until there was virtually no FFA. The product, after removal of the enzyme by filtration, was stirred at 60 ° C. with 50 g of basic alumina in 100 ml of hexane. Alumina was removed by filtration.

Batch 2 The free fatty acids were divided into 4 samples which were reincorporated into triglycerides on a scale of 12-15 g in 55 ° C. glass vials in a magnetic hot block. Typically 14 g of free fatty acids were mixed with 1.3 g glycerol and 0.7 g Rhizomucor miehei. The surface was blown with nitrogen to remove the water. The reaction was continued for 1 week. After removing the enzyme by filtration, 50 g of product was stirred with 270 g of basic alumina in 100 ml of hexane at 60 ° C. Alumina was removed by filtration.

"Reincorporation into triglycerides" The oil from batch 1 is called D58.

The transesterification experiments were carried out on the following blends: 75/25 fish oil concentrate (= D58) / tricaprine 75/25 fish oil concentrate (= D58) / (BOO) s The transesterification experiment of Example II Followed method.

Fish Oil Concentrate with Tricaprin and (BOO)
The transesterification experiment with s was stopped after 115 hours. FAM
Analysis of E and carbon number was performed. The results are shown in Tables 16 and 17.

Tables 18 and 19 show the calculated amounts of C2 to C12 and / or C20 to C24 bound to L1 and / or L2 on the triglyceride molecule of these samples.

Example V Transesterification experiments were conducted according to the method of Example II. At this time, the transesterification reaction was stopped after 46 hours.

The following two transesterification blends were used: 70/30 wf (tuna) f (= D40) / tributyrin 70/30 wf (tuna) f (= D40) / (BOO) s These transesterification mixtures FAME and carbon number 20
And Table 21.

D40 is a tuna oil olein fraction having a DHA of about 38% by weight, obtained by cryogenic solvent fractionation.

Example VI A blend was prepared from two transesterification mixtures (= in (fish)) and a complementary fat / fat blend for the following uses:

[0059]

[Table 2] Reference N-value range and N measured for blends
-Values are shown in Tables 22a and 22b.

Example VII A range style dressing was prepared according to the following composition:

Three different liquid oils were used in the above composition. The reference liquid oil was sunflower oil. The liquid oil according to the invention was as follows: -Sunflower oil / in (D40 / tributyrin) 90 / 10-Sunflower oil / in (D40 / (BOO) s) 90/10 in (D40 / tributyrin) and in (D40 / (BO
The results of FAME of O) s) are shown in Table 20. The results of the NMR measurements of the two blends according to the invention are shown in Table 22b.

A large batch of aqueous phase was prepared and used for all dressings. Silverson Mixer (Sil
The water and maltodextrin were first blended using a verson mixer). The egg yolk, xanthan gum, and vinegar were subsequently added, while stirring was continued with a Silverson mixer until thoroughly mixed. At this stage the pH is 3.
25, so no further pH adjustment was done.

While mixing with a Silverson mixer,
The oil was slowly added to the aqueous phase. Mixing was continued until all the oil was dispersed. The dressing was transferred to a 200 ml sterile plastic container.

Brookfield Viscome with a No. 4 spindle rotating at 10 rpm
ter) was used to measure the viscosity of the sample. Since the sample was put in the same 200 ml plastic container,
The viscosities can be compared directly with each other. Each sample was averaged from 3 measurements and the samples were allowed to relax for 1 minute between each 1 minute of shear. The results of dressing viscosity are shown in Table 23.

Oil drop size distribution was measured using a Malvern Mastersizer using a 45 mm filter. The results of these analyzes are shown in Table 23 as Sauter-mean particle diameters.

Example VIII Spreads were prepared according to the following composition: Fat Phase Fat Blend 40% Hymono 7804 0.3% Colorant (2% β-Carotene) 0.02% Total 40.32% Aqueous Phase (up to pH 5.1). Water 56.44% Skim milk powder 1.5% Gelatin (270 bloom) 1.5% Potassium sorbate 0.15% Citric acid powder 0.07% Total 59.66%

Three different fat blends were used in the above composition. The reference fat blend was HS1 / Sunflower oil 13/87. The fat blend according to the invention was as follows: -HS1 / sunflower oil / in (D40 / tributyrin) 13/77 / 10-HS1 / sunflower oil / in (D40 / (BOO) s) 13/77/10 in (D40 / tributyrin) and in (D40 / (BO
The results of FAME of O) s) are shown in Table 20. The results of the NMR measurements of the two blends according to the invention are shown in Table 22a.

Spreads were prepared according to the following procedure.

2 kg of material was prepared and processed.

The micro-votator processing line was set up as follows: premix conditions agitator speed 60 rpm temperature 50 ° C pump metering pump set to 60% (30 g / min) A ₁ condition shaft speed 1000 set in the setting C ₂ conditions shaft speed 1000 rpm temperature 13 ° C. to set the rpm temperature 8 ° C. C ₁ condition setting shaft speed 1000 rpm temperature 10 ° C. a ₂ conditions shaft speed 1000 rpm temperature 10 ° C.

Heat the required amount of water to about 80 ° C., then
The aqueous phase was prepared by slowly mixing the ingredients using a Silverson mixer. 20% as needed
The pH of the system was adjusted to 5.1 by adding lactic acid solution.

Stir the fat phase in a premix tank,
The premix was then prepared by slow addition to the aqueous phase. After the addition was complete, the mix was stirred for an additional 5 minutes and pumped through the line. When the process stabilized (about 20 minutes), the product was collected for storage and evaluation.

Typical process conditions were as follows:

[0074]

[Table 3] For all three systems, very good oil continuous low fat spreads were produced using this system.

The evaluation was carried out on C-value and conductivity. g
C-values in cm / cm ² were measured using a cone penetrometer. The conductivity in μ Siemens / cm is Wayne
It was measured using a Kerr (Wayne Kerr).

[0076]

[Table 4]

All samples spread very easily on greaseproof papers, without showing any obvious signs of water loss.

Example IX An ice cream was prepared according to the following composition: wt% fat blend 10.0 skim milk powder 10.0 icing sugar 12.0 corn syrup solids 4.0 dextrose monohydrate 2.0 Sherex IC9330® 0.6 water 61.4 total 100.0

Shellex IC9330® is a product of Quest International and contains mono- and diglycerides in combination with different stabilizing agents.

Three different fat blends were used in the above composition. The reference fat blend was PO / sunflower oil 90/10. The fat blend according to the invention was as follows: -PO / in (D40 / tributyrin) 90 / 10-PO / in (D40 / (BOO) s) 90/10 in (D40 / tributyrin) and in (D40 / (BO
The results of FAME of O) s) are shown in Table 20. The results of the NMR measurements of the two blends according to the invention are shown in Table 22a.

All ingredients except water and fat were mixed. Then cold water was added to this mixture. The mixture was heated in a water bath to a temperature of 70 ° C. Then completely liquid palm oil was added to the mixture being stirred in the ultra-turrax. The emulsion was cooled in a 20 ° C. water bath to a temperature of 30 ° C. The emulsion was stirred again in Ultra-Turrax. The batch ice cream machine was kept at -28 ° C for 24 hours before use. The emulsion was placed in a batch ice cream machine and stirred for 15 minutes. Store the resulting ice cream at -20 ° C for 24 hours,
Then evaluated.

The viscosity of the ice cream emulsion was measured before freezing. Overrun and hardness were measured. Viscosity is measured by Haake vicomet
er) was used for the measurement. Hardness was measured using a Stevens texture analyzer at a cone angle of 45 ° to a depth of 2 mm at a rate of 0.5 mm / sec.

[0083]

[Table 5] The viscosities of the emulsions were similar.

[0084]

[Table 6]

[0085]

[Table 7]

[0086]

[Table 8]

[0087]

[Table 9]

[0088]

[Table 10]

[0089]

[Table 11]

[0090]

[Table 12]

[0091]

[Table 13]

[0092]

[Table 14]

[0093]

[Table 15]

[0094]

[Table 16]

[0095]

[Table 17]

[0096]

[Table 18]

[0097]

[Table 19]

[0098]

[Table 20]

[0099]

[Table 21]

[0100]

[Table 22]

[0101]

[Table 23]

[0102]

[Table 24]

[0103]

[Table 25]

[0104]

[Table 26]

[0105]

[Table 27]

[0106]

[Table 28]

[0107]

[Table 29]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A23G 3/00 A23L 1/24 A 9/02 C11C 3/06 A23L 1/24 A23D 7/00 502 C11C 3/06 9/00 516 (72) Inventor Stephen Raymond Moore UK, N14.4 UH, Northamptonshire, Slapston, Wayne Wright Avenue 2

Claims (14)

[Claims] 1. At least two long-chain polyunsaturated fatty acids L ₁ and L ₂ are included, both L ₁ and L ₂ being at least 3
Has two unsaturations and has at least 20 carbon atoms, then L ₁ is the most abundant and L ₂ is the second most abundant,
A triglyceride composition, said triglyceride composition comprising at least 20% by weight of L ₁ , and L ₁ : L
₂ weight ratio is at least 2, also the triglyceride composition comprises at least 2 wt%, preferably at least 5 wt%, more preferably at least 15 wt%, and most preferably at least 30 wt%, 2-12 and / Or
Containing saturated fatty acids having 20 to 24 carbon atoms, while
The triglyceride composition comprises more than 10% by weight of 16-18
Saturated fatty acids having 1 carbon atom, saturated C ₂ ~
At least 5% by weight of C ₁₂ or C _{20 to} C ₂₄ fatty acid residues,
Preferably at least 10% by weight, most preferably at least 20% by weight, at least L ₁ and / or L ₂ are attached on the triglyceride molecule on which they are present. 2. A triglyceride composition according to claim _{1, wherein} the amount of L ₁ is more than 30% by weight and the weight ratio L ₁ : L ₂ is at least 3. 3. The amount of L ₁ is at least 40% by weight and the weight ratio L ₁ : L ₂ is at least 3.5.
Or the triglyceride composition of 2. 4. The triglyceride composition according to claim 1, wherein the C ₁₆ -C ₁₈ saturated fatty acid concentration is lower than 8% by weight, in particular lower than 5% by weight. 5. The triglyceride composition according to any one of claims 1 to 4, wherein L ₁ is DHA (= C _{22: 6} ). 6. The triglyceride composition according to any one of claims 1 to 5, wherein L ₂ is EPA (C _{20: 5} ). 7. The triglyceride composition according to any one of claims 1 to 6, wherein L ₁ is EPA and L ₂ is DHA. 8. A blend of triglycerides, comprising:
3 to 95% by weight of the triglyceride according to any one of claims 1 to 7 and 99.7 to 5% by weight of a complementary fat, 10% of the triglyceride according to any one of claims 1 to 7. Solid fat index in ° C
Blends of triglycerides containing fat, with at least 5% greater, or at least 5% less N ₁₀ than (N _10). 9. Triglyceride according to claim 1, in an amount of 5-80% by weight, in particular 20-70% by weight, and
9. The blend according to claim 8, consisting of 95 to 20% by weight, in particular 80 to 30% by weight of complementary fat. 10. The complementary fat has a solid fat content of greater than 15 at 20 ° C. (NMR-pulse method; unstabilized), preferably a solid fat content of greater than 20 at 20 ° C. 8. Or a blend of 9. 11. Complementary fats from cocoa butter equivalents, cocoa butter, palm oil or fractions thereof, palm kernel oil or fractions thereof, transesterification mixtures of said fats or fractions or hardened components thereof. 11. Selected from liquid oils such as sunflower oil, high oleic sunflower oil, soybean oil, rapeseed oil, cottonseed oil, safflower oil, high oleic safflower oil, corn oil, or MCT oil. The blend of claim 1. 12. The blend exhibits a solid fat content (NMR-pulse method; unstabilized) of 0-85, preferably 10-70, most preferably 20-60 at 5 ° C. and 30 at 35 ° C. Blend according to any one of claims 8 to 11, exhibiting a solid fat content of less than 20, preferably less than 20, most preferably less than 5. 13. Any of claims 1-12, comprising an effective amount of an oxidative stabilizer selected from the group consisting of natural or synthetic tocopherols, BHT, BHA, radical scavengers, enzymes with antioxidant properties. A triglyceride composition of claim 1 or a blend comprising them. 14. Spreads, margarines, cream substitutes, infant foods, chocolates, confectionery, bakery products,
Foods containing a fat phase, such as sauces, ice creams, ice cream coatings, cheeses, soups, mayonnaises, dressings, enteric-coated or parenteral products, the fat phase containing fats according to claims 1-13. .