CZ296A3 - Aromatic preparation and process for preparing thereof - Google Patents

Abstract

PCT No. PCT/EP94/02026 Sec. 371 Date Dec. 28, 1995 Sec. 102(e) Date Dec. 28, 1995 PCT Filed Jun. 20, 1994 PCT Pub. No. WO95/01106 PCT Pub. Date Jan. 12, 1995Process for preparing a flavoring composition suitable as a butter flavor block by subjecting triglyceride fats, fatty acids or fatty acid derivatives to oxidizing conditions, comprising: (a) admixing an anti-oxidant to triglyceride fats, fatty acids or fatty acid derivatives at least to a concentration which is sufficient to increase the induction period of the fat by a factor of 1.5, (b) heating the mixture for 0.5 hours-1 week at 50 DEG -150 DEG C. under access of atmospheric oxygen and in the presence of water, under the condition that the triglyceride fats, fatty acids or fatty acid derivatives contain at least one poly-unsaturated fatty acid with an omega-3 non-conjugatable double bond system in an amount of >0.01 wt. %. Such fatty acids or derivatives of fatty acid are preferably obtained by partially hydrogenating a natural vegetable glyceride fat.

Description

Aromatizing agent and process for its preparation, Z J. DiNlSVTA

On Jap I, * j g-dd ¹ .. 1 σ / yo

Technical field

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The invention relates to a flavoring agent, manufacturing process, its use for the flavoring of food produl 4i ^M j 't S5 γ'Μ - * \ ·' H T | Γ '-γ *' * 7 · ·. T '

In this context, T ' refers to both cicna and taste.

BACKGROUND OF THE INVENTION

The use of flavoring agents for flavoring food products is well known in the art. Generally, such compositions are prepared by mixing various aromatic compounds or ingredients. However, when flavoring agents are used to mimic the flavor of a known foodstuff, for example a butter flavor, the sensory effect does not fully capture the intended flavor.

One of the most commonly used applications of flavorings is the imitation of real butter aroma. Adding a certain amount of butter or butter fat to food products, such as margarine, is a well known method of imparting the most desirable butter flavor to these food products.

EP 0 298 552 further discloses that 20 balanced buttery flavor can be given to food products by adding butterfat that has been subjected to an oxidation process. The flavored food product is prepared by the addition of at least 0.05% by weight of such an oxidized butter fat containing more than 0.5 ppm of n-pentanal and / or more than 0.05 ppm of 2-trans-nonenal. The buttery aroma obtained can hardly be distinguished from real butter. Compared to unoxidized butyric

- 2 fat is an oxidized butterfat that requires substantially less to achieve the same taste and olfactory sensation.

EP 0 377 239 describes the preparation of a flavoring agent which is prepared by the controlled oxidation of fats based on natural triglycerides in the presence of an antioxidant. This method yields products that retain the original flavor but with substantially fat, buttery aroma is enhanced. When starting from peanut oil, controlled oxidation enhances the peanut flavor.

EP 0 463 660 describes the oxidation of fats based on natural triglycerides or fatty acids in the presence of antioxidants to obtain a flavoring composition.

All known methods for preparing flavorings are based on natural glyceride fats. For the preparation of, for example, buttery ts flavor, it is always based on butter or butter fat, which is an expensive starting material, as well as other aromatic oils. Therefore, a cheaper alternative of starting fats is very desirable.

SUMMARY OF THE INVENTION

A flavoring agent has been found that can be obtained by 2o oxidation of an oleo compound from the group of non-lactic glyceride fats, fatty acids or fatty acid derivatives containing at least one polyunsaturated fatty acid containing an omega-3 unconjugated double bond system in an amount> 0.01% by weight of fatty acids. The invention further encompasses a flavoring agent obtainable by oxidation of an oleo compound of the group of non-milk fat glyceride fats, fatty acids or fatty acid derivatives comprising at least one polyunsaturated fatty acid containing an omega3 non-conjugable double bond system in an amount of> 0, 01%

3 wt.%, Preferably in an amount of > 0.1 wt.% Of the amount of fatty acids.

Further, a process for the preparation of such a flavoring composition has been found which comprises using a modified oleo compound which is either a natural glyceride fat or a fatty acid or fatty acid derivative. Therefore, the invention also encompasses a method of an oleo compound which is either a natural glyceride fat or a fatty acid or fatty acid derivative, having an oxidizing action, characterized in that the opioid compound has been subjected to a treatment that causes the fatty acid composition to be modified to contain at least 0.01 % by weight of the amount of polyunsaturated fatty acids containing an omega-3 non-conjugable double bond system. Such action includes mainly hydrogenation, interesterification and fractionation.

In contrast to these known methods, the process of the invention does not primarily enhance the natural flavor, to some extent already present in the starting fat, but produces an unexpected flavor that was not present before processing in the starting fat. Aromatizační

A composition suitable for flavoring foods that require a buttery flavor can now be prepared by oxidizing a taste and olfactory neutral soybean oil that has been partially hydrogenated. The resulting aroma contains a characteristic sweet, creamy ingredient, highly desirable for buttery flavor.

A flavoring composition within the meaning of the present invention means any composition which can be used to flavor food products, either alone or with an addition of other flavoring agents, ingredients or compounds with which it can form an aromatic composition. Therefore, it may be flavoring

3o a composition of a single compound, or more often a mixture of several compounds,

- 4 some of which may be present in trace amounts and which together and at the correct concentrations have the responsibility for the desired flavor. For flavoring agents which are not comprised of a single compound and achieve appropriate properties upon addition of one or more other flavoring agents, the term aromatic block, aroma and / or flavor of true butter is often used. This is not to say that the flavor imparted by the flavoring agent is necessarily the same in all respects as the flavor of real butter (referred to as 'natural buttery flavor'). One object of the present invention is to provide an aromatic block suitable for preparing a butyric aroma.

According to the present invention, the glyceride fat that is used to prepare the flavoring agent is essentially a fat with a relatively high content of polyunsaturated fatty acids with an omega-3 non-conjugable double bond system (e.g., see Figure 1). Such fatty acids should be present at a concentration of > 0.01% by weight (unsaturation condition A). The preferred amount is > 0.1% by weight and the optimal amount is 1-5% by weight of the amount of fatty acids.

Such fats have not been described as a starting material for flavoring. According to the invention, they can be conveniently obtained by any treatment which results in a modification of the fat.

The modification of fat within the meaning of the present specification means that the fatty acid composition has changed compared to the original fatty acid composition. The fat modification does not include treatments such as lipid hydrolysis that has no effect on the fatty acid composition.

The fat modification should produce a sufficient amount of at least one polyunsaturated fatty acid or fatty acid residue

- 5 with an omega-3 non-conjugable double bond system. Such a double bond system comprises at least two double bonds, one in the omega-3 position, and all double bonds are separated by at least two methylene groups. Typical examples are 9,15s octadecadienoic acid, 10,15-octadecadienic acid and 11,15octadecadienic acid as opposed to 9,13,15-octadecatrienoic acid and 11,13,15-octadecatrienoic acid which contain conjugatable. It has been found that the oxidation of oils containing such fatty acid residues also results in flavor products containing a characteristic sweet, creamy component, highly desirable in the aromatic blocks used to form the buttery flavor.

The modification of the triglyceride fat fatty acid composition may also be appropriately affected by one or more of the following treatments: hydrogenation, interesterification and fractionation, provided that the change in fatty acid composition results mainly in the formation of polyunsaturated fatty acids with omega-3 unconjugatable double bond system.

In general, hydrogenation aims to convert unsaturated fatty acid residues of the glyceride fat to less unsaturated or saturated acids, such as linoleic acid to oleic acid, or oleic acid to stearic acid. To obtain glyceride oil containing an increased amount of poly-unsaturated fatty acids with an omega-3 unconjugated double bond system, the oil to be oxidized should contain a poly-unsaturated fatty acid which can be hydrogenated to poly-unsaturated fatty acids with an omega-3 unconjugated double bond system The reaction scheme for the formation of such fatty acids via hydrogenation is shown in Figure 2.

A conventional hydrogenation method may be used to modify the fatty acid composition by hydrogenation. This includes not only chemical hydrogenation using nickel, palladium or platinum catalysts, but also biohydrogenation where hydrogenation is achieved in the presence of a hydrogenation enzyme.

The modification via interesierification involves the addition of a source. glyceride fat, to natural glyceride fat, and at least a partial fatty acid exchange between the natural fat and the added fatty acid. Any interesterification method may be used, including chemical and enzymatic interesterification.

Another way to modify the fatty acid composition is to fractionate the natural glyceride fat, fatty acid or fatty acid derivative, either dry or in a solvent.

The term glyceride fat usually refers to a mixture consisting mainly of triglycerides. However, when this fat is not completely purified, it may additionally contain significant amounts of free fatty acids, mono- and diglycerides and phospholipids. Although not wishing to be bound by theory, it is believed that compounds contributing to aroma formation are formed by the decomposition of unsaturated fatty acid residues in the oleo compounds. Therefore, it is not essential if the above-defined fatty acids are present as free molecules or bound as derivatives, such as mono-, di- or triglycerides. Their carbon chains disintegrate during the oxidation to form the flavoring agents of the invention both in free form and in derivative form.

The glyceride fat when used as a starting material for the present process usually contains at least 60% by weight triglycerides.

- 7 The terms grease and oil can be used interchangeably when used. Any type of fat can be used, including animal fat and fish oil, but preferably vegetable oils are used if they contain a fatty acid which may be a precursor of the process of the invention. The fatty acid precursor is characterized in that, after hydrogenation, it provides a fatty acid with an omega-3 non-conjugable double bond system. Such fats are

- j - y '' íi j · i - '- ^j s ~ ~ H ^J. j - Other vegetable oils such as sunflower oil, palm oil, palm kernel oil, peanut oil, olive oil and sesame oil and mixtures thereof are less suitable because they do not contain fatty acids which can act as precursors for the process of the invention and therefore cannot be used on their own, but only as an admixture of fats of the previous group.

For the purposes of this invention, the term fat also includes sucrose fatty acid esters which can be used as low calorie replacements for some or all of the triglyceride material.

The most preferred method for obtaining and modifying compositions for the

The fatty acid base is hydrogenation for which any conventional methods can be used. Hydrogenation should not continue until fully saturated, otherwise the double bond system necessary for the subsequent oxidation process will disappear. The iodine number preferably remains greater than 50. The optimum extent of hydrogenation depends on the nature of the fat and can be readily determined by experiment.

Although not wishing to be bound by theory, partial hydrogenation is believed to saturate the double bond that would cause foreign aroma during subsequent oxidation (see Table II).

For oxidation, fats with a relatively low x polyunsaturated omega-3 fatty acid conjugated or

- 8 conjugatable double bond system. Oxidation in the presence of such fatty acids can produce an unpleasant raw, oily aroma. In any case, the fat for oxidation contains 0-5% by weight, preferably 0-1% by weight of such acids (condition of unsaturation B). As a rule, the percentages are calculated on the total amount of fatty acids.

the unsaturated fatty acids with the omega-3 non-conjugatable double bond system and the polyunsaturated fatty acids with the omega-3 conjugated or conjugatable double bond system are greater than 1 (unsaturation condition C).

According to a more preferred embodiment, the hydrogenated fat is hydrogenated soybean oil with a slip melting point of 30-45 ° C, preferably about 35 ° C. Oxidizing this hydrogenated fat gives a flavoring agent useful as a butyric aromatic block. When this aromatic block, optionally suitably diluted, is admixed with butyric aromatic compounds such as diacetyl, delta-lactones and methyl ketones, a suitable buttery aroma is obtained which is very similar to the natural butter aroma.

The flavoring agent is obtained by exposing said chemical with a particular fatty acid composition to oxygen, preferably air oxygen. Fat oxidation already occurs at room temperature but economical rate of oxidation is achieved at temperatures above 50 ^e C. Therefore, the reaction temperature is preferably increased to> 50 ° C.

Figure 3 shows the relationship between temperature and minimum heating time required to produce a noticeable aroma. Generally, the modified fat is heated at 50-150 ° C for 0.5 hours to 1 week. A disadvantage of the relatively high temperatures is that volatiles may escape from the reaction mixture.

At 50-85 ° C, heating times of 5 to 50 hours are suitable. Often good results are obtained within 8 - 36 hours. Heating to about 100 ° C for one hour is often sufficient.

Good and reproducible results are obtained when oxidation 5 is carried out under reflux. A good compromise between speed of reaction and the release of volatile substances, the temperature of 85-95 ° C ^and

Ι- »W 4 <wi i vj d '** V · J H' r -iU u p. Sz f -. . • ú,. . % by weight of water at a temperature of 50-150 ° C. Obviously, if temperatures above 100 ° C are used, the pressure must be increased. If water is no longer present in the starting materials, it is added to the reaction mixture.

The presence of a certain amount of salts during oxidation has a beneficial effect on aroma formation. Preferably, the reaction mixture contains 3 to 40% by weight of kitchen salt (based on the amount of water contained).

The oxidized fat should substantially not contain compounds capable of entering the Maillard reaction. For the purposes of this specification, this means that the total amount of protein and reducing sugar - the food is present - should not exceed 1% by weight.

Preferably, the oxidation of the modified fat is a controlled oxidation, which in this sense means a process in which an antioxidant is present in the

2 so much that it acts to slow the oxidation slightly. If the antioxidant is no longer present in its natural form in the oxidation stream, it may be added to the reaction.

The antioxidant may be either a single compound or a mixture of different compounds. Suitable antioxidants are;

(1) natural or identical antioxidants such as tocopherols, tocotrienols, guaiac gum, nordihydroguayaretic acid, ascorbic acid;

- 10 (2) synthetic antioxidants such as butylated hydroxyanisole (SHA), butylated hydroxytoluene (BHT), tertiary butylhydroxyquinone (TBHQ), trihydroxybutyrophenone, 4-hydroxymethyl-2,6 diterc. butylphenol, dilaurylthiodipropionate, gallates, anoxomer (condensation product 6HA, BHT and

TBHQ), ascorbyl palmitate;

ethylenediaminetetraacetic acid (EDTA).

Preferably, the antioxidant is from the group of natural or identical antioxidants, citric acid, tartaric acid and precursors thereof. The most preferred antioxidant is α-tocopherol and mixtures of tocopherols which are commercially available. At the same time, alpha-tocopherol is present in vegetable fat as a natural antioxidant.

Approximately 0.1% by weight (based on fat) of alpha-tocopherol is sufficient to prolong the fat induction period by a factor of 1.5 (effective concentration). The induction period is determined at 100 ° C by the method described in J.Am.Oil.Chem.Soc. Vol. 63, 6 (1986), 192-195.

In general, the effective concentration of the antioxidant depends on both the nature of the fat and the nature of the antioxidant. The antioxidant may be incorporated in an amount of 1

2 to 100 times the effective concentration.

When alpha-tocopherol is the only antioxidant present in the flavoring composition of the invention, its concentration is at least 0.01% by weight.

The object of the present method is a slight fat oxidation, which in this sense means following the peroxide number after the oxidation, which is usually at least 2 and not more than 20. The peroxide number indicates the amount of peroxides present in fat and expressed in milliequivalents of oxygen per kilogram fat. Possible method for determining

11 of the peroxide number is described in: P.G. Powick, J. Agric. Res. 26, 323 (1923).

Since the aromatic compounds produced are rather volatile, the oxidation step is preferably carried out in a substantially closed system, i.e. a system from which such volatiles cannot escape. In this sense, the term closed system also includes, as well as the volatile flavorings produced, present in the fat-containing oxidation mixture, during oxidation, which may take a relatively long time, to avoid this.

Performing the present process may be followed by the step of obtaining the volatiles present in the oxidized fat. For example, their isolation from the mixture may be by distillation, supercritical extraction or solvent extraction. The volatiles are preferably isolated by distillation. The distillate contains a mixture comprising (C ₅ - C ₂₎ -alkanals, (Cs - C ₂₎ and -2'alkenalú _(C7 - _C12) -2,4-alkadienalů.

The volatiles may optionally be distilled during oxidation. In such a case, heating helps to accelerate both oxidation and evaporation of volatile flavorings.

The invention also encompasses the use of the flavoring agents of the invention for flavoring food products and food products themselves. The flavoring agent is added to the food product alone or in admixture with other flavoring agents in an amount of 0.001 to 10% by weight, preferably 0.5 to 6% by weight, based on the food product.

Food products are: products which are suitable and intended for human consumption, ie products which are not toxic when ingested in normal quantities. A typical flavoring agent is a buttery flavoring block that is

- 12 very suitable for flavoring spreads, non-dairy creams, confectionery products, ice creams, syrups, bakery products and baked goods, greases, juices, soups, sauces, dressings and desserts, generally products with a successful buttery aroma.

Aromatic compositions typically have a continuous fat phase, and thus can be added to products that also have a continuous fat phase such as can be emulsified in water, and can then be readily admixed to emulsion-type foods such as creams which may be continuous phase also water.

The obtained flavored food products preferably contain 10-95% by weight of water and 5 - 90% by weight of fat (oxidized fat according to the invention and non-oxidized fat). The total fat and water content is at least 70% by weight. Such food products are, for example, high fat spreads containing, for example, 80% by weight fat phase, of which 3% by weight is oxidized fat, and low fat spreads, containing eg 40% by weight fat phase, of which 1% by weight are oxidized fat.

The non-oxidized fat that is present in the flavored food product has a low peroxide number, preferably less than 2, and even more preferably less than 0.1. In addition, this non-oxidized fat has an anisidine number of less than 1 and a total oxidation number of less than 5. For anisidine number determination, see: IUPAC, Standard Methods for

2s Analysis of Oils, Fats and Derivatives, 6th Ed. (1979), Pergamon Press, Oxford, Method 2504, page 143.

The total oxidation number (TOV) is calculated from the peroxide number (PV) and the anisidine number (AV):

TOV = 2 x PV + AV

- 13 See: J. Am.Oil.Chem.Soc. 51, 17 (1974) G.R. List et al.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows an omega-3 polyunsaturated fatty acid with a chain length of 18 carbon atoms and conjugatable

The double bonds (Fig. 1C).

Figure 2 illustrates a method of forming polyunsaturated fatty acids with a non-conjugable double bond system in the hydrogenation of polyunsaturated fats and oils. Linolenic acid (FIG. 2A) is first converted to the positional isomer of linolenic acid (FIG. 26) and then to a mixture of positional isomers of linoleic acid (FIG. 26).

C).

Figure 3 shows the temperature dependence of the oxidation step. i5 The graph shows for each oxidation temperature the minimum reaction time hours required to produce a noticeable aroma.

The invention is illustrated by the following examples:

DETAILED DESCRIPTION OF THE INVENTION

Examples 1-9

A composition imparting a buttery aroma, its preparation and an organoleptic evaluation

Several vegetable oils were neutralized, bleached and partially hydrogenated by the usual hydrogenation process on the oil until the slip melting point was reached, as shown in Table I.

- initial temperature 14 140 ³ C hydrogenation was increased up to 185 ° C. Unless otherwise stated (see Table 1), a nickel quartz catalyst was used at concentrations up to 0.3% nickel by weight. Table I shows the composition of the ^H- fusions of natural oils and each hydrogenated oil. The number after the oil name indicates the slip melting point.

hydrogenated, tasteless or odorless. It should have a peroxide value of less than 1.0. 500 0,2 0.2 g of tocopherol mixture (60% solution in oil containing alpha, gamma and delta-tocopherols in a weight ratio of 1: 3) was added to 500 g of freshly refined oil. , 13: 3.46 (Eisai Co., Ltd.)) and 125 g of a 16% by weight salt solution in demineralized water.

The emulsion was heated with stirring (93 ° C) in a 1 L 3-neck round bottom flask equipped with a reflux condenser on an oil bath (108 ° C). After 24 hours (48 h in Example 6), the aqueous salt phase was separated from the fat phase by centrifugation or decantation (if the oil solidified).

- 15 Table I

Example Oil Fatty acid composition (%) C18: 3 C18: 2 C18: 1 tot. Omega-3 3) C18: 2 Ng ²⁾ AND BO 7.7 53.0 22.8 8.0 0 ί AND ^; and

AND

_ ... . . , ..... * .... .... . · 1 BO 32 low trans 0.0 1,8 71.6 0.4 0.6 2 BO 35 0.0 0.6 66.9 0.3 3.4 3 BO 35 ^υ 0.0 0.2 74.1 0.4 3.0 4 BO 36 low trans 0.0 0.3 69.5 0.3 1.0 5 BO 43 0.0 0.5 65.1 0.3 Ί 2.5 6 BO 65 0.0 0.1 2.2 0.0 0.4 (B) RP 8.6 20.0 58.1 nestanoveno ^! 7 RP 32 0.5 3.0 70.3 not specified 8 RP 36 0.3 2.4 67.3 not specified 9 RP 44 0.1 0.3 53.5 not specified C AFTER 0.3 10.1 38.5 0.3 0.0 E PO 45 0.0 1.0 42.5 0.0 0.0

BO = soybean oil RP = rapeseed oil PO = palm oil ¹⁾ hydrogenated on a catalyst sulfurized nickel on S1O2 ²⁾ nc = nekonjugovatelný, term refers to polyunsaturated fatty acids in which the double bonds are separated by more than one methylene group ^{3 >} Total poly-unsaturated fatty acids with omega-3 conjugated or conjugatable double bond system

Analysis of the oil of Example 3: Volatiles were collected from oxidized fat by degassing under high vacuum (1.33 mPa, 90 ° C, 5 hours) and analyzed by gas chromatography:

ug / kq (ppb) with oentanal ........................ 590 hexanai ...... 720 ne ρ i 211 ji ..... ............ ϊ oo octanal ......................... 530 nonanal ........ ................ 570 and decanal ........................ 440 undecanal ..... .................. 85 dodecanal ....................... 30

2-pentenal ........................ 120

2-Hexenal ..................... 340

2-heptenal .............................. 840

2-octenal .................... 1180

2-nonenal .................... 1340

2-decenal 1615

2-undecenal 1350

X 2-dodecenal ................. 460

2.4- Heptadienal ............. 100

2.4- octadienal ............... 135

2.4- nonadienal .............. 700

2.4- decadienal ............ 2520

2,4-undecadienal ........ 430

2.4- dodecadienal 40

For comparative purposes, fats which do not meet the above-mentioned unsaturation conditions were also exposed to the oxidation conditions (Examples A, B, C, D and E).

- 17 Organoleptic evaluation% by weight of oxidized oils and comparative oils were dissolved in taste and olfactory neutral oils (medium chain triglyceride oil).

Dilute oil samples were assessed by a group of ten

- margarine aroma experts (see Table 11). In addition to the similarity, it has been judged to be an oily, creamy flavor which has been a highly appreciated contribution to the buttery flavor. It should be noted that Comparative Example D also has a very strong foreign flavor. Although the oil has been hydrogenated, it does not satisfy the conditions of unsaturation B and C. Comparative Example E does not have a foreign flavor because it satisfies condition B but also an improved aroma because it does not satisfy condition A.

- 18 Table II Organoieptic evaluation

Example Oil Sensory evaluation ² ) raw, oil. ¹¹ sweet, creams. similarity to butter AND BO 5 1 í ^{1 ! (0} '69 25 4 ...? ..... 1 1 BO 32 low trans 1 4 3 1 2 BO 35 1 5 4 3 BO 35 high, trans 1 5 4 4 BO 36 low trans 1 4 3 5 BO 43 1 5 4 6 BO 65 ³⁾ 1 2 1 i (B) RP 5 1 1! 7 RP 32 1 4 3 8 RP 36 1 5 4 9 RP 44 1 5 4 C AFTER 4 1 1 E PO 45 1 2 2

foreign flavor ²⁾ mean, results (n = 10); Scale from 1 = weak to 5 = strong A, B, C are comparative examples for unhydrogenated BO, RP, PQ with D and E are hydrogenated soybean and palm oil that do not meet the unsaturation conditions ³⁾ fully hardened soybean oil containing approximately 0, 4% by weight of polyunsaturated fatty acids

- 19 Example 10

Preparation of croissants using oxidized hydrogenated soybean oil as an aromatic preparation

Using a Votator ™ wiped heat exchanger, it was prepared by an aqueous phase (17% by weight) consisting of (% by weight):

86 % demineralized water 10 2.4 % modified starch 5.5 % salt 5.5 % sucrose 0.4 % citric acid 0.2 % potassium sorbate 15 Dec 8 ppm diacetyl

and with a fat phase (83% by weight) consisting of:

40% hardened palm oil (melting point 42 ° C) 30% hardened rapeseed oil (melting point 32 ° C) 11% soybean oil 20 May 15% lard 4% the flavoring oil of Example 2

-20 Rolls were prepared from dough with the following composition:

1000 G flour 40 G peka / yeast 25 G salt 100 ALIGN! G sucrose G water

After kneading, the dough was placed in a covered container to avoid crusting. The dough was rising for one hour at room temperature and overnight in the fridge. Then the dough was cut into pieces. For turning, the piece was rolled and half was covered with 500 g of pre-kneaded margarine. The dough was then folded to cover the margarine and the edges joined together. It was then rotated, folded three times and then four times (i.e. single and double fold). The dough was rolled to a thickness of approximately 3 mm.

For molding, the dough was cut into 20 cm wide strips and divided into triangles of 40 to 50 grams. The triangles had a longitudinal shape with a length of 13-20 cm and a width of 9-10 cm. Then the dough was rolled up.

Rolls continued to swing at 30-35 ° C covered before draft or in a leavening room. The roasts were fast (about 250 ° C) without dampening for about 12 minutes. The rolls were twice coated with an egg and again before the last leavening.

Comparative example F

Example 10 was repeated but margarine was prepared using the oxidized butterfat prepared according to Example 1 of

EP 0 377 239 instead of the oil of Example 2 of the present specification.

- 21 Organoleptic evaluation

The rolls prepared according to Example 10 and the rolls prepared according to Comparative Example F were compared by a group of ten aroma experts with rolls prepared from real butter. Both types of rolls with (examples 10 and F) received a good score from the referees, but the results of the first type were slightly better.

Making dough sticks using oxidized hydrogenated soybean oil as a flavoring agent and using a Votator- ¹ wiped heat exchanger, a baked margarine for rolls (so-called Danish dough margarine) with an aqueous phase (17% by weight) consisting of (% by weight):

15 Dec 86 2.4 5.5 5.5 0.4 0.2 % % % % % % demineralized water modified starch salt sucrose citric acid potassium sorbate 20 May 8 ppm diacetyl 16 ppm a 1: 1 mixture of δ-decalactone and δ-dodecalactone 1 ppm a mixture of 2-pentanone, 2-heptanone and 2-nonanone 1 - 1

and with a fat phase (83% by weight) that consisted 40% hardened palm oil (melting point 42 ° C) 30% hardened rapeseed melting point 32 ^and C) 11% soybean oil 15% lard 2% aromatizing oil according to Example 2

Dyio dough prepared from the following ingredients:

500 G Columbus ™ flour (Meneba) 260 G water 200 G margarine 300 G margarine for rotation

and the following (Scottish-Danish) method was used to prepare the bars:

- knead flour, water and margarine into a dough in a kneading machine

Diosna 200 cycles

- let the dough rest for 10 minutes - roll out the dough to a thickness of 5 mm - hand spread the margarine over the dough surface - fold the dough three times and let it rest for 20 minutes

- repeat the last step twice more

- roll the material to a thickness of 3 mm, cut into 12 x 2 cm bars - bake at 200 ´C

Comparative Example

Example 11 was repeated, but margarine was prepared using the oxidized butterfat prepared according to Example 1 of

EP 0 377 239 instead of the oil of Example 2 of the present specification.

- 23 Organoleptic evaluation

The dough sticks prepared according to Example 11 and the sticks prepared according to Comparative Example G were compared by a group of ten aroma experts with sticks prepared from 5 real butter as standard. Both types of rods (11 and G) received a good score from the judges, but the results of the first type (Example 11) were slightly better than those of your second example.

Represented by:

Claims (24)

PATENT CLAIMS ·. >? -1 - / - -i. is not less than 50. A flavoring agent obtainable by oxidation of a fatty acid or fatty acid denvate or mixtures thereof; A flavoring agent according to claim 1, characterized in that the fatty acid comprises at least one fatty acid selected from the group consisting of 9,15-octadecadienoic, 10,15-octadecadienoic and 11,15-octadecadiene, A flavoring agent according to either of claims 1 or 2, characterized in that the fatty acid or fatty acid derivative contains 0-5% by weight, preferably 0-1% by weight, based on the amount of A flavoring agent according to any one of claims 1 to 3, characterized in that the weight ratio between 25 polyunsaturated fatty acids with an omega-3 unconjugated double bond system a -25 poly-unsaturated fatty acids with an omega-3 conjugated or conjugatable double bond system is greater than 1. 5. A flavoring composition which is obtainable by oxidation of a natural glyceride fat which has been subjected to a treatment which has modified the fatty acid composition of the fat glycidide. 5 '»!« · »:>. R 3 r '· ₌ *>i') comprising said fatty xyseiina aiespoh one polyunsaturated fatty acid with an omega-3 non-conjugatable double bond system in an amount of> 0.01 wt%, preferably> 0.1% by weight, 6. A flavoring composition according to claim 5 wherein the modifying treatment is selected from the group consisting of hydrogenation, interesterification and fractionation. A flavoring composition according to claim 5, which is suitable for use as a butyric aroma block in food compositions and is obtainable by oxidizing soybean oil which has been hydrogenated to a slip melting point of 30-45 ° C. 8. A process for the preparation of a flavoring composition, characterized in that the natural glyceride fat or fatty acid or fatty acid derivative is subjected to an oxidizing action, wherein the natural glyceride fat or fatty acid or fatty acid derivative is a natural fat which has been subjected to a treatment leading to an increase. a polyunsaturated fatty acid content with an omega-3 unconjugated double bond system up to at least 0.01% by weight based on the amount of fatty acids. -26 The method of claim 8, wherein the modifying treatment provides a fatty acid product containing 0-5% by weight of an omega-3 conjugated or conjugatable double bond system. ^ 0. -f λ < ob NORC as claimed ⁱⁿ fatty acid composition with a weight ratio between the poly-unsaturated fatty acids with an omega-3 non-conjugatable double bond system and polyunsaturated fatty acids with an omega-3 conjugated or conjugatable double bond system greater than 1. 10 based on the amount of fatty acids. Process according to any one of claims 8-10, characterized in that the natural glyceride fat or fatty acid or fatty acid derivative has been subjected to hydrogenation. The method of any one of claims 8-10, wherein the natural glyceride fat or fatty acid or fatty acid derivative has been subjected to an interesterification treatment. The method of any one of claims 3-10, wherein the natural glyceride fat or fatty acid or fatty acid derivative has been subjected to fractionation. - 27 10 The method of any one of claims 8-13, wherein the natural fat is selected from the group of fats, including soybean oil, rapeseed oil, cottonseed oil, corn oil and sesame oil, and mixtures thereof. The method of claim 11, wherein the natural glyceride fat or fatty acid or derivative 16. The process of claim 11 or 15 wherein the fat is soybean oil hydrogenated to a slip melting point of 30-45 ° C. Method according to any one of claims 8-16, characterized in that the modified fat or fatty acid or fatty acid derivative is oxidized by heating in the presence of oxygen, preferably air. 18. The method of claim 17, wherein the modified fat or fatty acid or fatty acid derivative is oxidized in the presence of an antioxidant that has been admixed with the modified fat at a concentration sufficient to prolong the induction period of the fat by a factor of at least 1.5. The method according to claim 17 or 18, wherein the modified fat or fatty acid or fatty acid derivative is heated for 0.5 hours to 1 week at a temperature of 50 to 150 ° C. A method according to any one of claims 17-19, wherein the modified fat is heated in the presence of water at a temperature of 50 to 150 ^and C. - 28 20 fatty acids, fatty acids with an omega-3 conjugated or conjugatable double bond system The method of any one of claims 17-20, wherein the starting material is substantially free of proteins and reducing sugars capable of entering the Maillardouy reaction. 5 22. The method of claim 21, wherein the total amount of proteins and reducing sugars capable of contributing to the reaction is not more than 1% by weight. Use of a flavoring agent according to any one of claims 1 to 7, or obtained by a process according to any one of claims 8 to 22, for flavoring food products. A food product flavored with a flavoring agent according to any one of claims 1 to 7 or obtained by a process according to any one of claims 8 to 22.