DE2106127A1 - Fat products and processes for their manufacture - Google Patents

Description

The invention relates to fat products, in particular margarine and similar plastic oil and water J emulsions as well as on fat compositions or Fat compositions suitable for the manufacture of such spreads.

The polyunsaturated fatty acids are a dietary one according to significant scientific knowledge Requirement to protect against fat deficiency or fat insufficiency symptoms and are believed to be responsible for the growth and maintenance of normal Skin conditions in a large number of living things including People required. Linoleic acid and linolenic acid are all the main · polyunsaturated

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Fatty acids, recognized as being bound in vegetable and animal fats and having a noticeable biopotence, are a counteraction against fat defects or deficiency tesitsen, Ss are margarine and similar plastic emulf.ion spreads on the basis of these fats, which have a: h-vivsn ¹ proportion of bound containing polyunsaturated fats. However, it is found wor; -'- r, J ate by following the widespread practice of ^lag::;. 5rig of perishable foods at Tiefgefrierteü ^ this Emulsionsauf temperatures bar means after a G-efrlgeinstabilität to a degree show which of the The location depends on the temperature, the duration and the composition of the remedies.

The products of the invention include margarine and similar spreads which provide an enriched source of linoleic acid and linolenic acid and yet are reasonably resistant to structural degradation from freezing or low temperature storage. The invention is based on the finding _s da3 in eiE3; r such margarine or similar Y / leaving approximately oils mvl .s ion trichinitt on s a ₅ in which the oil phase is represented by a plastic mixture of fats, at least DIE a component having a Include polyunsaturated fatty acid content of 65 / S or more, such a tendency to structural instability as it exists _} can be reduced if at least a part of this component is uncontrolledly interesterified or randomized.

The amount of fat in the edible spreads according to the invention is preferably 80 to 95% by weight. However, there may also be a lower fat content.

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The invention also provides a margarine fat composition or margarine fat compositions for use in the manufacture of margarine and similar emulsion spreads is suitable, which is a mixture of usually liquid and usually solid food; ;. ,,, ■■ fat components including an unguidedly transesterified liquid fatty acid component, of which at least 65 $ of the combined or total fatty acid content are polyunsaturated. -

The oils containing 65 or more polyunsaturated fatty acids suitable for use in accordance with the invention include safflower oil and tobacco seed oil, although any triglyceride oils, types of which with ■ high. Linoleic acid content can be grown, provided that they are made with a hard component Can be compounded to create a margarine that has a polyunsaturated ratio too saturated acid of at least about 3.5: 1. As far as can be seen, these uncontrolled interesterified oils are new.

Sunflower oil is an example of an oil where A has one or more types with higher linoleic acid content than the common type. Safflower oil, on the other hand, has the highest linoleic acid content of vegetable oils available in large quantities and is the preferred oil used in the compositions according to the invention.

In practicing the invention, the sometimes liquid component a single oil with a polyunsaturated fatty acid content of at least etv / a 65 $ or a mixture of such oils that

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preferably form a major part of the liquid component. The liquid oil component can also contain a minor proportion of oil with a polyunsaturated fatty acid content slightly less than about $ 65, for example between about $ 50 to $ 65, provided that the margarine made therefrom is both liquid as well as hard components, has a ratio of polyunsaturated to saturated fatty acids in the range from about 3.5 s 1 to about 5 : 1. The higher, polyunsaturated oil or the higher polyunsaturated oils, alone or in a mixture with the oil or the oils with the lower, polyunsaturated content, can be uncontrolled transesterification, provided that in all cases at least 25 $ oil with a high, polyunsaturated content is uncontrolled be transesterified.

The fat products according to the invention preferably contain between 80 and 94% by weight, based on the total fat, of liquid oil component.

Preferably, the fat products according to the invention normally contain a solid component having an iodine number from about 35 to 60 and a saturated fatty acid content of 25 to 35 $ based on total fatty acids in fat composition. The ratio of multiple unsaturated fatty acids to saturated fatty acids is preferably 3.5 to 5 in the fat products:

The effect of unguided transesterification is the onset of structural instability in the margarine or similar water-in-oil paints due to storage to withstand freezing temperatures. The unguided one Transesterification is through a transesterification in which the fatty acid residues be exchanged on the glyceride residue of the fat in an arbitrary way. The exchange is carried out

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performed when the oil is in the liquid state, under the influence of a catalyst and continued - until the Mixture of molecular configurations is in equilibrium.

Articulated transesterification includes randomized

Position of the fatty acid residues in the triglyceride molecule in relation to the S · - ^ position as well as in relation to the arbitrary distribution of the fatty acids on the glyceride residues. j

Can limes esterification procedures leg hinged all .bekannten catalysts _s as Natriumalkoxyd having up to 4 carbon atoms, alkali metals and their oxides and Hydrosyde, verv / ends are Hatriumalkoxyd is preferred, however, the method can at a temperature of about 15o ° ö to 15 ⁰ O provided that the treated oil remains liquid. The treatment time is usually between 1/2 to 1 hour.

^J The extent of the structural instability of a margarine "can be shown by cutting or scraping of the plastic mass, if signs of structural instability J by the accumulation of liquid oil in the disturbed areas are visible, or by the development of a lumpy, granular structure.

Preferably, the margarine products are according to Invention of soft products. They are usually packaged in kegs and have the following range of solid fat index values. These values were obtained from dilatometric measurements as described in AOOS sample procedure pd lo-57 (1961) are described and were also used in the examples.

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29 _f H Me 9 at O ⁰ C (32 ⁰ F)

1, £ The β at 21.1 ⁰ C (To ⁰ P)

o _? 4 to & 3.5 at 33.3 ⁰ C (92 ⁰ P)

ν to L, c at 40 ° C (lo4 ° P).

Σ.,. :: "? T"rt; il of the invention is that the effect is a: scrnis, li ":: - v-6i £ e fixed Fattkojnponente to increase the?": - F: if;: -. ':''■■ 5 ~ r PeTtprociuirbe ingenious of the invention »in ds-Λί-r is :. ^; ; "-: .- rlie £ t <^ nimpeded, since they are not to be ^ älsrjrten. Transesterification of the normally liquid X-ossponirv ^ jd; .s is also present, - is subjected to"

Γ4-ΐ I'ettprccvxte according to the invention contain ziigsvfeLzz. Z'-Nizzhen about 6o and 755 ^ polyunsaturated? Ettsä ::::; s - Although aei * G-ehait an, polyunsaturated ?? et-ts £ .. «; rs look a little lower, e.g. 58 $ may _f is the SrfiiidiiK, g of great utility when wirdj applied to fats bie a content of poly unge3ättigtei "· fatty acid in the upper range of 60 to about 75 ^ _s preferably of 'about 64 about 7o ^ _f based on the 3-ewicfct ess total fat content.

The liquid component preferably has a lineal acid content of about $ 65 to $ 79 and a content of saturated fatty acids, which preferably consist of palmitic and stearic acid, between $ 5 and $ 12.

The solid component obtained preferably has an iodine value of 35 to 60, in particular from 40 to about 55i a content of saturated acids of preferably $ 23 to $ 60, especially $ 33 to $ 53 based on the Total fat content. Suitable fats for this purpose include partially hydrogenated rapeseed oil with an iodine number from 53 to 55, partially hydrogenated cottonseed, soy

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bean, peanut, corn egg, safflower and mustard seed oil or Mixtures thereof with an iodine number between about and 60 and equal parts by weight of cottonseed winter oil stearin and peanut oil with an iodine number of 4o to 5o. In general, the higher the proportion of is a solid component in margarine, the iodine number should be higher in the range given above.

Cottonseed winter oil stearin is preferred

obtained by winterization carried out at 45 to 50 ° C. The iodine number of stearin is usually between 75 and loo.

The aqueous phase of the water-in-oil emulsion fat products, which is provided according to the invention may contain in addition to water: salt, preservatives, e.g. potassium sorbate, spices and flavorings, ground soybeans or milk in the form of whole milk, Cream, skimmed milk or redissolved skimmed milk. Some suitable compositions of the aqueous Phase are given in Table I below, in which the amounts are listed as parts by weight, if nothing other is indicated.

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Table I. 1 2 2 4th 5 Area ^ 1.75 1.0. 4, o 1.75 salt 0-4 18.8 - - - - Skimmed milk 0-19.7 1.63 l, 8o Skimmed milk
solids 0-2 16.3o - 15.77 16.3o 17.87 water 0-19.7 o, Io - - o, Io o, Io Potassium sorbate 0 - o, l o, o3 - o, o3
ppm o, o3
1.63 o, o3 Spice and
Flavorings
ground
Soybeans'
Disodium
potassium ethy
diamine
tetraacetate 0 - o, o3
0-2
0-75
ppm

(a) Up to a total of 19.7 to 20 parts.

The emulsion products according to the invention can also contain emulsifiers and other additives as are customary Margarine compositions are used. Suitable such edible emulsifiers include Mono- and diglycerides, lecithin and sodium monostearin sulfoacetate. Colorants such as carotene (keratin) and vitaraine can also be present.

In the production of margarine or similar spreads according to the invention there is a water-in-oil emulsion at a temperature at which the usually plastic fat mixture is liquid, preferably from 40 to 42 C. The aqueous phase, for which skimmed milk can be used instead of water, can also be used

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contain other additives as described. The emulsion is preferably through a scratch ~ heat exchanger, such as a votator, pumped in which it is cooled in order to achieve subsequent crystallization of the fat, and processed. The product can be prepared by adding an inert, harmless gas such as nitrogen or air to the Emulsion must be aerated before entering the heat exchanger,! Times the exit from the heat exchanger becomes the essentially liquid composition through a B-unit is carried out in which the pressure of all sase present is reduced and the fat crystallizes.

You preferably have margarine exiting the B-unit a consistency in which it can be poured into containers that serve as molds. In it she will then Heated for solidification into a solid mass for 24 hours, preferably between about 7 and 10 ° C.

In the following examples, the safflower oil used had the following analytical values:

Iodine number .145 f

Palmitic acid 7il $

Stearic acid 2.9 #

Oleic acid 14, ο $

Ifinoic acid 75.5 5 »

Linolenic acid ο, $ 2

other acids o, $ 3

Pest fat index 0 at O ⁰ O.

The acids given above are of course in the form of glycerides.

All values _r indicate the percentages of fatty acids in an oil in the description, refer to the

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velvet fatty acid content of the oil.

Bas oil was uncontrolledly transesterified as follows;

About 4-54 kg (looo lbs) of the oil was pumped into a container equipped with a jacket cooler, stirrer, evacuator, and exhaust valve. The oil was refined by alkali treatment and then at 150 ° for 1 hour The oil was then cooled to about 70 ° with stirring; then 0.2% sodium methoxide powder was added and stirring was continued for a further hour at 70 ° C. under a sticky layer to prevent oxidation, turning the oil into an oil was transesterified with an arbitrary configuration «The oil was washed with water to inactivate the catalyst and to remove alkaline substances such as sodium hydroxide and soaps that arise from the sodium methoxide catalyst, then refined, bleached and deodorized»

The invention is explained in more detail below with the aid of examples,

example 1

9o parts unguided interesterified safflower oil and Io parts consisting of a generally solid hard component having an iodine value of 42.3 »of a mixture of equal parts of peanut oil and Baumv / ollsamenwinterölstearin were weighed into a kneader at about 55 ⁰ C and a Llonoglycerid selected from BauUiWollseed Oil (iodine number 82) was made, along with lecithin, vitamin A and carotene added in customary amounts.

In a separate container put non-fat, dry skimmed milk containing ten times the weight of water

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was redissolved, pasteurized and ^{refrigerated to 4.5 0} O (40 ° F). About 1/10 of this dairy product was cultivated and returned to the container. Salt, potassium sorbate and herbs and spices were then added in the usual amounts.

19.8 parts of the aqueous mixture was mixed with 8o.2 parts by weight of the liquid oil mixture to form a water-in-oil emulsion. The temperature of the emulsion was adjusted to 4o ⁰ to 42 G, and this at a feed rate of about loo kg (22o

"ι

lbs) per hour passed through a cooled scraped surface heat exchanger after about 12 to 14 vol .- $ nitrogen gas have been dissolved under pressure in the emulsion in order to ensure a predetermined specific weight of the margarine. The cooled and processed margarine was then (oz. 8) in a semi-liquid state to a Behäl ter of about 227 g were charged and at a temperature of about 14 to 15 ⁰ C cooled to about 7 ⁰ C until it solidified. The composition of the margarine is given below:

Fat phase Parts by weight Glycerides 79.794 Mono / diglyceride emulsifier o, 18 Lecithin 0.22 Vitamin A and Beta Carotene o, oo6 Aqueous phase

redissolved skimmed milk

(9 »1 # solids) 17.924

Salt ■ 1.75

Potassium sorbate ο, io

Spices or flavorings o, o26

loo.ooo

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the polyunsaturated fatty acid content was $ 69.3 by weight

The penetration of the product betrug'2 * 55 at 7.22 ⁰ G F) and 4o2 ~ at 21.1 ⁰ C (7o ° F). The margarine was
stored at -23.3 ⁰ O (-lo ° F) for 26 weeks. At the end of this time, the texture of the product when it was painted on at room temperature was smooth.

Example 2

A number of margarine products have been made according to
prepared according to the procedure of Example 1 by ungoverned transesterification of some or all of the safflower oil, and its stability was determined after storage at -23 ', 3 ⁰ C (-lo ° F) by examining the degree of development of a lumpy, granular texture of the Product compared.
The results are given in Table II below. A particularly preferred product has been that in which about $ 50 of the liquid oil has been undirectedly transesterified. With this mixture there were the structure and the
The mass after storage at -23.3 ⁰ C (-lo ° F) is satisfactory and the free oil formation is minimal at room temperature. For comparison with the products of this example, the results in Table II include a non-unguided interesterified sample of the same composition.

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Table II

Üngelenkt umgeester- tes safflower oil #

Hard component penetration

Structural stability

Worth iodine

I 021.1 ι week 4 weeks 6 weeks 12 weeks 26 weeks

ο co co ω

ο ro to

loo

5o

35

25th

Io 43.3 235 4o2

Io 43.3 ² 5o

lo, 75 49.7 248

lo, 75 49.7 255

Io

43.3 223

S. S. S. - S. S. * I. S. S. S. _s (a) H
V> J S. S. S. _s (a) I. S. ^{u (b)} U

U S

■ <a> _

unstable, lumpy, granular structure and loss of substance in less than 1 week stable, smooth structure

it is believed to be stable for a long time, but no observations have been made carried out beyond the specified time

= stable for more than 2 weeks, but less than 4 weeks.

Example 3

A margarine was made as described in Example 1 on the basis of $ 89.25 of $ 50 unguidedly interesterified safflower oil and $ 0.75 or similar hard component with an iodine number of 41.6 and a plague fat index value of 71.5 at 21.1 ⁰ C, 62.6 at 33.3 ⁰ C and 41.7 at 40 ° C. -

The structure of the margarine did not deteriorate after storage for more than 4 weeks at -12.2 ° C (lo ° P). The penetration at 7.22 ⁰ C (45 ⁰ P) was 23o and at 21.1 ⁰ C (7o ° P) 343rd

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* · IS -

Example 4

A margarine was produced as in Example 1, on B / kais from $ 88.5 of unguided safflower oil and $ 11.5 of a similar hard component with an iodine number of 42.3. The margarine had a penetration of 231 at 7.22 ° o '(45 ⁰ P) and 339 at 21.1 (70 ° F), the structure remained at <-25.3 ° C (- 1O ⁰ P) stable * The polyunsaturated oil content was $ 68, based on the weight of the total fat,

Example 5

A margarine was prepared according to the method of the game 1, based on $ 8.5 of an unguided transesterified Safflower oil and $ 15 hard component, the other one Iodine number consisted of 54.7 hydrogenated rapeseed oil.

The margarine had a penetration of 195 at 7.22 ° 0 (45 ⁰ F) and 335 at 21.1 ⁰ C (7o ° F). The polyunsaturated oil content was $ 65.5, based on the weight of the total fat. The structure was stable after 13 weeks storage at 12.2 ⁰ C (-1O ⁰ F).

Example 6

A margarine was prepared according to the procedure of Example 1 on a $ 92 basis of unguided interesterification Safflower oil and $ 8 hydrogenated rapeseed oil made to an iodine number of 53 to 55.

The margarine had a penetration of 399 can at 7 "22 (45 ° F) and was too soft to be measured with the apparatus used at 21.1 ⁰ C (7o ° F).

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The polyunsaturated fatty acid content was $ 7o, $ 8,.

Example 7

50 parts of safflower oil, in which 76 $ of the fatty acids linoleic acid, $ 1 linolenic acid and lo, o $ saturated fat were, with 40 parts of sunflower oil, in which $ 52 of fatty acids mnolic acid, $ 2 linolenic acid and $ 17 saturated Fatty acids were mixed. The mixture was uncontrolledly transesterified according to the method described.

9o parts of the transesterified mixture given above and Io parts of a hard component which is a mixture of Containing equal parts cottonseed winter oil stearin and peanut oil and having an iodine number of 49 were mixed and prepared therefrom according to the procedure set forth in Example 1, a margarine. The hard component had no polyunsaturates and $ 43 saturated. Fatty acids. The ratio of polyunsaturated Acids to saturated acids in the margarine was 3.7: 1. '

Example 8

9o parts sunflower oil, in which the fatty acids contained 7o, 4 $ linoleic acid and 12.3 $ saturated acids, were uncontrolled transesterification according to the procedure of Example 1. Became the unguided interesterified mass Io parts of a hard component made from a mixture of equal parts cottonseed winter oil stearin and peanut oil with an iodine number of 49, in which the fatty acids are not polyunsaturated and 43 $ saturated fatty acids included, admittedly. The mixture became too

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Margarine processed according to the procedure of Example 1. The linoleic acid content of the fat composition the margarine was $ 63.4 and the saturated content Fatty acid was 15 »4%, which is a ratio of 4.1: 1 revealed.

The products of Examples 6, 7 and 8 showed, like the products of the previous examples, good structural stability after storage at deep-freezing temperatures.

In all of the above examples, the Pene ™ tration values obtained by placing a cone of 67 g with an acute angle of 15 ° 46 'perpendicular to the Drops margarine mass from a height of 20 mm. The number of tenths of a millimeter that the cone under the Surface penetration was reported as "penetration".

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Claims (20)

Claims / 1. Non-directionally interesterified cooking oil, in which at least 65 $ of the combined fatty acid content is polyunsaturated. 2. edible oil according to claim 1, characterized in that it is safflower oil, tobacco seed oil or oil of a suitable one Includes type of sunflower. 3 · Edible oil according to claim 2, characterized in that it contains safflower oil with a linoleic acid content of $ 73 to $ 79 and a saturated fatty acid content of $ 9 to $ 12. 4. Margarine fat composition suitable for use in the manufacture of margarine and similar emulsions middle of the line is suitable, from a mixture of edible, usually liquid and usually solid edible fat components, characterized in that as a liquid component of an edible oil according to any one of claims 1 to 3 is applied. 5. fat composition according to claim 4, characterized in that the main portion of the usually liquid Component an edible oil with a polyunsaturated fatty acid content of at least $ 65 of the at least $ 25 unglued is applied. 6. Fat composition according to claim 51, characterized in that that the oil has transesterified loo $ ungoverned. 109837/1022 7. fat composition according to any one of claims 4 "to 6, characterized in that one usually solid component with an iodine number of 35 to 6o and a saturated fatty acid content of 23 "to 6o # the total combined fatty acid content in the mixture is applied. 8. Fat composition according to claim 7, characterized in that the usually solid component partially hydrogenated rapeseed oil with an iodine number of 53 ^ up to 55, 9. Fat composition according to claim 7 »characterized in that the usually solid component comprises a mixture of cottonseed winter oil stearin and peanut oil having an iodine number of 4o to 5o. 10. Fat composition according to one of the claims 4 to 9 »characterized in that 8o to 94 $ one usually liquid component and 6 to 20 $ one usually solid component are used, with the ratio of polyunsaturated fatty acids, to saturated fatty acids in the mixture 3 »5 to 5: 1 ™ amounts to. 11. Fat mixture according to claim lo, characterized in that that about 90 $ of the usually liquid component is used. 12. Hargarine fat composition according to any one of Claims 4 to 11, characterized in that it contains from 60 to 75% of polyunsaturated fatty acids. 109837/1022 I (06127 - 2ο - 13. margarine or similar emulsion spreads, characterized in that a fat composition according to one of the claims for the fat phase 4 to 12 is applied. 14. Margarine according to claim 13, characterized in that it has the following plague fat index values: 29.9 to 9 at ⁰ ° C, 1.8 to 6 at 21.1 ⁰ C, · o 4 - 3.5 at 33.3 ⁰ C, O - l, o at 4o ° C. 15. A process for the production of a margarine fat, which is suitable for use in margarine and similar edible fat emulsion spreads, wherein a high content of polyunsaturated fatty acid is combined with an acceptable structural stability in freezer storage, characterized in that one usually mixes solid and liquid edible fat components, for the a highly unsaturated fat component with a combined, polyunsaturated fatty acid content of at least 65 $ is used, which is undirected before being incorporated into the mixture. 16. The method according to claim 15, characterized in that the highly unsaturated Pett component at the mixture is used both in an uncontrolled interesterified form and in a non-uncontrolled interesterified form. 17. The method according to claim 16, characterized in that the unguided unesterified shape and the not unguided interesterified form of the highly unsaturated Pett component be used in approximately equal amounts in the mixture. 109837/1 022 -21- 2 JÜ6127 18. The method according to any one of claims 15 to 17, characterized in that the highly unsaturated fat component safflower oil, tobacco seed oil or oil of a suitable one Includes type of sunflower. 19. A process for the preparation of margarine and similar edible fat emulsion spreads, in which one a highly unsaturated edible fat with a combined polyunsaturated fatty acid content of at least $ 65 unguided interesterified, the unguided interesterified Fat incorporated into a mixture with an usually solid fat, the mixture deodorizes, the deodorized Mixing at a temperature at which the mixture is completely liquid with an aqueous phase mixes to form an emulsion and works the composition into a plastic mass, cools and annealed, with crystallization of the fat and the emulsion occurring. 20. The method according to claim 19, characterized in that that a composition according to any one of claims 4 to 12 is used in the mixture. 109837/1022