DE1170231B - Process for making margarine that does not splash or splash when frying - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: A23d

German class: 53 h -1/02

Number: 1170231

File number: N 16332IV a / 53 h

Filing date: February 28, 1959

Opening day: May 14, 1964

The invention relates to a method for producing little or no when frying splashing margarine.

Many attempts have been made to find substances whose presence in margarine is beneficial for the Consumers annoying splashes when frying margarine reduced or completely eliminated. Under the Additives with such an effect are lecithins or phosphatides in the form of egg yolks or of Plant phosphatides from oilseeds have been known for the longest. In more recent times it is also used as an additive synthetic lecithin was added. These substances reduce the tendency to splash somewhat, but are far from being effective. In addition, they degrade the taste and the shelf life of margarine, if it is sufficient to achieve a remarkable effect Amount to be added. A number of chemical substances were also tested. Although some of They significantly reduce the splash of margarine, against their use health-wise Concerns. Other physiologically harmless additives have too little effect.

A number of chemicals intended to prevent splashing when frying margarine are described in U.S. Patents 1,917,249-1,917,253 and 1,917,255-1,917,260. These substances are monofatty acid esters of polyhydroxy compounds including oxyacids, fatty acid sulfonates, sulfates, phosphates and phosphites as well as nitrogen compounds containing fatty acid residues, ζ. B. Amides from fatty acids and amino acids. Apart from the fact that the addition of the mentioned sulfates, sulfonates, phosphates, phosphites and nitrogen-containing compounds to margarine is not physiologically harmless, using sulfuric and phosphoric acids or their chlorides and oxides and using large amounts of pyridine and acid chlorides He also did not prevent the splashing of margarine to the desired extent. Of all the compounds listed, only the sodium salt of monostearin sulfoacetate (US Pat. No. 1,917,256, page 3, line 7) has found commercial use as a component of the commercial product "Emargol". However, it is far inferior to the additives according to the invention. Its use in the spraying test described later resulted in an injection loss of 4000 mg with the addition of 0.12% and an injection loss of 3000 mg with the addition of 0.2%.
The addition of fatty acid esters of polyhydroxyl process for the preparation of when frying
little or no splashing margarine

Applicant:

N.V. Koninklijke Stearine Kaarsenfabrieken

»Gouda-Appollo«, Gouda (Netherlands)

Representative:

Dr. W. Beil and A. Hoeppener, lawyers,

Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority:
Netherlands 5 March 1958

compounds to margarine is harmless, but the effect achieved is less than that with the Additives according to the invention achieved, as can be seen from investigations described later. Of the Stearic acid ester of sucrose, which according to the table on p. 9/10 of US Pat. No. 1,917,250 The most potent compound of this class is when used in an amount of leads 0.5% to an injection loss of 400 mg.

Also those from the USA patents 2,485,631, 2,485,632, 2,485,634 and 2,485,638 known additives, namely monoalkyl and monoalkenyl citrates, which may be used together with solubilizers, dialkyl and dialkenyl citrates, also in a mixture with monoalkyl and monoalkenyl citrates, as well as mixtures of mono-, di- and trialkyl- or alkenyl citrates in connection with mono- and diglycerides of aliphatic monocarboxylic acids, which are supposed to delay the rancidity of margarine, have no effect on that Splash of margarine while frying. The same applies to that of US Pat. No. 2,701,203 known esters of acyl glycols and aliphatic tricarboxylic acids, which are added to glycidic oils, to increase their durability.

It has now been found that margarine splashes little or not at all when frying

409 58J / 243

a mixed ester of a polyol containing three or four hydroxyl groups, in which one Hydroxyl group is esterified with a fatty acid having 8 to 24 carbon atoms, one with a Fatty acid having 1 to 24 carbon atoms and having one or two hydroxyl groups can be esterified a polycarboxylic acid, namely tricarballylic acid, aconitic acid or acylated or non-acylated oxypolycarboxylic acids are esterified, the polycarboxylic acid residues having at least one free carboxyl group must contain. Mixed esters with two acyloxypolycarboxylic acid residues in which the number of acyl residues is four or more per ester molecule, but are excluded. Instead of a mixed one Several of these esters can also be added to the margarine.

The mixed esters according to the invention have the following general formula:

Polyalcohol residue

- (OH) _n ,

O ■ CO · R '

- (O · CO · R ") n

Polycarboxylic acid residue

o-co

- (COOH) ^ - (COOX) ₉ - (OH) _r

- (O · CO · R '") _s

η the O · CO · R 'is a fatty acid residue with 8 to 24 C atoms, O · CO · R "and O · CO · R'" is a fatty acid residue with 1 to 24 C atoms, X is one reduced by one HO group Residue of a polyol, t - 1 or 2, q + r + s = O to 3, r = O, 1 or 2, q = O or 1, t + s ^ 3, p - \ - q = 1 or 2, s = O, 1 or 2, P = I or 2 and p + r + s = 2 or 3 and, a) if the mixed ester is derived from a triol, m - O or 1, η - O or 1, m + η + 1 = 2 and, b) if the mixed ester is derived from a tetrol, m = \ or 2, η - O or 1, m + η + 1 = 3.

The addition of the above-mentioned esters to margarine causes the water contained in the margarine to evaporate completely smoothly during frying or baking without local explosive phenomena, so that little or no loss of splash occurs. The splash loss was determined by adding the additives in a certain ratio to a standard margarine which did not contain emulsifiers and had been made with acidified skimmed milk and contained 0.8% salt. The aqueous phase was adjusted to a pn value of 5.2 to 5.3 with buffer substances. 80 g of the margarine to which the additives to be investigated were added were placed in a flat, non-enamelled pan with a diameter of 21 cm. The margarine was heated using a gas ring burner in 6 minutes at 175 ⁰ C, first being heated with full flame and when this was necessary, smaller introduced to maintain the temperature to 175 ° C. A pre-dried and weighed filter paper with a diameter of 32 cm was placed horizontally above the bottom of the pan at a distance of 10 cm. When the margarine no longer splashed, ie when all the water had been driven out, the filter paper was dried for 1/2 hour at 100 ° C. and then weighed. The weight gain in milligrams indicates the injection loss.

The margarine produced according to the invention also has other advantageous properties. Contains she z. B. still ingredients that form a brown deposit when frying, so cause the added Ester, that it is finely divided and does not stick together. Various of the procedural added esters also cause the surface of the molten margarine to partially expand covered with a stable, fine foam, a property that is very desirable in margarine. The margarine according to the invention consists of a clear yellow top layer after frying with tanned particles floating freely underneath. The addition of the preferred esters is beneficial for the most part also a good browning and foaming of the margarine with it.

The anti-splash esters can be added at any stage of margarine production where good distribution in the margarine is possible. You can z. B. the oils and fats after their deodorization, preferably when the temperature is not above 10O ⁰ C, add. Instead of the esters, you can also add substances that are converted into the active ingredients in the margarine. The amount of the esters depends on their composition, in particular on whether the esters used consist of mixtures with esters of less activity or mixtures with unreacted proportions of the starting materials. For example, when using the reaction product from the esterification of technical-grade monoglycerides, which contain 35% pure monoglycerides, with an acylated or non-acylated oxypolycarboxylic acid, 0.2 to 0.3% suffice.However, if the mixed ester has a monoglyceride of 90% purity 0.05% may be sufficient.

The simultaneous addition of phosphatides of vegetable, animal or synthetic origin in the same order of magnitude as the mixed ester causes one over the sum of these individual effects Ingredients going beyond effect, so that in this case often an amount of about 0.1% of mixed ester is sufficient. Even amounts of 0.01 to 0.05% can be sufficient. The phosphatides can be added in purified form or in the form of so-called lecithin, which is derived from vegetable oils is obtained and contains approximately 60% phosphatides and 30 to 40% vegetable oil. The phosphatides mentioned here are in each case such materials with a pure phosphatide content of around 60%.

The synergistic effect achieved by the simultaneous use of phosphatides comes out the following table.

Table 1
Experimental series with margarine batch A

Mixed ester
from equimolar
Sets of Z
Ester sentences (
Soy-
leci-
thin 7.)
Glycerin
mono
stearate Spray
loss
(mg) (No additions) - 0.04
0.12 0.1
0.1 4250
1700
400 Citric acid and
Glycerol monostearate
(about 50%) 0.12 0.1 250 Citric acid and
Glycerol monostearate 0.12 0.04 0.1 Citric acid and
Glycerol monostearate
(about 50%) 0.04 0.04 0.1

Similar results were obtained with the analogous ester made using malic acid as shown in the table below.

Table 2
Experimental series with margarine batch B

Mixed esters of equimolar
Sets of

(No additions)

Malic acid and glycerol monostearate (90%)

Malic acid and glycerol monostearate

Malic acid and glycerol monostearate (90%) ....

Additions ( ⁰ I ₀ )

Soy lecithin

Ester

0.12
0.24
0.12

0.04
0.12
0.3

0.04

Loss of injection (mg)

10,000

2,500

475

200

600

The above tables show that the invention Esters in connection with extremely low additions of phosphatides prevent the margarine from splashing completely when frying switch off.

The optimal ratio of mixed esters to phosphatides changes with the composition the ester. In general, the amount of phosphatides should be the same as the amount of mixed esters or less, about 30% of these.

The esters according to the invention can of course also be mixed with other fats and oils If necessary, along with phosphatides, the splashing of these fats and oils when frying to prevent.

Most processes for the preparation of mixed esters of the general ones given earlier Formula do not of course result in a uniform product, but mixtures of esters. If z. B. 1 mole of glycerol monostearate is esterified with 1 mole of malic acid, the esterification with a carboxyl group of malic acid formed esters of glycerol monostearate the main component of the reaction product. At the same time, however, even if in smaller quantities, all possible combinations between the hydroxyl groups of the glycerol monostearate and the carboxyl groups malic acid occur. For the purpose according to the invention it is not necessary to break down the reaction mixture into the individual esters, but rather

ίο this can be used as it is.

Glycerol and pentaerythritol are advantageously used for the production of the esters used according to the invention or sorbitan, a saturated or unsaturated fatty acid with 8 to 24, preferably 8 to 20 and especially 12 to 18 carbon atoms, a polycarboxylic acid, namely tricarballylic acid, aconitic acid and acylated or non-acylated mono- or dioxypolycarboxylic acids having 4 to 6 carbon atoms used.

By a simple method is effective esters obtained by about 15 minutes long to 10 hours of heating a Fettsäuremonoesters a triol or tetrol or a Estergemisches containing such Monoester with a Oxypolycarbonsäure at 110 to 150 ⁰ C. The reaction time of the reaction temperature is inversely proportional. It is advantageous to use approximately equimolar amounts of the monoester and the oxypolycarboxylic acid. As can be seen from the following table, an optimal effect is then achieved. 0.10% glycerol monostearate, 0.04% soy lecithin and 0.12% ester mixture according to the invention had been incorporated into each of the samples examined.

Table 3

Ester off

1 mole of malic acid and
1 mole of glycerol monostearate

0.33 moles of malic acid and
1 mole of glycerol monostearate

3 moles of malic acid and

1 mole of glycerine mono-

stearate

1 mole of citric acid and
1 mole of glycerol monostearate

0.4 moles of citric acid
and 1 mole of glycerol monostearate

3 moles of citric acid and
1 mole of glycerol monostearate

Tempe
rature
( ⁰ C) Reak
ions
time in
Stun
the Ester
(° / o) 130 2 0.12 130 2 0.12 130 2 0.12 130 2 0.12 130 2 0.12 130 2 0.12

Splash loss

(mg)

190

If 3 moles of acid are used per mole of glycerol monostearate, some of the excess remains Acid undissolved after the reaction. . When converting a maximum of 1 mole of oxypolycarboxylic acid with 1 mole of fatty acid monoester, the acid, which is usually the most expensive, becomes at the same time Component represents, largely exploited, and

any excess monoester in the margarine is useful as an anti-exudate agent. A ratio of 0.8 to 1.2 mol to 1 mol is preferred, but in particular a ratio of 1 mol to 1 mole.

The monoester used for the reaction with the oxypolycarboxylic acids should optionally be contained therein contained triol or tetrol exempted, as the free polyalcohol rapidly to form a

cleavage occurred during prolonged heating, reversed.

Monoglycerides are very suitable as starting material for the production of the invention mixed ester. Although the chain length dvs or the fatty acid ester and the fact whether this is saturated or unsaturated are not critical, monoglycerides are those derived from stearic acid or oleic acid or mixtures of fatty acids as described in

rubbery deposit, which does not contain any effect on edible fats, is preferred. The esters of

the spray has, reacts with the oxypolycarboxylic acid. Are oxypolycarboxylic acids with glycerol monostearate

In the fatty acid monoester, a maximum of 0.3% polyol are solid substances, those with glycerol monooleate are highly viscous

permitted. Next is prolonged heating on reaction liquids.

temperature, because if significantly less The term "monoglycerides" includes before 1 mole of oxypolycarboxylic acid per mole of monoester 15 is not only technical monoglycerides that was used, a second carboxyl group usually 35 to 50% mono-, 30 to 40% diester can be, increasing the effectiveness against and contain 10 to 20% triglycerides, but also splashing is reduced. But even if there is no purified monoglyceride, which is caused by a special excess has been used in fatty acid monoesters, has been enriched in monoglycerides, can be prolonged heating, or only brief heating 20 These result from their esterification with polycarbonate too high temperature, e.g. B. to 150 ° C, in particular more effective products than monoglycerides with the other when using negative pressure the effective lower content of real monoglycerides. reduce the ability to prevent splashing. If you heat z. B. Useful anti-splash esters while passing nitrogen through, 1 mole of glycerine monostearate also from diglycerides and oxypolycarboxylic acids (in the form of a technically preserved 25; but they require esterification

Mixture of glycerides with a content of 70% monoester) with 1 mol of citric acid under vacuum (30 mm) at 130 ^° C., the following values are obtained:

To
1 hour To
10 hours Reduction in glycerol mono
stearate, mole
Decrease in citric acid,
Mole 0.75
0.82
0.90
138
10 1.0
1.0
1.95
37
1000 Formed moles of water
Acid number
Loss of splash on margarine that
0.12% of the generated react
mixture, 0.04% soy
lecithin and 0.10% glycerin
contained monostearate, mg

temperatures of over 150 ⁰ C. A useful ester is z. B. obtained from 1 mole of glycerol distearate and 1 mole of citric acid by heating to 155 ^° C. for 1 hour.

Instead of oxypolycarboxylic acids, unsaturated polycarboxylic acids can also be used for the esterification which, under the esterification conditions, result in oxypolycarboxylic acids due to the addition of water to the double bond. For example, when maleic anhydride is esterified with 1 mol of glycerol monostearate containing 2% water at 130 ^° C. under atmospheric pressure, after half an hour to one hour, an ester that is moderately effective against splashing is obtained. The ester obtained after 2 to 5 _{hours for 2} hours, on the other hand, was highly effective against splashing. After 8 hours of heating, the effectiveness decreased again. When esterified using anhydrous starting materials, similarly effective products were obtained, but the effectiveness of the product obtained after 5.5 hours was much lower. Good effectiveness can also be achieved under reduced pressure if sufficient water vapor tension is maintained. When using citraconic acid instead of maleic

Although it has not been clarified exactly what other reactions after prolonged heating or Heating to a higher temperature is clear,

that in order to avoid a loss of effectiveness 50 acid anhydride the results were similar, after the end of the period required for the primary esterification For the preparation of the ge according to the invention

lent time the heating should be stopped.

The ester obtained from glycerol monostearate and malic acid is more resistant to prolonged heating
on z. B. 130 ⁰ C under normal pressure. For the 55th
Esterification of the polycarboxylic acids with Fettsäuremonoester is 1- to heating for 2 hours at about 130 ⁰ C
with stirring, reduced pressure and / or passing through an inert gas and cooling the
Reaction mixture can be esterified after completion of the primary 60. If diglycerides are used, esterification is preferred. or diesters of pentaerythritol and sorbitan

The are from 1 mole of glycerol and 1 mol again heated to a higher temperature, about 150 obtained to citric acid esters, which by prolonged 18O ⁰ C,. Glyceride or a partial fatty acid ester that had lost its effectiveness from 1 mole of mono-heating regains glyceride or a partial fatty acid ester, which is at least partially caused by the other polyols mentioned for weeks and 1 mole of acylated storage of the margarine hydride containing this ester when added. Are likely to this margarine anhydride in an amount from 0.12 to 0.24% e ^em formations and other reactions, the striking effect under water. The effect of the is even stronger

Mixed esters can, as mentioned, also acylated oxypolycarboxylic acids, such as acylated tartaric acid or Citric acid, can be used.

Acylated tartaric acid is advantageously used as the anhydride because acylated acids are obtained in this way and practically by simply heating for 2 hours with 1 to monoglycerides or Monoestern of pentaerythritol and sorbitan to 100 to 150 ⁰ C completely

without the addition of strong mayigarine, if 0.12% ester and 0.04% soy lecithin are added. For example, in the case of a margarine that showed an injection loss of more than 10,000 mg without addition, after incorporation of 0.20% of an ester composed of 1 mol of glycerol _{monostearate (90 ° / 0} content) and 1 mol of diacetyltartaric anhydride, an injection loss of only 200 mg observed. After incorporation of 0.12% of the ester and 0.04% soy lecithin, no loss of splash was observed at all. With the addition of 0.12% ester of 1 mol glycerol _{monostearate (70% content) and} 1 mol acetyl citric acid, the same margarine showed an injection loss of 100 mg.

When 0.12% ester and 0.04% soy lecithin were added, no loss of splash was observed.

A low splash loss of only 90 mg was also observed when using 0.12% margarine Esters from 1 mole of glycerol monostearate and 1 mole of stearoyl citric anhydride and 0.04% lecithin added.

In contrast, the injection loss without lecithin 2000 was mg and mg in combination with lecithin in 1800, when zusetzte an ester of 1 mole of glycerol and 2 mol of diacetyl tartaric acid long by heating for 10 minutes at 160 ° C, or by 1-hour heating at 12O ⁰ C was obtained and contained four acyl residues in the ester molecule.

The mixed esters of polyols, fatty acids and polycarboxylic acids to be added to margarine according to the invention are harmless and are produced under physiological conditions by enzymes of the digestive tract hydrolyzed, as can be seen from the following studies.

In vitro investigation

1 g of ester obtained by reacting glycerol monooleate with citric acid was in 50 ecm of a Suspended solution containing 100 mg of pancreatic extract (USP pancreatin), 100 mg of dried intestinal mucosa and contained 100 mg bile salts. The mixture was adjusted to the pn value 7.0 and in one Incubator kept at 37 ° C for 48 hours. The pH was readjusted approximately every 12 hours. The mixture was then made alkaline, extracted with ether, the ether extract washed, the Ether removed and the residue weighed. The experiment was then carried out with glyceiyl lactopalmitate (Atmul 200) and repeated with corn oil as substrates.

Results:

(Continuation of the table)

sample Ether soluble
Residue
after
digestion
(G) digestibility
(° / o) Corn oil
1.
2. «
3. 0.2734
0.2532
0.2649 72.7
74.7
73.5
Average 73.6

Ether soluble digestibility 75.7 sample Residue
after 73.7 digestion (° / o) 65.3 (G) Average 71.6 Oleic acid glyceride citrate 1. 0.2432 81.0 2. 0.2636 77.3 3. 0.3474 64.1 Average 74.1 Glyceryl lacto- palmitate 1. 0.1903 2. 0.2267 3. 0.3594

From the above figures it can be seen that the enzymes of the digestive tract add the oleic acid glyceride citrate digest. The resulting products, namely citric acid (it has been identified as a digestive product) and glycerol monooleate, are known to be non-toxic.

In preliminary tests, digestion values were obtained with all substrates after an incubation period of 3 days has been obtained by over 90%. An incubation time of 2 days was therefore selected because of differences in digestibility, if present at all, if digestion is interrupted in the intermediate State more clearly. However, the above results show that the rate of oleic acid glyceride citrate digestion is comparable to that of glyceryl lactopalmitate and corn oil.

In vivo experiments

The method of C a 11 ο w a y et al.

(Food Research, Vol. 21, p. 1, 1956) used to determine the digestibility of fats.

Thirty newly weaned rats were divided into three groups of five males and five females Rats were subdivided, taking care that there was equality between the individual groups body weight and origin. Group 1 was fed a basic forage, its Composition is given in Table la. Group 2 receives 80 parts of basic forage and 20 parts

Oleic glyceride citrate. Group 3 receives 80 parts of basic forage and 20 parts of glyceryl lactopalmitate (Atmul 200). Both the oleic acid glyceride citrate and the glyceryl lactopalmitate were added to the diet neutralized.

The rats were placed individually in cages with wire mesh floors, in which they kept their respective cages for 7 days Diet and water were given ad libitum. During this time, the body weight and food intake were monitored registered. The corresponding values are compiled in Tables 2a and 3a.

The feces of each rat were collected daily. At the end of the experiment, the collected Grind samples to a homogeneous mass, dry and weigh some of them for fat determination. The values determined from the fat values of the faeces and the added fat are shown in Table 4 a listed.

It should be noted that the digestive values are actually a combination of digestion and absorption represent. However, they show that oleic acid glyceride citrate is equally effective and possibly is digested and adsorbed even more effectively than glyceryl lactopalmitate.

409 589/243

1

Those with oleic acid glyceride citric acid and glyceryl lactopalmitate The fed rats grew slower than the control animals because of the lower feed consumption. It is due to the poor palatability of the ingredients containing the additives in such high concentrations Feed back. However, the feed containing the additives was used just as well like the control feed. According to this, toxic symptoms cannot be ascribed to the additives used will.

Table la Composition of the basic feed

Wheat flour (including meal) 32.80%, _

Ground yellow corn 32.80%

Dried milk (skimmed) 17.50%

Fish meal (60% protein) 5.30%

30th

Soy flour (44% protein) 5.30%

Dehydrated alfaalfa flour 2.10%

Dried brewer's yeast 2.10%

Liver 1.05% * ^S.

Steamed bone meal 0.49%

Iodized salt 0.42%

Trace elements (Delamix) 0.04%

dl-methionine 0.10%

100.00%

Table 2a Average weight of the individual rats

group Initially
(G) Over
(G) Weight
increase
(G) 1 (control)
2 (oleic acid glyceride
citrate)
3 (glyceryl lacto-
palmitate) 55.1
54.0
53.4 84.7
77.5
77.8 29.6
23.5
24.4

Table 3a

group Average
Feed intake of the
single rats
(G) Average
Amount of faeces
collected per rat
and dried
(G) fat
in faeces
(7o) 1
2
3 60.2
51.5
49.9 7.4
7.1
6.3 3.90
5.05
19.67

Table 4a

group Average
Recording of
added fat
(G) Average
in the faeces
retired
Total amount of fat
(G) Ver
daulich
speed
CU) 1
2
3 0
10.3
9.98 0.29
0.36
1.24 99.3
90.5

% Digestibility =

ingested amount of added fat - (fecal Fat per test animal - fecal fat per control animal)

absorbed amount of added fat

100

summary

The results from the in vitro and in vivo experiments show that oleic glyceride citrate is digested and absorbed as well as glyceryl lactopalmitate and corn oil. They thus prove the non-toxicity of oleic acid glyceride citrate after oral ingestion.

The investigation of esters from soybean oil or Rapeseed oil monoglycerides and citric acid and esters of soybean oil fatty acid monoglycerides and diacetyltartaric anhydride gave no clues for physiologically questionable properties of the esters to be used according to the invention. the Studies were carried out on groups of ten male and ten female Wistar rats carried out. This was done ad libitum over a period of 12 weeks

a) a standard two-thirds diet Wheat flour, one third whole milk powder and 1% salt mixture (water as desired) and 2, 4, 8 or 10% soybean oil fatty acid monoglyceride citrate,

b) a standard diet of two-thirds unlubricated Wheat flour, a third of skimmed milk and 1% salt mixture (water to taste) and 10% soybean oil fatty acid monoglyceride citrate and

c) a standard diet consisting of two thirds of unbagged wheat flour and one third of whole milk powder and 1% salt mix (water ad libitum) and 10% soybean oil fatty acid monoglyceride citrate or rapeseed oil fatty acid monoglyceride citrate or soybean oil fatty acid monoglyceride diacetyl tartrate

fed. There were no pathological changes prohibiting the administration of these esters observed.

The oral LD ₅₀ of soybean oil fatty acid monoglyceride citrate in rats is about 50 ml / kg, but cannot be determined precisely because a maximum of 50 ml / kg can be administered orally at one time. The administration of 30 and 40 ml / kg was not fatal in any of ten rats.

The intraperitoneal LD ₅₀ is 17 ml / kg. The administration of 10 ml / kg was not fatal in any of ten rats.

The use of 0.3% of the mixed esters according to the invention in foods is thus harmless. However, as far as the addition of mixed esters is concerned, the claimed process can the constituents of which are foreign matter, based on the general foreign matter ordinance of December 19 1959 not currently used for the production of margarine, which is for sale in the

Domestic is provided. According to § 5b of the law on However, this prohibition does not apply to changes and amendments to the Food Act of December 21, 1958 for products that are intended for delivery abroad.

The following examples explain what is in accordance with the invention Procedure.

example 1

The ester of glycerol monooleate and citric acid added to margarine according to the invention was manufactured as follows:

100 g of glycerol monooleate (about 50% purity, less than 0.1% free glycerol) and 15 g of citric acid were heated with stirring to 12O ⁰ C, was until the mixture completely homogeneous (1 hour). This mixture was not yet effective against splashing when it was dispersed in margarine and the margarine fried. ^{The mixture was therefore kept at 130 °} C. for a further 2 to 3 hours while stirring and passing nitrogen through. The addition of 0.12% of the ester obtained in this way together with 0.1% glycerol monostearate and 0.04% soy lecithin gave a margarine which splashed very little when frying and formed a finely divided brown batch. The foam was good too.

Example 2

100 g of glycerol monostearate (57% pure content, less than 0.1% free glycerol) and 30 g of diacetyltartaric anhydride were ^{stirred at 100 to HO 0} C until a solution was formed. After 10 minutes the monoglyceride content in the mixture had decreased to 19%; the acid number was 87. At this point in time the reaction mixture against splashing was only moderate. After further 2 hours of heating at 13O ⁰ C the acid number to 76, the monoglyceride content had decreased to 10%. After adding 0.12% of the end product together with 0.1% glycerol monostearate and 0.04% lecithin to margarine, like that mentioned in Example 1, this showed particularly good frying properties.

Example 3

100 g (glycerol monolaurate (about 50% purity) and 30 g acetylcitric anhydride were heated with stirring to 120 ⁰ C, was homogeneous to the mixture. After 2 hours further heating to 130 ⁰ C under a nitrogen flow, a product with very good efficacy was compared syringes The percentage of monoglyceride at this point was 17 and the acid number was 40. The addition of 0.12% of the reaction product together with 0.1% glycerol monostearate and 0.04% lecithin resulted in a margarine which splattered extremely little when frying Sentence was satisfactory.

Example 4

100 g of glycerol monostearate (containing 52% monoglyceride and 0.2% free glycerol) and 20 g of citric acid were esterified as in Example 1. After 3 hours heating at 13O ⁰ C of monoglyceride had fallen to 29%. 0.12% of this product was added to margarine along with 0.1% glycerol monostearate and 0.04% lecithin. The resulting margarine splashed very little on frying and formed a satisfactory brown batch.

E xample 1 5

100 g of pentaerythritol monostearate and 48 g of citric acid were stirred and passed through heated by nitrogen to 120 ° C until the citric acid was almost completely resolved. After a further hour of heating at 130 ° C, there was a product with the acid number 130 was created. The addition of 0.12% of this product along with 0.1% glycerol monostearate and 0.04% lecithin produced a margarine with very satisfactory frying properties (reduced splashing, good set and foam).

Example 6

100 g of 50% sorbitan monooleate and 25 g of citric acid were heated with stirring and passing through nitrogen at 12O ⁰ C, was virtually homogeneous until the mixture. After 2 hours of further heating to 130 ⁰ C, the acid number was 64. The addition of 0.12% of the product together with 0.1% glycerol monostearate 0.04% lecithin obtained is a margarine which is not injected and set in relation to the type and foaming was good.

Example7

Ester prepared according to Example B of US Pat. No. 2 192 907 by heating 3 mol of glycerol and 1 mol of citric acid to 140 to 155 ^° C. for 6 hours, which still contained unesterified carboxyl groups, was treated in the cold with 1 mol of stearoyl chloride. After isolation of the ester in the manner indicated in the USA patent by extraction with petroleum ether, the ester had an acid number of 65. An acid number of 75 is calculated for an ester which still contains a carboxyl group of citric acid. The ester therefore does not contain mainly fully esterified citric acid, according to the formula given in the patent, but citric acid in which one carboxyl group is unesterified.

Margarine containing 0.12% of this product plus 0.1% glycerol monostearate and 0.04% lecithin, causes very little loss of spatter and gives a very nice set.

Examples

100 g purified glycerin distearate (80% glycerin distearate, 10% glycerin monostearate, 10% tristearate) and 34.6 g of diacetyltartaric anhydride were stirred under nitrogen and heated to 170 ° C until the mixture was homogeneous. After 2 hours at 170 ° C. the acid number was 69 and the hydroxyl number 24. By addition 0.12% of the product, 0.1% glycerol monostearate and 0.04% lecithin gave a margarine which caused a low splash loss on frying and formed a satisfactory brown set.

Example 9

354 g of technical grade glycerol monooleate (47% purity) and 67 g of malic acid were stirred under nitrogen and heated to 130 ⁰ C, was homogeneous until the mixture. Then the pressure was lowered to 40 mm and the mixture was further heated for 2 hours. 205 grams of acetic anhydride was added to the completely dry product. The mixture was then ^{heated to 120 °} C. for 1 hour. Then the acetic acid and the excess acetic anhydride were mixed

distilled off under reduced pressure. The product, the malic acid ester of glycerol monooleate monoacetate, showed a hydroxyl number of 5. By adding 0.12% the product together with 0.1% glycerol monostearate and 0.04% lecithin resulted in a margarine, which caused no loss of splash when frying and formed a nice set.

Example 10

A mixture of 60 g of aconitic acid and 71 g of acetic acid anhydride was ^{heated to 90 to 100 °} C. for 2 hours. The acetic acid and remaining acetic anhydride were then distilled off under reduced pressure.

The residue, aconitic anhydride was mixed with g of pure glycerol monostearate and heated with stirring in a nitrogen atmosphere to 13O ⁰ C. The mixture was then almost homogeneous, but a sticky set deposited on further heating. Apparently only part of the aconitic anaohydride had reacted with the glycerol monostearate to form the desired ester. Nevertheless, the addition of 0.24% of the top layer along with 0.1% glycerol monostearate and 0.04% soy lecithin resulted in a margarine that caused fairly little splash loss.

Claims (8)

Patent claims: 1. Process for the production of margarine that does not splash or splash when frying, characterized in that one or more mixed esters are added to the margarine one adds polyalcohols with three or four hydroxyl groups, one of which with a fatty acid is esterified with 8 to 24 carbon atoms and another with a fatty acid and 1 to 24 Carbon atoms can be esterified and one or two hydroxyl groups with a polycarboxylic acid, namely tricarballylic acid, aconitic acid or acylated or non-acylated oxypolycarboxylic acids are esterified, the polycarboxylic acid containing at least one free carboxyl group and mixed esters with two acyloxypolycarboxylic acid residues, the four or more acyl residues in the molecule of the mixed ester are excluded. 2. The method according to claim 1, characterized in that the mixed ester is the general formula Polyalcohol residue - (OH) _m
- O CO R '
(O · CO · R ") n Polycarboxylic acid residue
-O-CO - (COOH) "
- (COOX) ₉
- (OC) _r - (O-CO-R "') * has, in which X is the radical of a polyalcohol reduced by one OH group, O · CO · R 'has a fatty acid radical with 8 to 24 carbon atoms and O · CO · R "and O · CO · R'" fatty acid radicals with 1 to Represent 24 carbon atoms, t = 1 or 2, q - \ - r + s = 0 to 3, r = 0, 1 or 2, q = 0 or 1, t + s S 3, ρ + q = 1 or 2, s = 0, 1 or 2, ρ = 1 or 2, ρ -fr + s = 2 or 3 and, a) if the mixed ester is derived from a triol, m - 0 or 1, η = 0 or 1, m + η + t = 2 and, b) if the mixed ester is derived from a tetrol, m = 1 or 2, η = 0 or 1, m + η + t = 3. 3. The method according to claim 1 and 2, characterized in that a carboxyl group of Polycarboxylic acid esterified with a hydroxyl group of an otherwise unesterified polyalcohol is. 4. The method according to claim 1 to 3, characterized in that the polycarboxylic acid tricarballylic acid, Aconitic acid or an acylated or non-acylated mono- or dioxypolycarboxylic acid having 4 to 6 carbon atoms. 5. The method according to claim 1 to 4, characterized in that the polycarboxylic acid is lemon or Malic acid is. 6. The method according to claim 1 to 5, characterized in that the margarine is about 0.01 to 0.3% of mixed ester or mixed esters is added. 7. The method according to claim 1 to 6, characterized in that the margarine in addition to the mixed ester or the mixed esters an equally large, but preferably a smaller one Amount, in particular 0.06 to 0.01 percent by weight of phosphatides, such as vegetable lecithin, is added. 8. The method according to claim 1 to 7, characterized in that one of the margarine Added esters of glycerol monofatty acid ester and citric acid. Considered publications: U.S. Patents Nos. 2,485,631, 2,485,632,
485 634, 2 485 638, 2 701 203. 409 589/243 5.64 © Bundesdruckerei Berlin