DE3001111A1 - EMULSIFIER PREPARATION AND THE USE THEREOF FOR IMPROVING THE QUALITY OF STARCHED FOODSTUFFS - Google Patents

Description

The invention relates to a new emulsifier preparation, which lead to a substantial improvement in the properties of. starchy foods.

Because of their mode of action and harmlessness, monoglycerides and diglycerides are widely used used in the food industry as emulsifiers / where their effect depends on their purity, their appearance, their physical and chemical properties and the type of fatty acid that forms the emulsifier.

In the case of starchy foods, such emulsifiers are required to be excellent in reactivity in particular in terms of strength possess. It is known that high purity distilled monoglycerides of saturated Fatty acids with 14 to 18 carbon atoms serve this purpose well.

When the monoglycerides and diglycerides are used in the fat phase, there are no restrictions in relation to this on the physical properties of the monoglycerides and diglycerides as they dissolve in the fat. In the case of starchy foods, however, it is necessary to remove the monoglycerides and diglycerides in the aqueous Phase to be used to improve the starch complexing effect to reach. In these cases or when the monoglyceride with the raw material is in powder form is mixed, exercise the physical appearance, physical and chemical properties, such as the Crystal form of the monoglyceride, and surface conditions have a strong effect on the behavior of the material the end.

Q3Q044 / 0562

TER MEER - MULUER - STEINMEISTER

RIKEN VITAMINE OIL CO., LTD, Case? 1147

It is known that monoglycerides can exist in polymorphic forms, i.e. the forms sub- &, Ct, β ¹ and β, in the order of decreasing melting points. It is known that the evaluation of the properties is in accordance with the sequence given above, the ß-crystal form being the most stable thermodynamically as the crystalline form, so that the monoglycerides are always sold in the ß-crystal form.

The CF crystal form is different because of its hydrophilic behavior in the aqueous phase more effective. One method of producing the o £ crystal form is the conjugate Crystal method in which the saturated fatty acid monoglyceride is used in combination with fatty acid propylene glycol ester (J. Am. Oil., Chem. 40 (1963) 725) or a method according to which the monoglyceride is in water at a temperature below its melting point dispersed. However, all of these methods have disadvantages such as low monoglyceride contents, the difficulty temperature control or conservation.

For this reason it would be advantageous if the β-crystal form had both a stable crystal state as well as having good properties. Studies have already been carried out on the hydrophilic Improve behavior of the monoglycerides. To increase the specific surface area of the crystalline material a method is known according to which small crystals are obtained by recrystallizing the material using of a solvent (see JP-PS TOKU-KO-SHO 50-34613), and a method according to which an aqueous dispersion the β-crystal form is obtained by adding a stabilizer to a dispersion or dry Powdered monoglyceride by adding binders to a dispersion obtained (see JP-PS TOKU-KO-SHO 44-26900).

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RIKEN VITAMIN OIL CO., LTD.

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These processes lead to a substantial improvement in the properties, but show with regard to

preparing powdery monoglyceride _n problems in that they are expensive from the standpoint of production efficiency, while pasty products are not satisfactory in their handling, their preservation and in their stability. Therefore, there has long been a need to develop simpler processes for the preparation of powdered monoglycerides which are effective in the aqueous phase. As a result of extensive investigations, the applicant has now found a new emulsifier preparation which leads to a significant improvement in the quality properties of starchy foods, which can be handled more easily, which is cheaper and which can be stored for longer periods of time

20 and has a stable quality.

The invention therefore relates to the emulsifier preparation and their use according to the claims.

It has now been shown that the present Invention underlying object to satisfy the above-mentioned need can be achieved can, that one emulsifier preparation from highly pure distilled monoglycerides, the 65 to 85% saturated

30 fatty acid monoglycerides and 35 to 15% unsaturated

Fatty acid monoglycerides and has an iodine number of 10 to 40, pulverized and this preparation is annealed for more than 30 minutes at a temperature of more than 45 ⁰ C, at which, however, the preparation does not melt. In the case of the fatty acid monoglycerides, the carbon number of the saturated fatty acids is preferably 12 to 22 and that of the unsaturated fatty acids is preferably 16 to 22.

030044/0562

RIKEN VITAMIN OIL CO., LTD,

TER MEER - MÜLLER - STEINMEISTER CeS6: 1147

~ t -

The preparation according to the invention can either thereby can be prepared using a fatty acid monoglyceride material having the definition given above met, or that one mixes two different types of fatty acid monoglycerides.

When the amount of unsaturated fatty acid monoglyeride is less than 15% and the iodine value is below 10 the desired results cannot be achieved. On the other hand, if the amount of unsaturated Fatty acid monoglyerides is more than 35% and the iodine value is above 40, deteriorates the ability to complex the starch and at the same time it becomes difficult to produce the material in powder form.

It has been shown that by tempering the emulsifier preparation obtained in this way for more than 30 minutes at a temperature which lies within the range extending from 45 ^° C. to the temperature at which the preparation does not yet melt, the properties of the preparation are drastically improved and the storage stability of the material is favored. When the tempering temperature is below 45 ⁰ C, it requires a longer treatment time to achieve the desired properties, at the same time the grain size coarsens. Therefore, working at such temperatures is not preferred in terms of both productivity and desired properties.

If one solidifies the fatty acid monoglyceride by cooling, it goes after successive conversion the crystal structure from the sub-tf-form to the oc-form and the ß'-Forni into the stable ß-crystal form. if however the conversion time becomes longer, one gets coarser

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RIKEN VITAMINE OIL CO., LTD, Case: 1147

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Crystals. It is therefore necessary to effect the conversion as quickly as possible in order to achieve the finest possible To obtain crystals that are required according to the invention. The most effective method involves using one Solvent. The use of a solvent such as water or alcohols has already been proposed and has also been implemented in practice.

However, as already mentioned above, problems arose with regard to handling and storage stability.

It has now been found that in this regard, fatty acid monoglycerides According to the invention, those whose unsaturated fatty acids are cis-coordinated with regard to their double bond are suitable are.

As indicated earlier, the amounts for the saturated fatty acid monoglyceride and the unsaturated fatty acid monoglyceride are 65 to 85% or 35 to 15%. With a view to complexing with starch, it would be more advantageous to to improve the properties one possible to apply high content of saturated fatty acid monoglyceride in the mixture.

Depending on the type of fatty acid, the fatty acid monoglyceride shows polymorphic melting points. With a difference in carbon numbers up to 4, the material forms but solid solutions. Hence, it doesn't make much difference if you look at the material from your behavior A fatty acid monoglyceride is considered here.

In the first stage of the preparation of the invention In the emulsifier preparation, this solid fatty acid monoglyceride solution is cooled to a temperature below the melting point of the sub-oC crystal form, that is, in normal

030044/0582

RIKEN VITAMIN OIL CO,

TER MEER - MÜLLER. STEINMEISTER CaSe °. 1147

_ ₉ _ 300111

Cases preferably to less than 35 ⁰ C. In this case, the unsaturated fatty acid monoglyceride contained as the minor constituent solidifies between the crystals of the saturated fatty acid monoglyceride. The second stage of manufacture involves crystal transformation by annealing. The temperature of the tempering process is preferably above the crystal melting point of the solid solution of the Sub-Ot or the Ot form. 'In normal cases, this is a temperature of more than 45 ⁰ C. With this annealing process melts the unsaturated Fettsäuremonoglyerid, whereas saturated fatty acid monoglyceride is crystallized in a fine form and stabilized. In this case, the appropriate degree of annealing and the solvent effect of the unsaturated fatty acid monoglyceride lead to an acceleration of the crystal stabilization. That

2Q normal annealing ranges from 2 to 8 days at 45 ⁰ C and from 30 minutes to 1 day at 50 to 55 ⁰ C.

The third stage involves cooling the material, the product being tempered by cooling the Receives monoglyceride. The product obtained in this way shows excellent properties and a stable behavior over long periods of time.

In the preparations according to the invention, the fatty acid monoglyceride is made from cis-unsaturated fatty acids is built up, on the one hand a good solvent and not well compatible with the saturated one Fatty acid monoglyceride and does not inhibit crystallization at low temperatures and on the other hand shows a strongly hydrophilic behavior even at low temperature. Hence, that favors next to the saturated Fatty acid monoglyceride used unsaturated fatty acid monoglyceride when mixed with water as a dis-

030044/0562

RIKEN VITAMIN OIL CO.

Case: 1147

TER MEER - MÜLLER. STEINMEISTER

3001Ί11

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integrator is added, the dispersion of the saturated fatty acid monoglyceride in the aqueous

Phase. Fatty acid monoglyerides based on trans-unsaturated fatty acids are structurally strong compatible with saturated fatty acid monoglycerides, so that they reach a state which, as assumed is similar to the state of a solid solution and has a high melting point. Hence can this material cannot be treated in the same way as the material in the cis configuration.

Furthermore, the properties of the invention Improve the emulsifier preparation to a great extent by using the substances mentioned below additionally used. This means that you can produce an emulsifier with good emulsifying power,

20 by using a mixture / that consists of the above-mentioned mono-

glyceride mixture, mixed with less than 5% of at least one, preferably more than one member of the group comprising alcohols, organic acids, lecithin and stearoyl lactylate, which components are compatible with the fatty acid monoglycerides, pulverized and optionally for more than 30 minutes at a temperature of more than than 45 ⁰ C, at which the mixture does not melt, annealed.

30th

The substance additionally used according to the invention ' acts thermodynamically and causes a refinement of the crystals of the saturated fatty acid monoglyceride and the formation of a thin layer of the unsaturated

35 th fatty acid monoglyeride, so that of the invention

underlying task can also be solved without a tempering process. However, by annealing it becomes

030044/0562

RIKEN VITAMIN OIL CO., LTD.

TER MEER - MÜLLER - STEINMEISTER CaSO! 1147

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possible, the desired properties even further to improve.

The alcohols to be used according to the invention can be selected from those comprising propylene glycol and glycerol Group, while citric acid, malic acid, fumaric acid, Succinic acid, glutamic acid, tartaric acid and lactic acid can use. Soybean lecithin can be used as lecithin and egg yolk lecithin, while stearoyl lactylate is used as lactic acid stearate (lactylic stearate), Sodium stearoyl-2-lactylate and / or calcium stearoyl-2-lactylate can use.

The emulsifier preparation obtained in this way has exceptionally good properties. However, since the product structurally made of saturated fatty acid monoglyceride whose crystal surfaces are covered with a thin layer of the unsaturated fatty acid monoglyceride are covered, arise in certain cases at certain temperatures during storage and the Distribution problems such as caking and sticking to the surface of handling devices.

These problems can be solved by 0 the preparation mentioned with 5 to 20% of a fat mixed, which has a melting point which is above the tempering temperature of the fatty acid monoglyceride.

In a preparation made from saturated fatty acid monoglyceride and the unsaturated fatty acid monoglyceride, the fat does not just form a solid solution with the former material, but also monotectic crystals, so that the crystal stabilization of the material

TER MEER - MÜLLER - STEINMEISTER

RIKEN VITAMINE OIL CO., LTD, Case: 1147

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10 15 20 25

rials is accelerated under the influence of this product. It has been shown that the fat turns into less to a large extent in the unsaturated fatty acid monoglyceride dissolves, so that the crystallization of the fat through the solvent effect of the unsaturated fatty acid monoglyceride is accelerated.

When pulverizing, for example by atomization cooling occurs, air, carbon dioxide gas or nitrogen can be used as the cooling medium use gas. In the flow of these ambient atmospheres, there is a segregation of the fat, the one has a lower polarity than the fatty acid monoglyceride on the surface of the granules, creating a rapid crystallization is caused. The powder obtained in this way shows a high surface density, low moisture absorption and better flow behavior. Compared to the Preparation which is built up solely from fatty acid monoglycerides shows that produced in this way Material excellent manufacturing properties and packaging properties, and has excellent Storage stability so that no problems arise in the later distribution route.

30 35

The fat addition should be limited to 20%. Another addition of fat would improve the properties of the material deteriorates and the emulsifier content is reduced, so that this addition would be uneconomical. The desired addition effect results from a fat content of 5%, whereby for the actual application an addition amount of 10% is preferred.

As used in the invention may be fat having a melting point of more than 45 ⁰ C., hardened beef tallow, hardened lard, hardened fish oil, hardened chicken fat, hardened palm oil, hardened rapeseed oil,

030044/0562

TER MEER - MÜLLER - STEINMEISTER

RIKEN VITAMINE OIL CO., LTD, Case: 1147

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use hardened soybean oil, hardened coconut oil and hardened castor oil, although the invention is not limited to these fats. These fats can be used individually or in the form of mixtures of two or more products of this type. The fat which is suitable according to the invention must have a melting point of more than 45 ^° C., preferably 50 ^° C., in order to provide optimal results. The fat-containing emulsifier preparation obtained in this way should be less hydrophilic than a preparation consisting only of fatty acid monoglyceride.

15th

20th

25th

When processing food, it is normal to use some degree of force. However, this is not a problem when using the emulsifier preparation according to the invention.

The pulverization mentioned above can be carried out in any way. Particularly preferred and effective It is, however, a matter of melting the emulsifier preparation and then pulverizing it by spray cooling.

Regarding the particle size of the powdery according to the invention In the emulsifier preparation, the granule distribution should be such that the average diameter of the granules is in the range of 0.177 to 0.35 mm 0 (42 to 8 0 mesh). If the particle size is too coarse will, the properties deteriorate while with smaller particles, the handling of the material deteriorates. However, the change is the Particle size is not harmful to a small extent as long as the range of variation is relatively small.

Like X-ray diffraction analysis and differential thermal analysis have shown that the crystals of

030044/0562

RIKEN VITAMINE OIL CO., LTD, Case: .1147

TER MEER - MÜLLER - STEINMEISTER

- 14 -

Fatty acid monoglyceride in the emulsifier preparation according to the invention predominantly in the β-crystal form and to a lesser extent in the β ¹ -crystal form. This results in the excellent stability of the properties of the emulsifier preparation according to the invention. When used as intended, the emulsifier preparation according to the invention can only be mixed with water or with a powdered food processing material. This illustrates the ease of handling the emulsifier preparation according to the invention.

15th

Since the advantageous properties of the invention In principle, emulsifier preparations can be detected by forming a complex with starch, the properties of this preparation can be determined via the so-called blue value (hereinafter referred to as BW) be rated. The blue value is obtained from the reaction of iodine with starch. When the strength with the fatty acid monoglyceride forms a complex, the color of the starch is disturbed by iodine. As a result one can determine the extent of the complex formation, and thus in other words the properties of the emulsifier preparation, evaluate by measuring the absorbance value by spectrophotometric analysis. Hence are The lower the blue value, the better the ability to form complexes and thus the properties of the material is.

For practical use, blue values of less than 0.300, as can be seen from the examples, are appropriate.

The emulsifier preparation according to the invention is suitable for improving the quality of starchy foods improve by adding them directly to the starchy

030044/0562

TER MEER - MÜLLER - STEINMEISTER

RIKEN VITAMIN OIL CO., LTD. Case: 1147

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10

20 25

Adds foods or mixtures thereof. The inventive Preparation leads to a significant improvement in the quality of bread, Pastries, pancakes, pasta, biscuits, fish and meat foods and mixtures thereof Products. Since the emulsifier preparation according to the invention exerts its excellent quality improving effect when mixed with water, is achieved comparable effects when used in fatty water-based foods or in protein-containing foods Food.

Since the emulsifier preparation according to the invention not only is limited to the aqueous phase, it can also be used in the fat phase.

The invention is described below with reference to FIG

the drawing represented the only one

1 shows the change in the blue value on the basis of curves

illustrated as a function of the tempering time.

The following examples serve to further illustrate the invention.

example 1

A mixture of equivalent amounts of refined, distilled palm oil monoglyceride and fully hardened, distilled palm oil monoglyceride is melted and, after spray cooling, a powder with an average particle diameter of 0.25 mm (60 mesh) is obtained. One converts the powdered material immediately in a curing room having a temperature of 50 ⁰ C, the material takes after 1 hour out of the curing room and lowers the temperature-

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RIKEN VITAMIN OIL CO., LTD,

TER MEER - MÜLLER. STEINMEISTER CaSC: 1 1 47

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temperature of the powder to room temperature. That way you get the product. The fatty acid compositions, the iodine value and the blue value (BW) are given in Table I below. These numerical values illustrate the excellent properties of the preparation in comparison to fatty acid monoglyceride in a bread mix made from untempered Material and commercially available hardened oleic fatty acid monoglyceride (Comparison) has been produced. The results of the bread making test are also given in Table I. The dough test and the aging delay are also favorable ascertain.

Example 2

Pulverizing a distilled monoglyceride which has been manufactured from a weakly hardened palm oil (iodine value 30), in a similar manner as indicated in Example 1, and heat-treating the material for 4 days at 45 ⁰ C, after which the material to form one of Product cools to room temperature. The results of the testing of this product are also summarized in Table I. The results of the investigation of the product stability are summarized in Table II. In all cases, favorable results are obtained.

30th

Example 3

A monoglyceride preparation is prepared according to the procedure of Example 1 using a mixture prepared by melting of 75% by weight of fully hardened, distilled soybean oil monoglyceride and 25% by weight distilled olive oil monoglyceride. The at The results obtained from testing this product are given in Tables I and II, with in show favorable results in all cases.

Ü3GCU / 0562

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ω
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ο

on

Table I.

Examination results regarding the fatty acid composition, the iodine value, the blue value and bread making

Exam
chung
No. Analysis own
societies
Examined
material Fatty acid composition
(%) ^C 18 ^C 18 ^C 18 " Iodine number BW dough
test Aging delay (g / mm) 2 day 3rd day 4th day 1 preparation
from example 1 ^C 16 28 17th 4th 20th 0.100 O .. Day 164 200 223 2 Non-temper
t product of the
in example 1
specified to
composition 48 ti » It 11 0.340 Δ 110 180 225 260 3 preparation
from example 2 II 6th 25th 3 22nd 0.080 O 125 168 213 248 4th Non-tempering
tth product of
Example 2 64 If 11 11 Il 0.329 Δ 121 178 223 270 5 Preparation of
Example 3 dd 65 20th 2 17th 0.100 ο 129 146 190 220. 11 103

-J

• »J Jf

O Cd

O CfI

Table I (continued)

Exam
chung
No. Analysis own
societies
Examined
material Fatty acid composition
(%) ^C 18 ^C 18 ^C 18 " Iodine number BW dough
test Aging delay
(g / mm) 2 day 3rd day 4th day 6th Non-tempering
tth product of
Example 3 ^C 16 65 20th 2 17th 0.420 Δ 1 day 188 230 267 7th *)
In the trade he
available accessories
riding for the
Bread making 11 64 t - 0.3 0.140 O 133 168 220 230 8th Blank sample 33 0.780 X 115 205 248 282 140

Γ Γ pl

Ü) H Pl 73

ι;

*) Powdered emulsifier with a monoglyceride content of
% (Emulsy-MM-100 from Riken Vitamin)

ο po

(B PJ

CJ ⁰

O
O

ir ¹

TER MEER - MÜLLER - STEINMEISTER

RIKEN VITAMINE OIL CO., LTD, Case: 1147

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10

Method for determining the blue value (BW): water is added 0.02 g of the material under investigation to 40 ml of a gelatinized starch 0,5prozentigen solution at 32 ⁰ C and allowing the material after shaking stand. Then 1 ml of a 0.02N iodine solution is added to 2.5 ml of the material, mixed by shaking and made up to 100 ml. The absorbance is then measured spectrophotometrically using a filter at a wavelength of 6-60 nm. The temperature of the liquid is kept ^{at 32 ° C. during the treatment.}

Bread making test: The sponge dough method (AACC method) is used. The emulsifier preparation (as an emulsifier) is added in an amount of 0.4% to wheat flour. The dough is checked organoleptically. The baked bread is stored at 20 ^° C. and the extent of the delay in aging is measured.

Determination of the aging delay: The aging is measured with the aid of a rheometer during a load of 200 g using a bread adapter. The values of five square test pieces are measured with an edge length of 5 cm and a thickness of 2 cm, cut out from the middle area of the bread have been. The lower the measured value, the greater the aging delay effect.

03CC44 / 0562

RIKEN VITAMIN OIL CO., LTD. Case: 1147

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- 20 -

Table II Stability of properties (BW)

10 15

investigation Number of ver 2 30th 60 180 No. past days examined material 0.075 0.080 0.080 0.085 9 Preparation of Example 2 0.090 0.100 0.100 0.110 10 Preparation of Example 3

Storage conditions: The material is stored at a room temperature of 25 to 30 ^° C.

Example 4

According to the invention, the emulsifier preparations are prepared by treating different combinations of melt-obtained mixtures of fully hardened, distilled soybean oil monoglyceride and distilled olive oil monoglyceride according to that described in Example 2 Procedural rules.

25 30 35

On the other hand, prepare a dispersion of fully hardened, distilled soybean monoglyceride and compare the characteristics of these products. The results obtained are shown in Table III below.

03CCU / Q562

TER MEER - MUUUER - STEINMEISTER

RIKEN VITAMINE OIL CO., LTD Case; 1147

! 001111

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Table III

Fatty acid composition, iodine number and properties (BW)

Under
search
No. Saturated unsaturated
Fatty acid mono-
noglyceride glyceride Evaluation of the properties 11 90/100 Iodine number BW 12th 85/15 9.8 0.370 13th 80/20 15.4 ■ 0.200 14th 75/25 20.6 0.150 15th 70/30 25.9 0.065 16 65/35 31.1 0.085 17th 100/0 dispersions
solution 35.8 0.090 18th Blank sample 0.085 0.745

Note: fatty acid composition (%)

'16

Fully hydrogenated, distilled soy monoglyceride

Distilled olive oil monoglyceride

^C 18 ^C 18 · ^C 18 "80

4 83

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TER MEER - MÜLLER - STEINMEISTER

RIKEN VITAMIN OIL CO., LTD. Case: 1--47

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It becomes difficult to pulverize the material when the content of the unsaturated fatty acid monoglyceride is more than 35%. The most preferred combinations range from 85/15 to 70/30.

From the results given above, the optimal combinations of fatty acid content and iodine number can be seen.

Example 5

Is fused fully hydrogenated, distilled and distilled Palmstearatölmonoglycerid, refined Palmölmonoglycerid (in a mixing ratio of saturated fatty acid to unsaturated fatty acid of 76.5: 23.5) together, pulverizing the material by the method described in Example 1 procedure and heat-treating it at temperatures of 40 ⁰ C, 45 ⁰ C and 50 ⁰ C. The blue value (BW) is then used to measure the changes that have taken place. The iodine number of these preparations is 23. The results obtained are shown in FIG.

25th

From the test results it can be seen that an improvement in a temperature of the annealing process of 40 ⁰ C can not be detected, while at an annealing temperature of 45 ⁰ C after 2 to 8 days an improvement and at an annealing temperature of 50 ⁰ C, a dramatic improvement the properties can be observed after 30 minutes to 2 hours.

35 Example 6 Citric acid, calcium stearoyl-2-lactylate and lecithin are added to the composition of Example 1

030044/0562

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10

and propylene glycol, melting and pulverizing the material according to the procedure of Example 1 and heat-treating it for 2 days at 45 ⁰ C to give the desired product. The results obtained are summarized in Table IV below. Although the non-tempered product already has good properties, it is found that tempering leads to a further improvement in properties and that the properties remain stable over a long period of time.

3CCA4 / 0 5S2

to ο

σ αϊ cn

Table IV Effect of adding various substances (BW)

Under
search
No. Annealing Yes. no
ABCD 0.100 0.110 0.360 0.380 '' ' '19 Retention period At the time of 3 months later At the time of 3 months later
Manufacture manufacture 0.075 0.080 0.250 0.260 '' 20th additive 0.080 0.080 0.180 0.185 21 none 0.095 0.105 0.280 0.295 22nd 1% citric acid 0.080 0.090 0.250 0.275 23 3% CSL *) 0.050 0.055 0.160 0.160 24 '2% lecithin '2'% propylene glycol 1% citric acid
2% lecithin
.2% .propylene glycol

*) CSL = calcium stearoyl 2-lactylate

I. to

η w

to sg

ro bd

·· 3

TER MEER · MÜLLER · STElNMEtSTER

RIKEN VITAMINE OIL CO., LTD Case; 1147

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11

The addition of citric acid and calcium stearoyl-2-lactylate lead to fairly favorable results even without tempering,

Example 7

Defined amounts of fully hardened beef tallow (melting point: 61 ^° C.) are mixed by fusing them with the products of tests no. 13 and no. Of example 4 and with a product obtained in test no. 24 in example 6, and the product is cooled Material from normal temperature by spraying and pulverized it at the same time (product temperature s 30 to 34 ⁰ C). The temperature of the products obtained in this way increases as a result of the static charge by itself on 47 to 53 ⁰ C. The products are then annealed for 30 minutes at 50 ⁰ C and then cooled to normal temperature. After sieving to package 10 kg each of the products obtained in a polyethylene bag in cardboard boxes, which are subjected to temperature cycles at daily intervals of 35 ⁰ C and room temperature (23 ⁰ C) for 2 weeks. The products are then examined. The results obtained are summarized in Table V below.

Example 8

Bread is prepared using the products identified in Investigations No. 11, No. 13 and No. 15 of Example 4 and No. 28, No. 34, No. 38 of Example 7 were obtained. The study of bread making and the dough were made according to the procedures relating to Table I.

35 specified methods.

Investigation of the aging delay: You can see that Central area of the bread five square test samples with a side length of 5 cm and a thickness of 1.5 cm

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and measures them on a texture measuring device (from the company General Foods) (punch diameter 5 cm, 10 cm flat disc, distance: 5 mm, slow speed, Voltage: 2 V).

The results obtained are summarized in Table VI below.

Table V Effect of adding fat

Exam
chung
No. Grundre
recipe Mix
relationship
of the present
benen fat BW Flow behavior Apply
tion 25th • 0 0.150 There is a
Baked in
round condition 2 26th at
game 4 3 0.180 Insignificant
Baked under
Education very much
crumbly agglo
merate 3 27 No. 13 5 0.200 Cheap flow
behavior 5 28 10 0.250 Cheap flow
behavior 5 29 15th 0.310 Cheap flow
behavior 5

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- 27 Table V (continued)

Exam
chung Grundre
recipe Mix
ratio of
admitted
Fat BW Flow behavior Apply
tion 30th 20th 0.380 Cheap flow
behavior 5 31 at
game 4
No. 15 3 0.120 Solid together
to bake 1 32 at
game 6
No. 24 5 0.195 Localized to
bake together, ever
but very crumbly
ge agglomerates 3 33 10 0.235 Flowable 5 34 15th 0.280 Cheap flow
behavior 5 35 20th 0.330 Cheap flow
behavior 5 36 3 0.080 Firm caking 1 37 5 0.120 Flow behavior 4th 38 10 0.180 Cheap flow
behavior 5 39 15th .0.245 Cheap flow
behavior 5 40 20th 0.290 Cheap flow
behavior 5

Comments: The evaluation is carried out with the help of the following five-stage Scale that varies from 5 (favorable) to 1 (unfavorable (caking) ) extends.

030044/0562
BATH ORIGINAL

TER MEER · MÜLLER · STEINMEISTER

KEKEN VITAMINE OIL CO., LTD. Case: 11 Ai

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From Table V above it can readily be seen that the addition of more than 5% fat results in inhibition of caking leads.

Table IV Bread making results

Under
see below
chung
No. Test sample No. 11
comparison Blind
sample Dough test Aging delay effect
(kcf / 10 mm) 41 at
game 4 No. 13
(invent
dungge
moderately Receives in trade
licher emulsifier
(for comparison) *) Δ 1st day 2nd day 3rd day 42 at
game 7 No. 15
(invent
dungge
moderate) O 0.93 1.36 1.48 43 No. 28
(invent
dungs
according to) O 0.78 1.13 1.31 44 No. 34
(invent
dungs
according to) O 0.80 1.18 1.33 45 No. 38
(invent
dungs
according to) O 0.81 "1.20 1.30 46 O 0.80 1.10 1.24 47 X 0.81 1.15 1.28 48 O 1.08 1.55 1.65 0.76 1.16 1.27

*) Identical to the sample from examination no. (See Table I)

030044/0562

RIKEN VITAMIN OIL CO., LTD. TER MEER · MÜLLER «STEINMEISTER Case :. 11 47

From the above Table VI it can be seen that the preparation according to the invention both with respect to the Dough tests as well as the aging retarding effect has excellent properties.

Example 9

The preparation described in Example 3 is mixed with citric acid, malic acid, propylene glycol, Soy lecithin and / or calcium stearoyl-2-lactylate, the material melts and powdered it in the manner described in Example 1 and

15, it is tempered at 50 ⁰ C for 40 minutes

Formation of the desired products. The results obtained are shown in the table below VII compiled.

TER MEER · MÜLLER · STEINMEISTER

RIKEN VITAMIN OIL CO., IflD. Case: 1147

- 30 Table VII Effect of the addition of various substances ((BW)

Under
search
No. J tempering ^a No
ABAB At the time
the manuf
lung 3 months
later At the moment
point of
Manufacturing 3 months
later 49 Keep
duration 50 additive 0.100 0.110 0.420 0.450 51 none
(Comparative
example) 0.077 0.082 0.255 0.260 52 1% Citro
nenic acid
(Invention) 0.080 0.085 0.260 0.266 53 1% apple
acid
(Invention) 0.082 0.090 0.256 0.269 54 2% propy
lenglycol
(Invention) 0.095 0.106 0.285 0.295 55 2% soy
lecithin
(Invention) 0.081 0.088 0.181 0.187 3% CSL *)
(Invention) 0.050 0.055 0.165 0.165 1% Citro
nenic acid
1% soy
lecithin
2% propy
lenglycol
(Invention)

*) CSL = calcium stearoyl-2-lactylate

030044/0562

RIKEN VITAMIN OIL CO., LTD. Case: 1147
TER MEER · MÜLLER · STEINMEISTER

- 31 -

As can be seen from the results in Table VII above, the addition of citric acid, malic acid, calcium stearoyl-2-lactylate or propylene glycol etc. is quite effective even without tempering
good results.

10 Example 10

The tests No. 49-A, -C (comparison), No. 50-A, -D, No. 54-B, -C and
No. 55-B, -D of Example 9, test products obtained from bread making experiments. The bread making, the examination of the dough and the examination of the aging delay are carried out using the
methods given above.

The results obtained are summarized in Table VIII below.

030044/0562

TER MEER · MÜLLER · STEINMEISTER

RIKEN VITAMIN OIL CO., LTD. Case: 1147

- 32 -

Table VIII

Results of the Brother production investigation

Test samples Dough test Aging delay effect
(kg / 10 mm) Investigation comparison
No. 49-A
Investigation comparison
No. 49-C O
X 1st day 2nd day 3rd day Investigation invention
No. 50-A
Investigation invention
No. 50-D O
O 0.82 1.23 1.32
1.07 1.50 1.63 Investigation invention
No. 54-B
Investigation invention
No. 54-C O
O 0.79 1.17 1.27
0.82 1.19 1.29 Investigation invention
No. 55-B
Investigation invention
Ur. 55-D O
O 0.80 1.17 1.28
0.83 1.19 1.30 Blank sample X 0.78 1.16 1.26
0.82 1.18 1.28 Commercial emulsifier *)
(Comparison) O 1.08 1.55 1.65 0.76 1.16 1.27

*) Powdery commercial emulsifier with a monoglyceride content of 80% (Emulsy-MM-100 from the company Riken Vitamin).

G300U / 0562

TER MEER · MÖLLER · STEINMEISTER

RIKEN VITAMIN OIL CO., LTD. Case :. Λ 147

- 33 -

The preparations according to the invention show both in the dough test and in terms of the aging delay effect excellent results.

10

15th

Example 11

Mixing predetermined amounts of fully hardened beef tallow (melting point = 61 ⁰ C) by fusing the preparation described in Example 1, the citric acid, calcium stearoyl-2-lactylate, soybean lecithin and propylene glycol containing the material mixed by the method described in Example 1 Procedure, it anneals for 30 minutes at 50 ⁰ C and cools it down to normal temperature.

After sieving, 10 kg of the products obtained are packed in a polyethylene bag and this in a cardboard box, which is then subjected to repeated temperature cycles from 35 ^° C. to room temperature (23 ^° C.) for 2 weeks at daily intervals. The products are examined at the end of this examination period. The results obtained are summarized in Table IX below.

030044/0562

TER MEER · MÜLLER · STEINMEISTER

RIKEN VITAMINS CO., LTD. Case: 1147

- 34 -

Table IX Effect of adding fat

Under
search
No. Encore Mix
relationship
of the train
given
Fat BW value Flow
behavior Be
evaluation Ver
equal to 56 no 0 0.100 There is a
Caking
in round zu
was standing 1 57 1% Ci
trone
acid 0 0.075 There is a
Caking
in pretty
round condition 2 58 Il 3 0.101 Insignificant
Caking 3 Invention 59
manure Il 5 0.130 Cheap flow
behavior 5 60 Il 10 0.190 Cheap flow
behavior 5 ¹¹ 61 11 15th 0.260 Cheap flow
behavior 5 ¹¹ 62 Il 20th 0.310 Cheap flow
behavior 5 63
same 3% cal
ciums tea
royl-2-
lactylate 0 0.080 There is a
Caking
in pretty run
the state 2 64 Il 3 0.110 Insignificant
Caking
with break
agglomeration
guess 3 Invention 65
manure Il 5 0.150 Inexpensive flow
behavior 5 66 Il 10 0.200 Cheap flow
behavior 5

030044/0562

TER MEER · MÜLLER. STEINMEISTER RIKEN VITAMIN OIL CO., LTD. Case: 1147

- 35 Table IX (continued)

Investigation No.

Encore

I have given it Fat

BW value

Flow behavior

Valuation

invention

67

3% CaI

cium-

stearo-

yl-2-lac-

tylat 15

0.270

Favorable flow behavior

68 20

0.330

Favorable flow behavior

comparison

69

2% lecithin 0.095

There is a caking in a round state

70 0.120

Slight caking

invention

71 0.160

Low flow behavior

72 10

0.220

Favorable flow behavior

73 15

0.280

Favorable flow behavior

74 20

0.330

Favorable flow behavior

comparison

75

2% pro

pylene

glycol 0.080

There is a caking in a round state

76

1% citric acid

2% lecithin

2% propylene glycol 0.050

There is a caking in a round state

77 0.080

There is a slight caking

030044/0562

TER MEER · MÜLLER. STEINMEISTER

RIKEN VITAMIN OIL CO., LOTD. Case: 1147

- 36 -

Table IX (continued)

Under
search
No. Encore Mix
relationship
of the present
low fat BW value Flow behavior Be
who
tion Invention 78
manure 1% Citro
nenic acid
2% Leci
thin
2% propy
lengly-
col 5 0.120 Low flow
behavior 5 79 Il 10 0.180 Cheap flow
behavior 5 80 Il 15th 0.245 Cheap flow
behavior 5 81 ti 20th 0.290 Cheap flow
behavior 5

20 Example 12

Bread production tests are carried out using the products that are used in the tests No. 56, No. 59, No. 66, No. 73 and No. 79 according to Example 11. The bread making, the Dough examination and the aging delay examination were carried out using the methods given above.

30th

The results obtained are summarized in Table X below.

Ö3Ö0U / 0S62

ϊΛΠ ;;: 0
BATH ORIGINAL

TEB MEER · MÜLLER · STEINMEISTER

RIKJBN VJ-XAiXUiMa Case: 1147

- 37 -

Table X Results of the bread-making study

Test samples Dough test Aging delay effect
(kg / 10 mm) 2 day 3rd day O 1 day 1.22 1.32 Investigation # 56
(Comparison) O 0.82 1.14 1.27 Investigation, No. 59
(Invention) O 0.80 1.14 1.28 Investigation No. 66
(Invention) O 0.80 1.16 1.30 Investigation No. 73
(Invention) O 0.81 1.15 1.28 Investigation No. 79
(Invention) X 0.81 1.55 1.65 Blank sample O 1.08 1.16 1.27 Commercial emulsifier *)
(Comparison) 0.76

*) Powdery commercial emulsifier with a monoglyceride content of 80% (Emulsy-MM-100 der Company Riken Vitamin).

30th

The preparations according to the invention show both excellent results in the dough test as well as in the aging retarding effect.

BATH ORIGINAL

l: VITAMIN OIL CO. , LTD. TER MEER - MÜLLER · STEINMEISTER Case:. ¹ J1 47

300111

- 38. SUMMARY

New emulsifier preparations are described which lead to an excellent improvement in the quality of Starchy foods and are obtainable by making a mixture of saturated foods Fatty acid monoglyceride and unsaturated fatty acid monoglyceride are pulverized in specific proportions and anneals.

010044/0562 BATH ORIGINAL

Claims (19)

■ · β οο α α ο «ο βι> · β "ο οοοο • * «· * αο ο ο 9Ο as a • · · β »EAST) O ··· · βΟ Ο * · QO Οβ PATENT LAWYERS TER MEER-MÜLLER »STE3N B ( Representatives authorized in the EuropUtchan Patent Office - Professional Representatives bofora tho European Patent Ofilco Mandatalres agrees pres ! 'Office auropien des brevets Dipl.-Chem. Dr. N. ter Meer Dipl -Ing. H. Stone master Dipl.-Ing, F. E. Müller linker-wail 7 Trittstrasse 4, Siokerwall 7, D-8000 MUNICH 22 D - 48OO BIELEFELD Case: 1147 tM / egg January 14, 1980 RIKEN VITAMIN OIL CO., LTD. No. 8-10, Nishi Kanda 3-chome, Chiyoda-ku Tokyo, Japan Emulsifier preparations and their use to improve quality of starchy foods Priorities: 16. April 1979., Japan, No. November 19, 1979, Japan, no. 7 December 1979, Japan, no. 7 December 1979, Japan, no. 54-46193 54-149770 54-159015 54-159) 516 ' PATENT CLAIMS 1. Emulsifier preparation, obtainable by a process that consists of a mixture of highly pure, distilled monoglycerides containing 65 to 85% saturated fatty acid mono- 0300A4 / 0562 RIKEN VITAMIN OIL CO. LTD. Case: 1147 TER MEER - MULLE «- STEINMEISTER glyceride and 35 to 15% of unsaturated fatty acid monoglyceride and having an iodine value of 10 to 40, after the pulverization for more than 30 minutes at a temperature which is above 45 ⁰ C, but the mixture does not melt at the to anneal. 2. Emulsifier preparation obtainable by a process which consists in a mixture obtained by fusing, - 80 to 95% of a mixture of high purity distilled monoglycerides that is 65 to 85% saturated Fatty acid monoglyceride and 35 to 15% unsaturated fatty acid monoglyceride and an iodine number has from 10 to 40, - 5 to 20% fats with a melting point of more than 45 ⁰ C, to anneal, after the pulverization for more than 30 minutes at a temperature which is above 45 ⁰ C, but does not melt the mixture in the. 3. Emulsifier preparation, obtainable by a process which consists in producing a mixture which, by mixing a mixture of highly pure distilled monoglycerides which contains 65 to 85% saturated fatty acid monoglyceride and 35 to 15% unsaturated fatty acid monoglyceride and has an iodine number of 10 to 40, with less than 5% of at least one member of the group comprising alcohols, organic acids, lecithin and stearoyl acetate, after pulverization, optionally for more than 30 minutes at a temperature above 45 ^° C., at which, however, the mixture does not melt to anneal. 030344/0562 RIKEN VITAMIN OIL CO. LTD. 'Case: 1147 TER MEER - MÜLLER - STElNMEiSTER 4. An emulsifier preparation obtainable by a process which consists in a fusion obtained Mixture of - 85 to SQ % of a mixture of highly pure distilled monoglycerides, which contains 65 to 85% saturated fatty acid monoglyceride and 35 to 15% unsaturated fatty acid monaglyceride and has an iodine number of 10 to 40, which with less than 5% of at least one representative of the alcohols , organic acids, lecithin and stearoyl lactylate has been mixed and - 20 to 5% fats with a melting point of more than 45 ⁰ C to anneal, after the pulverization for more than 30 minutes at a temperature which is above 45 ⁰ C, but does not melt the mixture in the. 20th 5. emulsifier preparation according to claims 3 and 4, characterized in that using propylene glycol and / or glycerine as alcohol, citric acid, malic acid, Fumaric acid, succinic acid, glutamic acid, tartaric acid and / or lactic acid as the organic acid, from soybean lecithin or egg yolk lecithin as lecithin or from lactic acid stearate, sodium stearoyl-2-lactylate and / or calcium stearoyl-2-lactylate is available as stearoyl lactylate. 30th 6. Process for improving the quality of starchy. Foodstuffs, characterized that the emulsifier preparation according to claims 1 to 5 either directly to starchy foods or mixtures thereof.