DE1183453B - Process for the production of baked products - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school KL: A 21 d

German class: 2c-3/02

Number: 1183

File number: C 24895IV a / 2 c

Filing date: August 17, 1961

Opening day: December 17, 1964

Process for the production of bakery products

Applicant:

Corn Products Company, New York, N.Y.

(V. St. A.) Representative:

Dr.-Ing. A. van der Werth, Hamburg-Harburg 1, Wilstorfer Str. 32, and Dipl.-Chem. Dr. F. Lederer, Munich 8, patent attorneys

Named as inventor:

Hans Walter Vahlteich, Englewood, N. J .; Daniel Melnick, Teaneck, N. J .; Raymond Theodore Bohn, Fairview Lake, N.J.

(V. St. A.)

The invention relates to a method for producing baked products from yeast dough with additives of preservatives.

There are three types of microorganisms at work in the production of baked goods made with yeast with. One of these types is yeast, which forms gas when sugar is fermented and thereby loosens the dough. Such microorganisms should not be inhibited as a suitable one Loosening is essential for breadmaking. The second type of microorganism is the class, too which belongs to the Bacillus mesentericus. The spores of these microorganisms are not destroyed by baking destroyed. These become active in the baked products and lead to a deterioration in odor as well as an inexpedient, paste-like structure, d. that is, it finds training in bread so-called "soggy" spots instead. The third type of microorganism is the group of Molds. These lead to an objectionable appearance and taste in the baked ones Products.

Commonly used preservatives inhibit the growth of all three

types of microorganisms specified here. The 25th

Inhibiting yeast fermentation is not intended and

the baker must use longer fermentation times, 2

or it must have very low concentrations

Preservatives are applied. This method will practically eliminate such disadvantages Summer critical, when it becomes necessary, larger 30 wounds. This is a preferred one Apply amounts of preservatives to microbiological inhibition, taking the Konso to avoid spoilage from mold. uses serving products in high concentration, It happens that the applied to so the desired effective inhibition of minimum concentration for the desired inhibi- tion of microbiological growth in the baked Cultivation of the fungal cultures close to the maximum concentration without influencing the yeast fermentation concentration of the preservative lies over the rend of the tire. Close the batter before baking achieve an inappropriate influence on the yeast fermentation.

entry. The invention is a method for

In the production of bakery products, the production of baked products from yeast dough with preservatives is added to the aqueous phase of the dough 4 ° of preservatives, which are thereby added. The preservative comes in direct is characterized by the fact that the preservative comes into contact with the yeast and can thus inhibit the fermentation process initially in the form of a suspension or solution. So far, attempts have been made to distribute a fat as a carrier substance, the fat mass preservative to the aqueous phase of the then converted into small particles and incorporated into a dough in the smallest concentrations for inhibiting 45 usual yeast dough, which is then clogged in the fungal cultures, so that only baked in a conventional way, with the result being reduced influence on yeast fermentation. On the other hand, one has also been satisfied with accepting fermentation coefficients of less than 20: 1, but longer fermentation times that are greater than 2.5: 1 in an amount of 1.25 to 30 Weight through the direct addition of higher concentrations 50 percent, based on the fat, which has a melting point of the preservative to the aqueous phase of at least 40 ⁰ C, as well as that of the dough. The preservative according to the invention with a distribution coefficient

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3 4

Efficiency of less than 0.25: 1 in an amount of greater than about 2.5: 1 and less than 20: 1 is 5 to 30 percent by weight, based on the fat, preservative in an amount of about 1.25 whichever one Melting point of at least about to 30 percent by weight, preferably about 3 to 5O ⁰ C, can be used. Preferably, 25 percent by weight, based on the total fat, is used as the first fungistat, an, unsaturated alumina mass. About 1.25 to 30 weight percent monocarboxylic acid or sorbic acid and percent of the preservative are then used, and an unsaturated, aliphatic carboxylic acid or sodium propionate when the distribution coefficient approaches infinity is used as the second fungistat. and at least 100: 1, preferably about 1.5 to. The melting point of the fat carrier is inversely 10%, applied on the same basis proportional to the preferred solubility of the io.

Preservative in the fat as opposed to As stated above, the amount of solubility in water stands. The solubility of the preservative is expressed in relation to its digestion by the distribution coefficient, the partition coefficient, but in any case the amount used in the ratio of the solubility of the preservative is greater than that in the fat to that in the same proportion in fatty substances for a microbiological weight of water. If preservation inhibition is used, even such an agent will support a partition coefficient of an- growth. It has been suggested to use near infinity and at least about 100: 1, up to about 1% preservative in fat, the fat carrier has a melting point of little products such as butter that is 15-19% at least 32 ° C and preferably about 32 to 40 ° C containing 20 moisture and fat of melting point handling contain a from the standpoint of ease 33-36 ⁰ C. After that at the bakery trade. If the art of distribution were no more than this coefficient greater than 2.5: 1 but less than 20: 1 amount for inhibiting microbial growth, the fat will have a melting point of at least apply as it will be wasteful 40 ⁰ C and preferably from about 40 to about 50 ° C. 25 and the so-protected product are unpalatable This melting point range is would characteristic. Furthermore, the presence of protein leads to solid, plasticized fat masses such as those used in the bakery and copper salts in the aqueous phase of the products. Where the distribution coefficient, such as butter, of the components to be neutralized, the cient of the preservative is capable of the value zero, preserving acids with less than 0.25: 1, the fat 30 has a distribution coefficient of greater than about 2 , 5: 1, and a melting point of at least about 50 ° C and less than 20: 1 in water-soluble components via preferably from about 50 to about 7O ⁰ C. the carry, the Verteflungskoeffizienten less fat is practically in all cases, free of moisture and when 0 , 25: 1 and approximately zero. Therefore it contains less than 1 weight percent water. This is the melting point of the butter fat substantially to the total mass contains less than about 4% by weight, and much lower than the melting point percent water, based on the moisture content of 50 ⁰ C, the required for the preservative of the fat and the moisture that by the con- will, and thus it does not show the desired serving agent being contributed, which can contain even up to preferred microbiological inhibition at an-10% moisture. A twist in yeast-risen baked goods. The melting point of the fat is thus reversed 4 °. Thus butter, which supplies the dough with sufficient proportions to the fat solubility of the preservatives, leads to preservatives. If the preservative is relatively effective against microbial water soluble in the baked product, the melting point of the fat to protect against spoilage is increased to a pronounced level, so as to more effectively contain or affect the yeast fermentation during ripening, protecting the preservative against the 45 of the doughs prior to baking . The same results give the aqueous phase of the dough. In this way, if the same preservation is obtained, the preservative is kept in the fat during fermentation directly to the aqueous phase of the doughs of yeast fermentation, so that little or no are added. According to the invention, this has no effect in practical application. The amount used must be greater so that while a preservative, which is very soluble in fat, the entire baked product is still slightly soluble and practically insoluble in water, any preservative sufficient to inhibit fat regardless of its melting point will inhibit the undesired microbiological work can be done, it is the other way round not possible.

borrowed. The water-soluble preservatives White bread made with yeast represents fat with fats of suitable melting points must be about 3 percent by weight of the total for manufacture be applied, the latter being inversely made of flour applied to the dough, and in some proportional to the distribution coefficient of the con-cases, this percentage can only be 1%, serving items are selected. To in the baked product made with 3% The concentration of the preservative in the desired amount of preservative too the fat is at least about 1.25 by weight; the fat must be about 33 times that amount percent and can contain up to 30 percent by weight, based on the final desired concentration, to the total fat mass. In the bread industry, the concentrations of partition coefficient of the preservative components regularly in relation to the flour zero approaches and is less than 0.25: 1 are roughly expressed by weight. So if you have the flour to 30 percent by weight, preferably about 10 to 65 as 100%, the others are at the Her weight percent, of the preservative in the position of the dough applied ingredients incorporated about the entire fat mass. For preserves - 60% water, about 7% sugar, about 3% yeast, about foodstuffs with a distribution coefficient of 3.5% milk powder (or an equivalent milk

amount) and about 2% table salt (NaCl). Smaller proportions include yeast foods and oxidizers, and they are present in concentrations less than about 1%. The inventive Process can be applied to any baked product made with yeast regardless of the relative Use proportions of the ingredients for as long as the preservative is fermenting influenced.

The two most common methods of mixing the dough are in the baking industry the so-called "one-step" and "sponge" procedures. The former procedure is a one-step process Process in which all components are mixed together in a single batch. Usually the fermentation time is around 4 to 5 hours including the time it takes for the dough to rise is needed in the baking pans. . The "sponge" method consists of two distinct types Working stages, namely the sponge stage and the dough stage.

A third method has recently been introduced in the United States of America, the one enables continuous dough production. In this procedure one leaves one made of sugar, yeast, salt and Water ferment existing broth, and this fermented broth is then pumped into a mixer, Introduced into the flour, milk solids, additional sugar, salt, oxidizer, and fat mass will. The batter usually turns out instantly

ίο divided and brought into pans. The fermentation period of the dough is about 1 hour with this procedure.

The problem that manufacturers of baked products made with yeast face with regard to the Achieving sufficient resistance to microbiological spoilage without influencing it the yeast fermentation in the dough stage is best seen by those given below Results explained. In the following Table I are

ao the basic dough compositions used specified.

Table I.
Dough compositions used for research purposes

Dough process

component

Parts by weight processing

One-step

flour

water

sugar

Milk powder

lard

yeast

salt

Conditioning agent ¹ )

Sponge step

flour

water

yeast

Conditioning agent ¹ )

Dough level

flour

water

sugar

Milk powder

lard

salt

Yeast, nutrients and oxidizing agents.

sponge

100 60

70 42

30 21

Temperature: 27 ° C

Fermentation time:

first section 2 hours

second section 1 hour 10 minutes

Ferment for 20 minutes

a total of 3 hours 30 minutes

Tire 1 hour 6 minutes

a total of 4 hours 36 minutes

baked at 232 ^° C. for 25 minutes

Temperature: 26 ⁰ C
'Fermentation time

3 hours 30 minutes

Temperature: 26 ⁰ C

Fermentation time:

Ferment for 20 minutes

Tire 1 hour 20 minutes

a total of 1 hour 40 minutes

baked at 232 ^° C. for 25 minutes

The following Table II shows the results obtained with two different preservatives which were dissolved in the aqueous phase of the doughs according to the prior art. As it is known that such preservatives affecting yeast fermentation became the additives in the water loosened during the dough stage using the sponge method. This will make the main part the yeast fermentation is carried out without the presence of the inhibitors. The preservatives could should not be added immediately before baking, as the dough will rise before Fermenting and, after being introduced into the pans, essential for making a suitable loaf of bread is.

Table II
Effect of preservatives on yeast fermentation

No. Additives
O/
/ 0 dough Maturation period ² ) in
Minutes bread Measurement ³ )
cm pH value ⁴ ) procedure 1 no Preservation
medium ¹ ) 66 104 5.32 2 0.025 68 105 5.35 3 0.05 SS 78 103 5.32 4th 0.10 SS 83 103 5.40 5 0.20 SS 240 96.5 5.38 One-step 6th 0.10 SS 66 105 5.32 7th 0.20 SP 78 103 5.40 8th 0.40 SP 98 99 5.35 9 no SP 80 117 5.41 10 0.025 ' 81 116 5.41 11 0.05 SS 97 116 5.39 12th 0.10 SS 125 113 5.39 13th 0.20 SS 250 110 5.35 sponge 14th 0.10 SS 82 117 5.36 15th 0.20 SP 85 114 5.48 16 0.40 SP 104 112 5.52 SP

') Percentages expressed on the flour basis. Values on the basis of flour are 55 ° / ₀ and on the bread base 66 · / "the specified percentages here. SS is sorbic acid of the class of the ", ^ - unsaturated aliphatic monocarboxylic acids, and SP is sodium propionate of the class of unsaturated aliphatic monocarboxylic acids.

² ) 510 g of the dough is allowed to rise in the pan at the same height for the single-stage dough and 568 g for the sponge dough.

³ ) Adding up the centimeters of the two circumferences of the loaf, once along the length of the center of the loaf and then across the breadth of the loaf, also measured in the center (this method of expressing the size of the loaf is commonly used in industry ).

⁴⁾ a 10 ⁰ / <> aqueous suspension.

It can be seen from the results given in Table II that as the concentration increases The preservative in the dough has an increasing effect on the yeast fermentation thus results in a longer ripening time. Only very low concentrations of these preservatives, namely 0.025% sorbic acid or 0.10% sodium propionate on a weight basis of the flour, can be added without inhibiting the yeast action. The critical one The amount at which an influence on the yeast action is first detected amounts to 0.0375% for sorbic acid or 0.15% for sodium propionate. Expressed in terms of one with yeast Risen baked product with 3% fat in the dough, the fat would have to contain 1.25% sorbic acid or 5.0% sodium propionate to make 0.375 or 0.15% of the preservative in question in the dough. With increasing concentration of the preservatives, a decrease in bread volume is also noted. What this effect However, a considerable increase in tolerance is found here, namely 0.05% sorbic acid or 0.20% sodium propionate can be tolerated here. By lengthening the maturing time of the dough one can thus obtain acceptable loaves of bread using these higher concentrations of preservatives obtain. However, such a solution is not practical when one has a specific Production quota, unless you have additional options for performing the The tire. At even higher concentrations of preservatives than those specified here lengthening the ripening period is not sufficient to compensate for the loss in bread volts. The use of a constant ripening time for the dough before putting it in the pans is conditional Such higher concentrations lead to the formation of so-called "young" doughs, and these in turn lead to to loaves of bread of smaller volume. Extending the ripening period could resolve this issue lead, but on the other hand, this reduces the efficiency of bread making. An enlargement the amount of yeast, slightly increased dough or maturing temperature and / or slightly lower amount of salt lead to an improvement in the Maturation time, however, such modifications are not sufficient to affect yeast fermentation to compensate if higher concentrations of preservatives are used. The pH values of the bread (and the dough) are all of the same order of magnitude and indicate that a change in pH is not responsible for inhibiting yeast activity.

To be more specific and with less effort the effect of the preservatives on the yeast fermentation were monitored using the Blish-Sandstedt pressure gauge method (Cereal Laboratory Methods, 5th Edition p. 101 [1947] published by the American Association of Cereal Chemists, St. Paul, Minnesota) Attempts have been made to reduce the volume of carbon dioxide formed,

ίο

pressed in mm Hg pressure, to measure that in the closed system at a temperature of 30 ° C is trained. One set of experiments uses flour, water and yeast and the other Test series additionally applied 3% sugar in the flour base. The results obtained here are summarized in the following Table III:

Table III Gas formation in single-stage doughs made with and without preservatives

I. Preservation the CC the 2 formation in Shape of mm Hg during the the all in all line medium ¹ ) 1 hour 2 hours the the 5th hour 6th hour 6 hours 97 146 3rd hour 4th hour 49 41 537 no 95 147 139 65 50 40 537 0.025% SS 86 131 138 67 51 39 539 0.05% SS 57 74 155 77 85 62 473 No sugar 0.10% SS 39 46 94 101 29 27 212 admitted 0.20% SS 86 140 39 32 45 38 510 0.10% SP 82 134 140 61 44 36 503 0.20% SP 52 70 147 60 79 54 438 0.40% SP 117 145 88 95 110 92 703 no 110 161 121 117 109 94 727 0.025% SS 92 164 135 118 118 85 735 3% sugar 0.05% SS 73 139 146 130 95 79 630 on the 0.10% SS 40 60 137 107 60 48 343 Flour base 0.20% SS 106 153 69 66 120 72 722 location 0.10% SP 101 154 136 135 111 70 703 give 0.20% SP 68 138 136 132 89 68 597 0.40% SP 134 100

^l ) See footnote to Table II.

The figures in Table III show that the preservatives do not adversely affect the amylase activity of the flour, so that the reduction in the substrate (sugar) available for yeast fermentation is not a factor responsible for a slow rate of gas evolution. In the presence of added substrate, the preservatives are just as effective in reducing the rate and extent of yeast fermentation. The added sugar only requires a greater development of carbon dioxide (CO ₂ ) in all systems. With the lower concentrations of preservatives, namely up to 0.05% sorbic acid or up to 0.20% sodium propionate, the evolution of gas at the end of the 6 hour period is normal. Only at the lower concentrations, namely 0.025% sorbic acid and 0.10% propionate, is the CO _a development during the first hour unaffected. These results show that only the smallest concentration would not affect the yeast activity in the dough. The slightly higher concentrations, namely 0.05% sorbic acid and 0.2% sodium propionate, can be used provided that a sufficient fermentation time is allowed. The highest concentrations, namely more than 0.10% sorbic acid and about 0.40% sodium propionate, are expediently not used because of the strong inhibitory effect on the fermentation rate. The available maltose and other fermentable sugars, which originate from the starch in the flour or from the added cane sugar, were not exhausted after fermentation for 6 hours. These results and conclusions are in agreement with those obtained from studies of the complete doughs described above (see Tables I and II).

The following Table IV shows some of the results obtained in evaluating the resistance to mold spoilage of breads made from the whole doughs described above. Three test methods are used here. Immediately after the temperature of the baked bread has fallen to about 38 ° C, the loaves of bread are sprayed on the top and the side with a suspension of a mold mixture obtained from moldy bread. The spray is allowed to dry, and then the loaves in Pliofilm- (Kautschukhydrochlorid-) bags are packed and inlcubiert at a temperature of 27-32 ⁰ C. In the second test, bread slices are sprayed with the mold suspension and the slices are then placed back into loaf form. The same are then stored in PMofilmsäcken at a temperature of 27-32 ⁰ C. In the third test, a slice of each bread is placed in a Petri dish and then sprayed with the mold suspension. A moistened filter paper is placed in the top cover of the Petri dish. The assembly is then stored at a temperature of 27 to 32 ° C. The inoculated samples are examined every 24 hours. The results obtained are shown in Table IV. The same relative picture of the preservative effect is obtained with earlier investigation times, but here the fungal growth is less.

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Table IV Protection of breads against mold spoilage

dough Testl Mold growth after Inoculation ³ ) Test 3 XT * Preservative ¹ ) on the crust after on exposed panes JNr. 96 hours after after 48 hours no XXX XXXXXX 1 0.025% SS XX XXXXX 2 0.05% SS X XXX 3 0.10% SS 0 X 4th 0.20% SS 0 0 5 0.10% SP X XXXX 6th 0.20% SP 0 XXX 7th 0.40% SP 0 X 8th no XXX XXXXXX 9 0.025% SS X XXXX 10 0.05% SS 0 XXX 11 0.10% SS 0 X 12th 0.20% SS 0 0 13th 0.10% SP X XXXX 14th 0.20% SP 0 XX 15th 0.40% SP 0 0 16 Test 2 between panes 72 hours XXXX XXX XX 0 0 XX X 0 XXXXX XXX XX X 0 XXX X 0

*) See footnote to Table II.

² ) See text regarding the description of the test methods; "0" means no growth, "X" means the amount of growth.

From the results given in Table IV it turns out that the extent of the mold growth is lowest on the crust surfaces (which have a low moisture content) and is largest on the exposed bread slice that stored in high humidity air (test 3). The sodium propionate turns out to be one third as active as sorbic acid in inhibiting fungal growth.

The larger percentages of preservatives provide good protection against mold spoilage obtain. However, this coincides with the inconvenient inhibition of yeast activity in the doughs (see Tables II and III) together. Thus, under the current working conditions, the baker must necessarily make a compromise. The baker needs sodium propionate in an amount of 0.10 to 0.20% and sorbic acid in an amount of Apply 0.025% to 0.050%, expressed on the basis of the weight of the flour.

Similar tests with sodium benzoate give results that the need for maximum Underline concentration that does not affect yeast activity in the dough, as well as a minimal one Concentration needed to achieve a measurable protection of the bread against mold spoilage necessary is. At a 0.2% concentration, sodium benzoate protects bread about the same Extent as 0.2% sodium propionate, but the effect on the yeast activity in the dough is the same as large as the one found when using 0.4% propionate. This indicates that sodium benzoate as a mold inhibitor in the bread made according to the state of the art is unsuitable.

Comparable investigations with inoculation of the dough with spores of the Bacillus mesentericus, to the Organism containing "slippery" places show that the formation of such "slippery" places a temperature of 29 to 32 ° C is inhibited at concentrations that are significantly below those which are necessary for effective protection against mold spoilage, namely 0.025% sorbic acid and 0.10% sodium propionate are effective in preventing the formation of such "slippery" spots.

In the course of the studies leading to the present invention, a novel one was discovered Process developed for incorporating preservatives into baked products processed with yeast, whereby by this method the desired preferred (differential) microbiological inhibition is achieved. The preservative and bacteriostatic properties of the additives have an effect the baked products completely, without the inexpedient effects of the additives related to inhibiting the yeast fermentation of the dough prior to baking. All relevant microorganisms grow in an aqueous medium. For the inhibitors to be effective, they must be in the aqueous phase. The invented the inventive method is that at least a major part of the preservative in the form of a novel mass in which the preservative is incorporated into a fat component of the dough, application finds. This results in reduced concentrations of additives in the aqueous Phase of the dough, whereby the negative influence on the yeast fermentation is kept as small as possible. It has been found that during the baking process, the melting of the fat leads to a release of the Preservative leads from the fat, whereby the same dissolves in the warm aqueous phase. With some forms of preservatives, namely with free carboxylic acids or their alkyl esters, their release from the fat is accelerated due to their property that these forms of Preservatives sublime or volatilize out of the fat at elevated baking temperatures and the same (especially the free acids)

show that a preservative in the form of the
«, ^ - unsaturated aliphatic monocarboxylic acid so
long the yeast fermentation does not affect until one more

show increased solubilities in warm water. With medium in the bread during the baking process too the non-volatile forms of the additives, and improve.

Although the alkali metal or alkaline earth metal salts it is possible to make a block of high melting point

Preservative acids, such as the sodium or carrier fat that the preservatives contain, Calcium salts, the extraction from the crushed 5 is done by grinding liquid fats in the aqueous phase through which it carries out or converting it into flakes. This represents elevated temperatures favored, which are however not a preferred method. It is expedient Baking. The sublimation of the volatile moderate, as much as possible the preservative Add preservative acids from the fat to the fat carrier, although most of the The aqueous phase during baking is surprisingly not dissolved in the fat, but rather the preservative not with a noticeable loss of this which is suspended. Once that the preservative acids tied together. Obviously, while the agent-containing fat is spray chilled, all will be skin crust formed in the first baking stage with sufficient suspended particles of the preservative to "lock in" the volatile preservatives - the fat is coated. If on the other hand a solid to condition mean acids. 15 block of such a fat mass ground or in

The results shown in Tables II and III flake may have a tendency to become

Breaking at the interface between the fat-insoluble preservatives and the fat occur, as a result of which the preservative is free of 0.025%, based on the flour, amounting to 20. When the preservative is fully concentrated is reached while a more than 0.10% is constantly in solution, the spray cooling is below Amount of concentration for a saturated ali- forming of spheres is preferred as the spheres phatic monocarboxylic acid is required. , a smaller surface than any other geometric

As mentioned above, the invention relates to having shapes of particles. A diminished Fats with specific melting points, in which preservation 25 surface is expedient for the aqueous extraction preservative with a specific distribution of the preservative from the carrier during coefficient (the ratio of the solubility of the manufacture and fermentation of the yeast-based preservative to keep the doughs put in fat to the solubility as small as possible. This is true in an equal weight of water) incorporated especially when high-melting fats are. 30 that are somewhat soluble in water are used,

If a grease applied with a high melting point and that glyceryl monostearate, which is optionally substituted as a fully hydrogenated cottonseed oil with small amounts of glyceryl distearate containing having a melting point of about 6O ⁰ C, or is available.

Glyceryl monostearate with a melting point of In the following Table V a number of examples

around 68 ° C, the melted fat is given with the contra-35, the preferred modes of manufacture Serving agents in suspension and / or in solution of the preservative concentrates according to the invention preferably spray-cooled to explain such small globules. These concentrates lead to the to train. These small spheres have preferential (or differential) microbiological be of such a size that virtually all inhibition in the production and distribution of Pellets through a sieve with a clear mesh 40 baked products which, using yeast, pass 0.84 mm wide and practically all of them have been placed. No impairment globules occur here through a sieve with an open mesh flow with the yeast fermentation during ripening and width of 0.18 mm can be retained. Of handling the dough before baking, The purpose of using the high-melting fats, however, is the full preservative effect in the form of spheres as a carrier material, there is 45 with regard to the protection of the baked products against therein, the uniform dispersion of the preservation - microbiological spoilage in effect.

Table V
Concentrations of preservatives for preferred microbiological inhibition

at
game link Distribution
coefficient ¹ ) product Enamel
Point
⁰ C shape Conservation
funds
in the carrier 1 Ethyl sorbate more than 100 lard 39 melted 5.0 2 Sorbic acid 3.0 hydrogenated vegetable oil 44 plasticized 5.0 3 Sorbic acid 3.0 hydrogenated vegetable oil 60 Globules 25.0 4th Sorbic acid 3.0 Glyceryl monostearate 68 Globules 25.0 5 Calcium propionate less than 0.25 hydrogenated vegetable oil 60 Globules 25.0 6th Calcium propionate less than 0.25 Glyceryl monostearate 68 Globules 25.0 7th Benzoic acid 6.1 hydrogenated vegetable oil 44 plasticized 5.0 8th Benzoic acid 6.1 hydrogenated vegetable oil 60 Globules 25.0 9 Sodium benzoate less than 0.25 Glyceryl monostearate 68 Globules 25.0

*) The ratio of the solubility of the preservative in the fat to the solubility in an equal weight of water.

The alkyl esters of the aliphatic carboxylic acids used according to the invention are so soluble in fats and oils and have such a low degree of solubility in water that they can be incorporated directly into the solution of the molten fats used in dough production. Sorbic acid is only soluble in fats at a concentration of 0.6% and in water at a concentration of only 0.2% at room temperature. These Konserbonsäuren include the saturated lower aliphatic acids, including propionic and diacetic acids and the «, / ϊ-unsaturated carboxylic acids of the following formula R ₁ - CR ₂ = CR ₃ - COOH, where 5 is the part of the molecule that contains the«, jö- Has unsaturated linkage, either an aliphatic or an aromatic hydrocarbon group. If there is more than one unsaturated double bond in the molecule, this should be one

tives should expediently a fat io to the '/ ^ - unsaturated bond conjugated double · with a melting point of about 41 to 49 ⁰ C to-action connection system. In the above formula, R _{1 is} to be put. Propionic acid and its sodium hydrogen, when R ₂ and R ₃ combined form a single or calcium salt, are so highly soluble in water that they form individual carbocyclic rings, and R ₁ is one (distribution coefficient approximately zero) that the carbon atom of an aliphatic hydrochloric acid is only Fats with a higher melting point, ie 15 substance group when R ₂ and R _{3 are} hydrogen atoms. from 49 to 71 ⁰ C, should be added, so that examples of such acids are croton, isocroton, suspensions of the preservatives in the fats / S-ethylacryl-, dimethylacryl-, α-hexanone-, sorbin- form. The same is true of sodium benzoate. Benzoic and p-hydroxybenzoic acid, etc.
Free benzoic acid, on the other hand, is essential in fat. A convenient group of preservatives,

more soluble than in water (partition coefficient of 6.1) 20 which leads to satisfactory results at room temperature, so that the same in fats lower those acids which have the following general

Have formula: R '- CR = CR - COOH, where R is a hydrogen atom or an alkyl group and R * represents an aliphatic hydrocarbon radical. 35 These acids include sorbic, α-hexanone, croton, isocroton, / 7-ethyl acetate and Dimethylacrylic acid.

The lower alkyl esters and the sodium and calcium salts of the above carboxylic acids can also

Thus, the addition of the preservatives 3 »if used satisfactorily,
does not improve the resistance The preservatives in the form of the invention

the fats per se compared to the mold spoilage. From alkyl esters contemplated according to possess For this reason, preservatives are not yet distribution coefficients that approach infinitely * has been added to moisture-free fats. The and are at least 100: 1. The unsaturated Fats used according to the invention have carboxylic acids with a preservative effect represent concentrates of the preservatives, the distribution coefficients greater than about 2.5: 1 and when working into an aqueous medium that is less than 20: 1. The sodium and calcium salts of the is then subjected to heat processing, acids and the unsaturated lower aliphatic «!! are able to distribute the preservative to the acids (as the free acids) possess aqueous Phase to be released, whereby the final product 40 coefficients of approximately zero and are smaller against mold and / or bacterial spoilage as 0.25: 1.

is protected. In the following Table VI are the results

In addition to those which are considered according to the invention and which are shown with the examples according to Table V Preservatives include the carboxylic acids, relative to the extent to which they affect the their alkyl esters, such as methyl, ethyl and propyl fermentation, have been obtained in doughs. For esters etc., and their alkali metal and alkaline earth purposes were also control systems on metal salts, like the sodium and calcium salts. This resulted in which the preservatives were added directly Acids, esters and salts can be used in the general form of the aqueous phase in the preparation of the doughs for the purposes of the invention as the "carbon" were added, as in the prior art Acid compound «. To this Car- 50 technique is carried out.

Table VI

Reduction of the influence on yeast fermentation in single-stage doughs,

which contain 3% added sugar when the preservatives are in the form of

concentrates according to the invention are used

Melting point can be incorporated. Both sorbic and benzoic acid can also be used in In the form of globules, they can be suspended in the high melting point fats.

It should be noted that moisture-free fats do not prevent mold or growth Bacteria can support, as they do not contain moisture in solution or in emulsified form.

Preservative ¹ ) the CO the Education in the form of mm Hg during the the the all in all example 1 hour 2 hours the 4th hour 5th hour 6th hour 6 hours no 119 134 3rd hour 122 112 74 678 Control a 0.10% SS in water 69 103 117 107 63 48 502 Control b 0.125% AS ² ) in fat 120 133 112 118 110 75 679 1 0.10% SS in fat 100 130 123 115 110 64 629 2 0.10% SS in fat 118 150 110 120 104 67 679 3 0.10% SS in fat 116 148 120 112 98 66 660 4th 120

See notes at the end of the table

Table VI (continued)

Preservative ¹ ) the CO ₂ formation in the form of mm Hg during the the the the all in all example 1 hour the 3rd hour 4th hour 5th hour 6th hour 6 hours 0.40% CP in water 75 2 hours 129 82 50 38 519 Control c 0.40% CP in fat 118 145 127 114 87 62 660 5 0.40% CP in fat 113 152 134 107 78 60 645 6th 0.20% NB ³ ) in water 70 153 140 79 50 36 534 Control d 0.17% BS in fat 95 159 134 102 75 60 606 7th 0.17% BS in fat 112 140 121 112 108 70 665 8th 0.20% NB ³ ) in fat 105 142 126 90 75 68 610 9 146

*) AS = ethyl sorbate, SS = sorbic acid, CP = calcium propionate, NB = sodium benzoate, BS = benzoic acid.

For a description of the preservative concentrates, see Table V, since the preservative concentrates corresponds to the examples shown in Table V. The stated concentrations are given on the basis of the weight of the flour.

² ) Corresponding to 0.10% SS.

³ ) Corresponding to 0.17 ⁰ Z ₀ BS.

In these tests again the pronounced inhibition activity (control vs. control b a) (expressed on the weight basis of the flour) to the yeast fermentation at a 0.107 ₀ weight concentration of sorbic acid found in water. If the sorbic acid is made insoluble in water by converting it into ethyl sorbate and an equivalent amount of this compound is dissolved in the molten fat, the yeast activity is not affected (see example). Free sorbic acid in the grease with an O, lO7oig ^s concentration (s. Example 2) shows approximately the same degree of inhibition than when 0.05 7o be added directly to the aqueous phase of the dough. This means that 0.10 7 ₀ sorbic acid can be used in the plasticized fat in doughs provided that a corresponding extension of the ripening time is used. No inhibitory effect on the yeast fermentation is then determined if 0.107 ₀ sorbic acid in one of the high-melting fats (see Examples 3 and 4;.. See also Table V) is added to the doughs. Thus, such concentrations can be used to add 0.17o sorbic acid without changing the fermentation times. Similar tests with 0.20 ° / ₀ of added sorbic acid to the dough have shown that no influencing the yeast activity occurs when a carrier material is applied from fully hydrogenated [Bold for the preparation of the fat globules. If glyceryl monostearate is used for this purpose, an O, 2O7oige sorbic acid can show a slight inhibiting effect on yeast fermentation. This is determined when the spheres have a mesh size of 0.3 to 0.2 mm, but not when they have a mesh size of 0.84 to 0.60 mm. Obviously, the tendency to inhibit yeast activity is greater, the smaller the beads are produced with a carrier material which shows a certain dispersibility in the water. But even in these latter cases, minor compensations for this inhibitory effect can be made by increasing the ripening time.

The test results obtained with calcium propionate support those obtained with sorbic acid Results. Propionic acid in low-melting fats in a concentration corresponding to 0.40 7o Calcium or sodium propionate is expediently not used, due to the high solubility in water, as this allows easy extraction of the compound by the water from the Fat is done out into the dough.

Therefore, calcium or sodium propionate in 0.407 ₀ sodium concentration can only be added in the dough, when the hochschmekenden fats (s. Examples 5 and 6) are used as the support for preparing the fat globules.

When using benzoic acid and its derivatives, such as p-hydroxybenzoic acid, conditional employing the free acid in the plasticized fat (see Example 7) to a large extent circumventing the inhibiting effect on the yeast fermentation of the easily water-soluble and in the aqueous phase of the dough (Control d) Sodium benzoate dissolved in an equivalent concentration. When used as a carrier to manufacture of the fat globules containing the free benzoic acid (see Example 8), a high-melting fat was used there is no influence on the yeast activity. The easily soluble in water sodium benzoate in the slightly water-dispersible glyceryl monostearate (see Example 9) shows a certain inhibiting effect Effect on yeast fermentation, but to a much lesser extent than if the the same concentration of sodium benzoate is dissolved in the aqueous phase of the dough.

The presence of low concentrations of carriers (the fats) in the dough has an impact on yeast fermentation no influence. Control tests carried out on doughs using the same amount of carriers without contain added preservatives, led to the same results as the control tests, which were carried out without added fat and without added preservatives.

The values given in Table VII below show to what extent the preferred (or differential) microbiological inhibition in bread production by means of the invention Preservation concentrates can be achieved.

409 758/82

Table VII

Achieve preferred microbiological inhibition in bread making with concentrations of the preservative according to the invention - sponge dough method -.

example Preservatives') Maturation time in
Minutes Bread size ⁴ )
cm Fungal growth ⁵ ) ¹ Control a no 78 114 XXXXX Control b 0.110 SS in water 121 109 X 1 0.125% AS ² ) in fat 79 114 XX 2 0.10% SS in fat 94 113 X 3 0.10% SS in fat 77 114 X 4th 0.1 OV ₀ SS in fat 80 116 0 Control c 0.40 7o CP in water 100 109 0 5 0.40% CP in fat 76 114 X 6th 0.40% CP in fat 79 116 0 Control d 0.20 7o NB ³ ) in water 108 109 XX 7th 0.177o BS in fat 88 113 XX 8th O.177o BS in fat 78 114 XXX 9 0.20% NB ³ ) in fat 83 113 XX

¹ J, -), ³ ) the same footnotes as in Table VI, same examples as in Table V.

⁴ ) See footnote in Table II.

⁵ ) The same series of tests carried out as indicated in Table IV. The values given in this table are average values of the results of three tests, "X" represents the extent of growth, and "0" indicates no growth after inoculation.

If ethyl sorbate is used in the molten lard (see Example 1), there is no influence the yeast activity. There will be quite a good inhibition of fungal growth following here achieved an inoculation carried out. The alkyl esters according to the invention of the preserving acids, the ethyl sorbate being characteristic of this group, but not the preferred ones Components of the preservative concentrates.

Sorbic acid in the plasticized fat mass (see Example 2) still shows a slight inhibition the yeast fermentation, but this is much less than it occurs with free sorbic acid, which occurs in the aqueous Phase of the dough is dissolved. The mold spoilage of a bread containing this concentrate will effectively delayed. Sorbic acid in the fully hydrogenated fat (see Example 3) or the glyceryl monostearate (see Example 4) are very good examples of preferred microbiologically inhibiting compositions This does not affect yeast activity, but there is very good inhibition of fungal growth. In fact, up to 0.2% sorbic acid can be added to doughs when the fats are high Melting point are the carriers, there is no significant influence on the yeast activity and one Increase in the resistance of the bread to mold spoilage is achieved.

When using calcium propionate in fats with a high melting point (see Examples 5 and 6) a good differential microbiological inhibition is achieved.

When using benzoic acid and sodium benzoate preparations (see Examples 7 to 9), a fairly good reduction in the influence on yeast fermentation is achieved. , The greater susceptibility of the fat globules obtained to mold spoilage merely means that the sodium benzoate is inferior as a preservative at a concentration of 0.27 weight ₀ a O, 47oigen Calciumpropionat- or O, lO7oig ^en sorbic acid concentration.

In a comparative study using single-stage doughs, sMt gives practically the same picture of preferred microbiological inhibition using the best series of examples. The study was extended to study doughs inoculated with Bacillus mesentericus spores.

Effective inhibition of the formation of soggy spots was achieved with the same series of examples using the same concentrations.
Glyceryl monostearate is preferred as a fat over completely hydrogenated fat when fats with a high melting point are used as carriers for the preservatives. Fully hydrogenated fat is not unsaturated and therefore only makes the preservative concentrates more expensive. Glyceryl monostearate is commonly used as an anti-aging agent in batter! added, whereby the bread is given a softness that is maintained over longer periods of time. Bead glyceryl monostearate containing the preservatives still acts as an anti-aging agent, although it does not do so to the same extent as when the monostearate is dissolved in the fat component of the dough. Thus, a certain compensation is obtained with regard to the costs of the glyeeryl monostearate when the latter is used for the production of the preservative concentrates according to the invention.

Further advantages in addition to the preferred microbiological inhibition are based on the incorporation the preservatives in the fats used to make the dough. The preservatives as these are available to the baker in a relatively pure form. When applied as pure chemicals this creates problems. The compounds are used in such small amounts that particularly sensitive scales often used to monitor the addition of the correct ones

Amount needed to make the dough. By incorporating the preservative in the correct Concentration in the fat masses usually used by the baker becomes two stages of work Brought to the dough production, namely the weighing of the preservative and the Dissolve the same in the aqueous phase. In order to be more flexible in terms of manufacture, can Concentrates made of preservatives suspended and dissolved in fat up to 25 percent by weight will. This enables the baker to use any concentration of the preservative apply taking into account the special seasonal requirements as well the requirements that are placed on the specific product to be manufactured. This is done by mixing during the dough production of the preserving fat with that usually used Reached fat that does not contain a preservative, ao

The terms "preservative" and "mold inhibiting agent" are not limiting To understand the meaning of preventing the growth of mold, but generally mean substances, which either retard or prevent such growth. These expressions also include the bacterial inhibiting properties of these substances. The terms "microbiological agents" and "microorganisms" are also to be understood in a general way and are intended to mean a number of types of bacteria as well as include mushrooms.

The term "preserving fat" is intended to refer to the novel concentrates or masses of one refer to a preservative-containing fat. The term "fat" is used in the usual sense and includes esters and ester mixtures of glycerol with fatty acids, both saturated and unsaturated acids. This also includes the mono-, di- and tri-esters of glycerol.

Claims (3)

Patent claims: 1. A process for the production of baked products from yeast doughs with the addition of preservatives, characterized in that the preservatives are initially distributed in the form of a suspension or solution in a fat as a carrier substance, the fat mass is then converted into small particles and incorporated into a conventional yeast dough which is then baked in the usual way, the preservative being one with a distribution coefficient of less than 20: 1 but greater than 2.5: 1 in an amount of 1.25 to 30 percent by weight, based on the fat, which has a melting point of having at least 4O ⁰ C, and a preserving agent having a distribution coefficient of less than 0.25: 1 in an amount of 5 to 30 weight percent, based on the fat which has a melting point of at least about 5O ⁰ C, are applied. 2. The method according to claim 1, characterized in that the first Fungistat an α, / 3-unsaturated aliphatic monocarboxylic acid or sorbic acid is used. 3. The method according to claim 1 and 2, characterized in that a second Fungistat saturated aliphatic carboxylic acid or sodium propionate is used. Considered publications:
French Patent No. 815,783;
"Bread and Pastries", 1955, pp. 26 to 30, and 1958, pp. 204 to 216;
"Food Research", 1955, pp. 629 to 648. 409 758/82 12.64 @ Bundesdruckerei Berlin