DE2227691A1 - Non-alcoholic beverages and concentrates for making them - Google Patents

Description

DlPL-INQ. DIETER JANDER DR.-INQ. MANFRED BÖNINQ Patent attorneys delivery address:

Teply to:

MÖNCHEN 80 (BOGENHAUSEN) 1 BERLIN 33 (DAHLEM) KOLBERGER STRASSE 21 HOTTENWEG 15 Telephone: 0811/9827 04 - Telephone: 0311/8324066 Telegrams: Consideration Berlin

97/13 855 DE 5th June 1972

Patent application

of the company NV CHEMISCHE I ¹ ABRIEK "NAARDEN"

P.O. Box 2, NAARDEN-BUSSUM / Netherlands

"Soft drinks and concentrates to their

Manufacture "

The invention relates to non-alcoholic beverages in which essential oils or mixtures of flavorings are dispersed with and without the addition of fruit juices. In particular, the invention relates to cloudy, alcohol-free Carbonated and non-carbonated beverages and concentrates to accompany them

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Potticheckkonto Berlin Weit 174384 Berliner Bank AG., Depoiltenkajse 1 DI PL.-1N Q. DIETER JANDER DR.-INC MANFRED BONINQ

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Manufacturing. The invention also relates to the production of said concentrates.

In the production of non-alcoholic beverages, essential oils or mixtures of flavorings used to make the beverages to seduce the desired taste.

Many of these additives have such a low water solubility that that they cannot be readily dissolved in the desired amount. It is therefore common to use the flavorings with the help of suitable devices, such as homogenizing machines. Such drinks are due the light scattering caused by the particles of the oily dispersion becomes cloudy.

Beverages made from! Fruit juices, especially those made from produced by the processing of whole fruits, are obtained, look cloudy. This cloudiness is partly caused from small bits of fruit tissue.

When the particles causing the cloudiness of the beverage do not remain permanently dispersed but form conglomerates or settle on the surface or the bottom, the cloudiness of the beverage decreases, and on the bottle neck a ring is formed or a sediment is formed. These phenomena affect the appearance of the drink and are therefore very undesirable.

Recently there is a complete overview of the literature on these phenomena, their theoretical basis and the measures taken appeared, with which these disadvantages can be avoided as far as possible (H. Goodall, Weighting and Clouding agents for soft drinks; Literature Survey No. 9, The British Food Manufacturing Industries Research Association,

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Leatherhead, Surrey, UK, December 1970).

This overview shows that no complete theoretical explanation has yet been found for the phenomena is. The practical measures that have been proposed so far, and most of which consist of them, are also definite Using additives from which, for theoretical reasons, a positive effect can be expected, has proven itself not proven final.

In order to facilitate the dispersion and the stability of the obtained To improve emulsions, substances known as emulsifiers and stabilizers are added and which are also used on a large scale in other areas of the food industry. Though on In this way dispersions can be obtained which are sufficiently fine, their stability is insufficient, what due to the difference in the specific weights of the beverage and the flavorings distributed in it is.

Attempts have been made to overcome this disadvantage by calculating the specific gravity of the flavor mixture that of the drink adapts. This can be achieved by adding a certain amount to the mixture of flavors dissolves a substance which has a high specific gravity, and by subsequently adding the mixture thus obtained dispersed.

The number of substances that have a sufficiently high specific gravity and that are used for this purpose can is very limited · Such a substance does not only have to be present in sufficient quantities in the flavoring mixture

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solve and must not have an adverse effect on the smell, or exert the taste of the drink, but must also not have any harmful properties. Long time brominated fatty oils such as brominated corn oil and brominated peanut oil have been used for this purpose. Recently are Objections to the use of brominated oils have been raised for health reasons, with the result that in a number of countries have banned the use of these oils.

There have also already been proposed for this purpose of abietic acid derivatives, such as the Methylester of hydrogenated abietic acid and Glycerylabietat (see U.S. Pat. 3,353,961), as well as .Saccharoseester one or more lower fatty acids such as sucrose acetate isobutyrate (British Patent 1 118 019).

Although the harmlessness of these compounds has been established according to the research results available so far seems, one can object to foreign additives to food based on fundamental considerations.

It has now been found that very stable emulsions for the production of non-alcoholic beverages that have a stable Have turbidity, can be obtained if you prepare aqueous emulsions and these with 'skimmed milk powder or condensed Stabilized skimmed milk.

These can be emulsions with essential oils or parts thereof and / or natural or synthetic triglyceride oils Act. So you can get a mix of common flavors emulsify with skimmed milk powder or condensed skimmed milk. You can also use a combination of one

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essential oil or part thereof, common flavorings and emulsify a triglyceride oil with skimmed milk powder or condensed skimmed milk. The "skimmed milk powder can have been produced both by spray drying and by roller drying.

The emulsion is preferably homogenized at a pH between 4.5 and 6.0, in particular at 5> 0.

Any oil which has a sufficiently neutral taste can be used as the glyceride oil. Extra-natural artificial oils can also be used, e.g. Triglycerides of fatty acids from coconut oil fractions.

So-called low-temperature, medium-temperature and high-temperature milk powder as well as roller-dried milk can be used will.

The stabilizing effect of proteins on oil-in-water emulsions is known. The polypeptide chains of proteins have both hydrophilic and hydropholic side chains, so that when the protein is adsorbed at the oil-water interface some orientation takes place, which can increase the stability of the emulsion. Milk is an example of such an emulsion stabilized by protein adsorption.

It is further known that milk protein fractions, e.g. Sodium caseinate, used as an emulsifier in emulsions for Food of the oil-in-water type can be used.

"From the Dutch published patent application 67.04578 and the British patent 1.158.103 it is known that interactions can take place in the interface which affect the structural properties of the food emulsion

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affect when different proteins are present.

In order to improve the heat stability of the emulsion, it may be necessary to change the protein, e.g. by acylation (Dutch published patent application 69.19619)

The stabilizing effect of proteins on oil-in-water emulsions is highly dependent on the pH of the surrounding aqueous phase and on the isoelectric point of the protein used. The influence of the pH value is greatest when it is at or near the isoelectric The point at which the solubility of the protein in water is lowest and the charge of the protein molecule as a whole practically O is. The isoelectric point of unfractionated casein is 4-.6, that of unfractionated whey protein is 5.2.

It is surprising that at a pH of about 4 in many Beverage stable emulsions can be obtained according to the invention. Namely, it is known that a slight shift the pH of milk, which is normally around 6.2, causes acidic coagulation, which in addition to The milk proteins also lose the milk fats brought into emulsion by them. The compositions according to the invention, which, in addition to powdered milk or condensed skimmed milk, may contain essential oils or tryglyceride oils are, however, both stable at the "pH of milk" as well as the much lower pH of soft drinks.

The adjustment of the pH value during homogenization to a value between 4.5 and 6.0, preferably 5.0, takes place with an acid commonly used in non-alcoholic beverages, such as citric acid, malic acid, tartaric acid, lactic acid

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acid and phosphoric acid.

The emulsions obtained can then be processed further immediately can be used, for example, as a syrup. However, if you want to store or ship the emulsion as such, it is preferable to adjust the pH to a slightly higher value, e.g. to 6.0 to 6.5 by adding a 10 # solution Solution of sodium hydroxide.

The compositions according to the invention non-alcoholic for making beverages are provided, have continued the ^v place eil that they do not lead to a bacterial "contamination of soft drinks produced with it. It has been shown that the inventive emulsions can be sterilized The sterilization can also take place after the dilution of the emulsion to the concentration of the beverages produced with it and after the adjustment of the pH value.

This sterilization can be carried out in portions by heating to 120 C for half an hour or continuously by heating briefly to a high temperature. But you can also use chemical substances for sterilization or preservation, such as pyrocarboxylic acid diethyl ester in a concentration of about 0.1 #.

Another advantage of the invention is that the addition of emulsions of triglyceride oils stabilized with milk powder, of terpenes that result from essential oils Distillation or extraction obtained or produced from mixtures of triglyceride oils and terpenes beverages which have a stronger cloudiness than that caused by the flavorings, or

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that even cloudy drinks can be obtained in those cases in which the flavorings alone are at all result in no turbidity.

As already mentioned above, the invention remains Emulsions stable when heated. This makes it possible to solidify the emulsions by spray drying.

Therefore, the invention makes it possible to produce powdery Prepare compositions that can give drinks a cloudy appearance. Flavors can be present in the powder may or may not be included. It has been found that these powdered compositions are very easily immersed in water can be distributed, resulting in cloudy emulsions of good stability.

It is also possible in the emulsions or the powdery ones Preparations to incorporate suitable dyes and other raw materials required for the manufacture of a beverage are.

Instead of checking the pH of the concentrated emulsion before homogenizing to the value 4.5 - 6.0, preferably 5 »0, to increase, the stability of the emulsion can be improved by adding polyhydroxy compounds such as sucrose, Glucose, invert sugar, sorbitol, glycerine, etc.

The stability can be increased by adding thickeners such as guar gum, locust bean gum, carragee wrack, Agar-agar, pectin, etc.

If polyhydroxy compounds with or without a thickener are added, the pH needs to be used for sterilization purposes Storage doesn't get increased. So you can be a focused one

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Obtained emulsion for the production of cloudy beverages, which is stable at the pH value, at the known preservative are effective.

Suitable combinations of polyhydroxy compounds can be used as well as from thickeners]! be used. The choice of the polyhydroxy compound to be used depends on the one desired Composition of the finished drink -ab, in particular on the ratio of the desired sweetness to the calorie content. In most cases, sucrose will be used .

The weight ratio of skimmed milk (based on solids) to the polyhydroxy compound should not be less than 1: 4. Of the Addition of larger amounts of solids from skimmed milk is possible, but it is limited for economic and taste reasons.

Of the above-mentioned thickening agents, pectin is preferably used. Pectins from citrus fruits and apples, and although those with both high and low methoxy content are useful. It has been found that the received Almost no emulsions when using pectin Show signs of separation in the finished drink that occur with the use of certain colors and fruit juices can. The amount of thickener that is added is not very critical. Very small amounts already increase the stability of the emulsions. The upper limit is given by the fact that the product begins to gel ..

In Hegel the weight of the thickener is about 30 to 60 % of the weight of the solids in the skimmed milk. The concentrated emulsions can be acidified with a fruit acid, preferably citric acid, up to a pH of 2

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without any separation occurring. This high stability in an acidic medium allows the emulsions to be preserved with known preservatives, such as benzoic acid and sorbic acid, which are known to be active only in the acidic range because the undissociated molecule is the active agent. With benzoic acid, a useful effect can only be achieved at a pH value below 5 _? 0 with sorbic acid below 5.5

According to the invention, compositions for the production of cloudy beverages can therefore be obtained which are stable · are ized by a content of skimmed milk solids at least one polyhydroxy compound and optionally a thickener that is preserved by preservatives that develop their activity only in the more acidic range, such as benzoic acid and sorbic acid.

Such sterilized concentrated emulsions for manufacture Clouded beverages can be stored for a long time without loss of stability and without decomposition by bacteria. They offer advantages over solid compositions in terms of handling, because the beverage industry as a rule is better equipped to handle liquids.

The increased stability of the emulsions, the polyhydroxy compounds and thickeners - if desired - contain, and the small influence of pH on it, enables the Preparing emulsions in various ways, as Examples 12-21 show.

example 1

Production of a concentrated emulsion and a powder with a neutral taste.

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480 g of skimmed milk powder (medium heated) are added to 1289 g of ^{water at 40 ° C. and dispersed by stirring.} Then 210 g of liquid triglyceride of fractionated coconut oil fatty acids, 14 ml of a 50% strength aqueous citric acid solution and 5 g of sodium citrate are added. The whole thing is mixed vigorously with a Homorex mixer or a Waring Blender. It may be appropriate to add a small amount of an anti-foaming agent suitable for use in foods to prevent excessive foaming.

Any air that may have been taken in during mixing is removed by gentle stirring under reduced pressure removed. The mixture is then homogenized twice using a Rannie homogenizer at 100 or 50 atm.

The mixture obtained in this way is spray-dried. The inlet temperature of the air is 195 ° C, the outlet temperature

Example 2

Production of a non-alcoholic drink with neutral cloudiness.

700 ml sucrose syrup (67%), 20 ml 50% citric acid solution, 2 ml of 25% sodium benzoate solution and 3 g of the example 1 obtained spray-dried product are mixed. It is then made up to 1 liter with water. 50 ml of this syrup are filled into bottles together with 250 ml of water and closed with a crown cork. The drink obtained possesses a neutral taste and a slight cloudiness. It shows no signs of being stored at room temperature for six weeks a ring or sediment formation.

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Example 3

Making a cloudy ginger drink.

3 g of the powder obtained according to Example 1 are dissolved in 100 ml of water at 40 ^° C. with stirring. Then 2 ml of 25% sodium benzoate solution, 560 ml of 67% sucrose syrup, 20 ml of 50% citric acid solution, 1 g of caramel and 4 g of commercially available ginger essence are added and made up to 1 liter. 50 ml of the mixture are filled into 300 ml bottles with carbonated water (3 vol. CO _2). A finely cloudy drink is obtained, which is still completely stable after storage for 7 weeks.

Example 4

Clouded peppermint drink

The flavoring emulsion is made analogously to Example 1 by mixing 642 g of water (40 ° C.) and 240 g of skimmed milk powder (heated to a low temperature), 90 g of peanut oil, 15 g of peppermint oil and 6 ml of 50% citric acid solution were obtained. The syrup is through Mix 12 g of the flavoring emulsion, 700 ml sucrose syrup (67%) t 20 ml 50% citric acid solution and 2 ml 25% sodium benzoate solution and make up to 1 liter.

The drink is obtained by filling 50 ml of the obtained syrup with water in 300 ml bottles. That pleasant tasting drink looks slightly cloudy. There was no change after 6 weeks of storage at room temperature.

Example 5

Bottles with the cloudy peppermint drink, which has been obtained according to Example 4, are heated to 75 ° C. for 20 minutes pasteurized. The stability of the drink seemed at least. ' to be the same as that of the unpasteurized beverage.

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Example 6

Clouded drink with orange flavor.

Analogously to Example 1, an emulsion is prepared by mixing 642 g of water at 40 ° C., 240 g of skimmed milk powder (heated to a high temperature), 70 g of sunflower oil, 35 g of Florida orange oil and 6 ml of 50% citric acid solution. To produce the syrup, 12 g of this emulsion, 700 ml of sucrose syrup (67%), 20 ml of 50% citric acid solution and 2 ml of 25% sodium benzoate solution are combined and made up to 1 liter.

50 ml of the syrup are filled into 300 ml bottles with carbonated water (3 vol. CO _2).

A drink is obtained with a constant cloudiness which remained unchanged after 6 weeks of storage at room temperature.

Example 7

According to Example 6, a drink was prepared, starting from an emulsion, the amount of orange oil of which was 95 g and at who replaced the sunflower oil with 10 g of coconut oil. The stability of the beverage was similar to that of Example 6 received beverage.

Example 8

Analogously to Example 1, an emulsion of 642 g at 40 ° C. was produced Water, 240 g skimmed milk powder (medium heated), 70 g orange oil Florida, 35 g triglyceride from fractionated coconut oil fat » acids and 5 ml of 50% tartaric acid solution.

The syrup and the drink were obtained analogously to Example 6. That Drink showed a cloudiness of comparable stability.

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Example 9

Drinks were produced analogously to Example 8 in which the tartaric acid in the emulsion was replaced by one of the following acids had been: 50 ml 50% maleic acid, 5 ml 50% lactic acid and 5 ml of 20% phosphoric acid. In all cases, drinks were obtained whose turbidity remained unchanged after 6 weeks of storage stayed.

Example 10

Emulsions which had been obtained according to Example 1, 4, 6, 7 or 8 were filled into metal containers with a capacity of about 1 l and then sterilized in an autoclave for 1/2 hour at 120 ° C. The same was done with the emulsions, after their pH was adjusted to 6.2 with sodium hydroxide. All made from the sterilized emulsions After 4 weeks, drinks still showed a constant cloudiness.

Example 11

Drink that contains a cloudy fruit juice.

An emulsion for clouding is prepared as follows: 150 g of skimmed milk powder (roller-dried) are dissolved in 500 g of 40 ° C. warm water and placed in a mixer. A mixture of 150 g Florida orange oil and 150 g vegetable oil, 60 ml 20 & Lge sodium citrate solution, 8 ml 50% citric acid and a small amount of antifoam are added. After trapped air has been removed by stirring in vacuo, the mixture is homogenized twice, first at 100 at, then at 50 at. The emulsion is then spray-dried. To prepare a syrup, 5 g of the powder thus obtained are mixed with 50 ml of water and 2 ml of 25% sodium benzoate solution, 700 ml of sucrose syrup (67 %) and 20 ml of 50% citric acid are added. It is then made up to 1 1.

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The drink is made by adding 50 ml of syrup and 2.5 Pour ml of concentrated orange juice (60 ° Brix) with carbonated water into JOO ml bottles. The drink has a pleasant natural orange taste and a constant cloudiness, which increases after 4 weeks of storage Room temperature did not change.

Example 12

A sodium benzoate or potassium sorbate solution and a citric acid elö solution are successively poured into a sucrose solution while stirring. Be in a second vessel Vigorously mix water, milk powder and oil. The mixture thus obtained is added to the stirred sugar solution and then added homogenized in a known manner.

Example 13

Milk powder and water are mixed with the oil by stirring. Then a sugar and a citric acid solution are added. The mixture is homogenized and heat sterilized,

Example 14

Sugar solution, oil and citric acid solution are mixed. Milk powder previously dispersed in water is added with stirring and the mixture obtained is homogenized in a known manner.

Example 15

The solution of the thickener is added to the mixture of Example 14 prior to homogenization.

Example 16

For a dispersion of milk powder in water, ground one after the other Oil, sugar solution, pectin solution and citric acid solution

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admitted. The mixture is then homogenized.

Example 17

The oil and sugar solution are added to a dispersion of milk powder in water. This mixture is homogenized and then a pectin solution and a citric acid solution are added.

When the milk powder is dispersed in water, the addition of a small amount of an anti-foaming agent can be useful be. If a dye is to be added, the dye solution is expediently added after Homogenize.

The following compositions can be used as desired one of the methods given in Examples 12-17:

Example 18

Water 800 g sucrose syrup 67 ° Brix 1500 g

Skimmed milk powder 400 g 25% sodium benzoate solution 13 ml

Orange oil 30 g 50% citric acid solution 14O ml

Example 19

Water 850 g invert syrup 67 ° Brix 1500 g

Skimmed milk powder 350 g 25% sodium benzoate solution 13 ml

Orange oil 60 g 50 ounce citric acid solution 110 ml Antifoam agents

Example 20

Water 400 g sucrose syrup 67 ° Brix 750 g

Condensed lean 25% sodium benzoate solution 10 ml milk (60% solids) 350 g 50% citric acid solution 110 ml.

Orange oil 15g 3% guar gum solution 2000 ml

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example

Water skimmed milk powder Orange oil glycerine (d = 1.26)

200 g 10% potassium sorbate solution 30 ml

10Og 50% citric acid solution 100 ml

12.5 g 3 ounce pectin solution 1000 ml 375 g

All emulsions specified in Examples 18-21, as well as the beverages made therefrom, could last longer than Can be kept for 3 months without any noticeable changes.

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Claims (2)

DIPL-INQ. DIETER JANDER DR.-INQ. MANFRED BDNINQ PATENT LAWYERS CCL / OOI Patent claims: Vl). Process for making concentrates and compositions for the production of cloudy non-alcoholic beverages, characterized in that aqueous Emulsions are prepared and that these are stabilized with skimmed milk powder or with condensed skimmed milk. 2. The method according to claim 1, characterized in that that emulsions of an essential oil or its parts are prepared in water and that these emulsions be stabilized with skimmed milk powder or condensed skimmed milk. 3. The method according to claim 1 or 2, characterized in that an emulsion of a natural or synthetic triglyceride oil is produced in water and that this emulsion is made with skimmed milk powder or condensed skimmed milk is stabilized. 4. The method according to one or more of the preceding claims, characterized in that an emulsion of a mixture of conventional flavors in water and that this emulsion is stabilized with skimmed milk powder or condensed skimmed milk. 5. The method according to one or more of the preceding claims, characterized in that an emulsion of a combination of an essential oil or of Parts of it, common flavors and a triglyceride oil is made in water and that this emulsion is made with skimmed milk powder and / or condensed skimmed milk is stabilized. 209852/0683 - 19 - DIPL..INCJ. DIETER JANDER DR.-INC /. MANFRED BCJNING PATENT ADVOCATE 222/691 - 19 - 6. The method according to one or more of the preceding claims, characterized in that the skimmed milk powder is spray dried. 7. The method according to one or more of claims 1-5, characterized in that the skimmed milk powder is roller dried. 8. The method according to one or more of the preceding claims, characterized in that the emulsion in a known manner at a pH of between 4.5 and 6.0, preferably at 5.0 is homogenized. 9. The method according to claim 8, characterized in that that the pH of the. After homogenization, the emulsion was adjusted to a value between 6.0 and 6.5 in a known manner will. 10. The method according to claims 1-7, characterized in that, in addition, polyhydroxy compounds, such as Sucrose, glucose, invert sugar, sorbitol, glycerin and the like are added. 11. The method according to claim 10, characterized in that that additionally thickeners such as guar gum, carob oil, carrageen oil, agar-agar, pectin and the like «; added will. 12. The method according to claims 1-11, characterized in that a preservative is additionally added will. 13. The method according to claims 1 -12, characterized in that the concentrated emulsion is spray-dried 209852/0683 " ²⁰ " DIPL.-INQ, DIETER JANDER DR..INO. MANFRED BONINO PATENTANWÄLTE / 227 69 I. - 20 - V -! -. Method according to claims 1 - 12, characterized in that g e k e η η ζ eich η e t that the concentrated emulsion is sterilized v: \ rd. 15. Enemy for the production of cloudy, alcohol-free Beverages by means of the method of one or more of Claims 1 to 14, characterized in that additional fruit juice is added. 16. Concentrate or composition, obtainable according to a or more of claims 1-15. 17. Use of the concentrates or compositions according to Claim 16 for the production of non-alcoholic beverages. DJ: 3D 2 O 9 8 S ? 1 Π Ρ