DE2065143A1 - Preservatives for liquid foods esp fermen- - ted products - Google Patents

Abstract

Preservatives for liquid food products such as liquid condiments, natural fruit drinks, beers, fruit wines, sake etc. comprise aromatic carboxylic acid esters or aromatic ketones contg. two OH gps. linked to the benzene ring formula: (where R is 3-8C alkyl; M is H, alkali metal or 1/2 mol. of an alkaline earth metal) in amt. of 5-300 ppm.

Description

Process for the preservation of liquid food.

[Separated from patent. (Pat. Ann. P 20 59 864.5-41)) The invention relates to a method for preserving liquid food. In particular the invention relates to a method for preserving liquid food, that consists in going to the liquid foods from the group consisting of liquid condiments, non-alcoholic beverages, fruit wine and sake, can be selected, a dihydroxybenzoic acid ester or a dihydroxyphenyl alkyl ketone adds.

The term "liquid food" as used herein Application and used in the claims means liquid condiments, such as soybean oil, Vinegar and sauces and non-alcoholic beverages, such as natural fruit juices and Carbonated drinks, fruit wine, wine and sake or rice wine.

Preservatives generally used in liquid foods are used are benzoic acid, salicic acid, dehydracetic acid salts, p-hydroxybenzoic acid esters and salts of sorbic acid.

With these preservatives it sometimes happens that a sufficient one Preservation effect will not be achieved if it in the crowds that are allowed by the food laws. Still hangs their effect depends on the types of foods to which they are added.

In the case of soybean oil, the propyl and butyl esters are p-hydroxybenzoic acid used to control putrefactive microorganisms such as wild yeast, but these esters are in the case of soybean oil, which does not last for 20 to 30 minutes had been heated to 8000 by esterase remaining in the solybean oil, decomposes and its effect is lost. In the case of rice wine in Japan it is allowed Silicylic acid to be used in an amount up to 250 ppm, the most important putrefactive bacteria, such as Lactobacillus homochiochi and @iochis Lactobacilli to control, but an addition of salicylic acid ren in such amounts results a sufficient preservation effect. Furthermore, there is almost all of salicic acid the @@ i @ ity problem. Against the main putrefactive bacteria of the Vinegar, like Acetobacter xylinum and other acetic acid bacteria, becomes butyl p-hydroxybenzoate mainly used as a preservative. However, butyl p-hydroxybenzoate has at a concentration sufficient to control such bacteria is effective, for example around 140 ppm the tendency, during storage at around 0 ° C, as it has limited solubility in vinegar and the vinegar becomes opaque and cloudy. Benzoic acid or sorbic acid are used to cause putrefaction Microorganisms in fruit juices @ such as yeast and mold, to control, so influence these acids adversely affect the smell and taste of the juices. Are dutyl p-hydroxybenzoate and sorbic acid used as a preservative for rice wine or fruit wine, so they have at their effective concentrations (70 to 100 ppm for the former and 200 to 400 ppm in the latter) has a very bad influence such drinks, with the result that the value of a drink is lost.

It has now been found that aromatic carboxylic acid esters or aromatic Ketones, which contain two hydroxyl groups attached to a benzene nucleus, are excellent have an antibacterial spectrum and have a very low toxicity because Precursors of these compounds occur in nature and in general for the are harmless to the human body.

It has also been found that these compounds can be found in liquid foods are excellently soluble and that they have excellent storage stability.

The present invention relates to a method for preserving liquid food, which is characterized in that a liquid food selected from the group consisting of liquid roots, non-alcoholic beverages, fruit wines and sake is selected with a compound of the formula : adds, wherein n is 2, R is an alkyl group having 3 to 8 carbon atoms and M is a hydrogen atom, an alkali metal or half a mole of an alkaline earth metal.

In the general formulas I and II, those expressed by R can be used Alkyl groups can be either straight or branched, but generally it is it is preferable that R is a straight chain alkyl group.

Compounds of formulas I and II used in the present invention used are given in Table I.

Table I. connec- Solubility (ml) Melting point dung structural formula water 150% aqueous Rings solution boiling point, } ir structure formula water zi S Lo sg 6 S3 depunkts ~ H ~ i HO5 COOC3H7 2. 50 x 102 7.02 »102 39. 2 b 00004119 1.0 x 102 5.13 x 102 60 - 61 3 1 000c5t111 3.88 x 10 8.62 x 10 [145 / 0.0S inrnllgJ 4 n -000061113 1s37 x 10 4.21 x 10 tl47 / Q, l mmHg] 5 1 c7} I15 5.82 2.50 x 10 [l56 / 0. 1 mmHg] 6 tr - COOCgHL7 3.28 1.61 x 10 tl60 / o. 2 intimate] OH 7 ffi $ / \ cooo3 <7 1.5? x 103 5.21 x 103 60 110 7, 011 1.57 x 103 5.91 x 103 60 8 "- COOC4H9 7.53 x 102 1. 35 - x 102 62 - 4 9 1I - COOCsHll 3.10 x 102 6.19 x 102 [145 / l mmHg] 10, 1 -COOC6H13 1.91 x 102 5.72 x 102 [170/2 mmHg] 11 1 -COOG7H15 5.65 x 10 1.13 x 102 [168/1 mmIIs3 12 "- COQC8H17 2.46 x 10 2.00 x 10 [178/1 mmHg | 13 HO HOOCOOC3H7 1.29 x 103 4.37 x 103 115 14 1l -000C4H9 5.45 x 102 1.49 x 103 113 - 5 15 | - COOCsHll 2.92 x 102 1 7.80 x 102 93.5 - 94.5 16 "- COOC6H13 1.81 x 102 5.43 x 102 117 17 -C °° C7} i15 7.20 x 10 1.45 x 102 84 - 86 18 1i -COOCgH17 1.91 x 10 2.75 x 10 101 - 103 HO 19 t3FCOOC3H7 1.86 x 103 7.29 x 103 60 - 61 110 20 "-COOC4Hg 6.48 x 102 1.35 x 103 [198 / 0.2 mmHgl 21 1 -COOCHll 2.14 x 102 6.48 x 102 1205 - 210 /0.15 mmHgJ 22 "-COOC6H13 8.22 x 10 4.87 x 102 [208 212 /0.1 mmHg3 23 1 'C00ll15 3.92 x 10 1.20 x 102 (215 / 0.1 romHg] lt -Co ° C8Nl7 2.12 x 10 6. 88 x 10 [220 / 0.1 rawnHg] 011 UQG3N'I lx iOX LQ-a) 3 52 26 11 - ONl52 3.9 x 10 X lo2, e93so2 57 - 60 27 - O0% t11 5.6 x 1, 18 x 102 53 - 5 28 "1l XT33 2, 50 2 10 l.Ag x 102 42 7 47 29 11 "@ OC6115 9.13 t 62 62 63 II 33 ß ° C32t? 2.61 x 102 53l x 102 79 - g2 110 31 11 (0OAF1H? F ^ 24 / FX) 0 2s93 x 102 51 - 4 32 8 wC00 3ç7fZ x 10 7.96 :: 10 77 - 9 33 1I 00C6¼3 1rf ,; 3 10 7 @ 21 like $ 8 "9C 34 II -C0O715 l x-; 6.4 ic SO 85 - 87 HO 35 HC; O 3i-17 7.70 l.99 X 103 144 - 6 X t 'COC; b9 Jfflg 3 9 @ Ab x 152 9 6 36 r -CICSII11 1.80 tl gnya8 x i0 x i2 77 - 37 - ° DO5} 77 5§58 x ic 77 38 lt -C6 (JH13 3.16 x 10 14½ x io2 83 - 85 33 lt -C0H15 3..3Q x 10 6.00 x 10 81 - 86 In the present invention, it is critical that the compound expressed by the formula I or II have an alkyl group R containing 3 to 8 carbon atoms.

Among the compounds expressed by the formulas I and II are those which contain alkyl groups with up to 2 carbon atoms as the radical R not suitable because their antibacterial effect is very weak and their Toxicity is very high. On the other hand, compounds represented as the group R are an alkyl group containing 9 or more carbon atoms, because of their poor solubility preferred.

The dihydroxybenzoic acid esters according to the invention or the dihydroxyphenyl alkyl ketones can be used in the form of a salt when the hydrogen atom is from one or more hydroxyl groups through an alkali metal such as sodium or potassium, or is replaced by an alkaline earth metal such as magnesium and calcium. When the invention Esters or ketones are used as salts, their solubility in water is still improved.

All compounds of the formulas I and II used according to the invention are easily soluble in liquid foods. Furthermore, they have Compounds of the invention have a structure similar to the structure of p-hydroxybenzoic acid ester is. The use of p-hydroxybenzoic acid ester is approved by the World Health Organization (WHO) and the Food and Agriculture Organization (FnO) are considered safe and harmless and it is believed that the course of internal metabolism of the invention Compounds similar to the metabolism of p-hydroxybenzoic acid ester. Other Compounds that are analogous to the compounds according to the invention, such as gallic acid, Protocatechic acid and phloroglucinic acid, are widespread in nature and their security is very high.

The compounds according to the invention can be used for many liquid foods, such as liquid spices such as soybean oil, vinegar and sauces and for non-alcoholic ones Beverages, for example natural fruit juices, beverages that contain carbon dioxide, Wine, Fruit wine and sake are used, but they are especially effective when they are for the preservation of fermentation products such as vinegar, soybean oil, bruised wines and sake.

When the above compounds are used for food, which are high in protein, they tend to get attached to the proteins and lose their preservative effect. Accordingly, it does not make sense to use the compounds according to the invention for preserving food, the proteins contained in large quantities. The compounds according to the invention show high solubility in liquid foods and even when in relative high concentrations, for example 300 ppm are added, they fall during of storage. Since the above compounds are generally high in antibacterial Having activity, one can get sufficient effect by turning it into liquid Adds food in amounts of 5 to 60 ppm.

In the practice of the present invention, the compounds of formulas I or II at each stage in the preparation of liquid foods They can be added in the form of an aqueous solution in alkali metal hydroxides, such as Sodium hydroxide and potassium hydroxide can be added. They coim also inflicted are after one or two of their hydroxyl groups in the corresponding alkali metal salts Have been convicted.

Furthermore, they could be in the form of phosphoric acid esters or glycerol ethers or in the form of a solution in ethanol, propylene glycol, or other edible harmless solvents such as glycerine and water are added. For example, they can used in a mixed solvent of propylene glycol and sodium hydroxide will.

The antibacterial activity of some compounds of the formulas I and II, which are used erfindungsge @@ d @, in Tables II and III specified the numerical values that given in the tables are values of the minimum growth inhibition concentration required for antibacterial Trials were obtained, the trials at 3000 for 4 days in one Potato dextrose medium or in an agar medium and where one used various bacteria, yeasts and fungi.

Table II Compound (γ / ml) Bacterium 1 2 3 7 8 9 13 14 15 19 20 21 Sthaphylococcus aureus 209F 100 100 25 400 400 100 400 400 200 800 800 800 Bacillus subtilis PCI219 100 100 25 400 400 50 400 400 100 400 400 400 Salmonella enteritidis 1891 400 200> 100 400 400 100 200 200 200 400 400 400 Escherichia coli 0-55 400 400> 100 400 400> 200 400 400 400 800 800 800 eu Prot ## s vulgaris HX19 50 50> 100 400 400 50 400 200 100 200 200 200 Aspergillus niger IAM3001 125 125> 250 250 250 125 500 500 250 1000 1000 1000 Rhizopus nigricens IAM6070 125 125 250 250 Saccharomyces cerevisiae 62.5 62.5 62.5 125 125 62.5 250 250 125 500 500 500 Hansenula anomala 62.5 62.5> 250 125 125> 62.5 250 250 125 1000 1000 1000 Candida utilis 62.5 62.5 125 250 250 62.5 250 250 125 500 500 500 Table III Compound (γ / ml) Bacterium 25 26 27 30 31 32 35 36 37 Sthaphylococcus aureus 209p 400 200 100 800 100 100 800 800 400 Bacillus subtilis PCI219 400 200 50 400 100 100 800 800 800 Salmonella enteritidis 1891 400 100 200 400> 200 200 800 400 200 Escherichia coli 0-55 400 400> 200 800> 200 200 800 800 400 Proteus vulgaris HX19 200 100 25 400 100 100 800 400 200 Aspergillus niger IAM3001 250 125 125> 250 625>31.25>500> 500 250 Saccharomyces cerevisiae 250 125 <7.85> 250 31.25>31.25> 500 500 250 Hansenula anomala 250 125 31.25> 250 31.25>31.25>500> 500 250 Candida albicans # 250 125 31.25> 250 31.25>31.25> 500 500 250 In Tables II and III the numbers of the compounds correspond to the numbers in Table I. These numbers are also used in the following tables.

In general, most liquid foods have one pH value from 2.0 to 5.0 and they contain certain amounts of organic acids, amino acids or of saccharides. Accordingly, they tend to be a culture medium for bacteria, such as lactic acid bacteria, molds and film-forming yeasts. Welzn the above-mentioned compounds of formulas d and II to form such liquid foods in the concentrations given above. are added, they show bessexe Preservative effect compared to the usual preservatives. Farther these compounds are not broken down by the liquid food products, but increase the shelf life of the food. Accordingly, the liquid Foods in which the compounds according to the invention have been incorporated, be eaten without fear of their toxicity and their harmlessness and safety is much better compared to known preservatives for Food.

The preservative effects and the antibacterial activities of the Compounds of the invention depend on the nature of the most putrefactive Microorganisms of the corresponding liquid food and the position of the Hydroxyl groups and the number of carbon atoms of the alkyl group and strong of the type of food in which the compounds are used. Accordingly becomes a suitable compound depending on the type of liquid food, the one to be preserved is selected.

For example, in the case of soybean oil, vinegar and fruit juices the number of carbon atoms of the alkyl groups is more important than the position of the Hydroxyl groups and it is desirable to use a compound that is in their alkyl part contains 3 to 5 carbon atoms.

To this day, butyl p-hydroxybenzoate is often used for soybean oil Preservatives used. However, this connection shows a relatively minor one antibacterial activity and it is therefore necessary to combine this compound in one Concentration before.

Use 50 to 100 6 / ml. So it sometimes happens that a part fails if a) black opacities form on the wall of the soybean oil bottle. In the winter the solubility of the compounds is often below their effective concentration humiliated. This preservative is also added to soybean oil that hasn't been heated sufficiently or becomes too raw soybean oil, it will through the esterase present in the soybean oil decomposes and it is impossible to carry out a pasteurization treatment which is suitable for the taste and To get smell of soybean. On the other hand, it has been found that the invention Dihydroxybenzoic acid alkyl esters at concentrations as low as 15 to 20 t / ml SoUabohnöl is sufficiently preserved and that it has the above disadvantages of the known Overcomes preservatives. It has also been found that the addition of Dihydroxybenzoic acid alkyl ester according to the invention at a concentration of 10 up to 20 d g / ml for sauces and liquids, e.g. for diluting Soybeans or liquids containing amino acid have excellent preservative properties as in the case of soybean oil itself.

The decomposition and putrefaction of vinegar are caused by acetic acid bacteria, like Acetobacter xylinum and Acetobacter aceti, causes and a film forms, Cloudiness occurs and the acidity is lowered. The use of salicylic acid and p-hydroxybenzoic acid esters as preservatives for vinegar are allowed, however Salicylic acid does not work at the permitted concentrations and p-hydroxybenzoic acid ester often fail at their effective concentrations (140 & / ml) in winter, which the vinegar becomes cloudy. The compounds according to the invention prevent decomposition and the putrefaction of vinegar at concentrations of 20-30 (/ ml and they overcome the above-mentioned disadvantages which the known preservatives for vinegar have.

Soft drinks are divided into types that contain carbonic acid, and those that do not contain carbon dioxide. It is allowed to use benzoic acid (600 γ / ml), Dehydroacetic acid (50 γ / ml) and a p-hydroxybenzoic acid ester (100 γ / ml) to use as preservatives for both types of soft drinks, but even if these substances are added in permitted concentrations, can the formation of turbidity caused by yeasts can often be observed. The invention Compounds prevent such decomposition from occurring at the concentration of 20 to 30 γ / ml.

Natural fruit juices are easily broken down by microorganisms from squeezing to filling in cans or bottles spoil and the like Decomposition causes the appearance of cloudiness and gas formation from mold, yeast, and acid-resistant lactic acid bacteria @ Soloche decomposition can be caused by Addition of benzoic acid in concentrations of 500 γ / ml to some extent Avoided, but this preservative gives the juice a special one @pleasant taste, so you get hardly acceptable ones with this preservative Results. Dehydracetic acid is unsuitable as a preservative for juice because it gradually decomposes in the juice and loses its activity, and therefore can decomposition easily occur if a juice bottle is opened after a long storage period will. The compounds of the invention of the formulas I or II are used as preservatives used at a concentration of 10 to 50 γ / ml, the above-mentioned can be used Disadvantages of the known preservatives are overcome.

Are the compounds of the invention used as preservatives used for rice wine, it is desirable that in the above-mentioned formulas I and II the two hydroxyl groups on the benzene nucleus in the 2,4 or 3,4 positions are bonded, and that the alkyl group R has a chain length of 5 to 8 carbon atoms is equivalent to. Compounds with these structural properties show excellent Solubility, they are stable, and they have high antibacterial activity. Furthermore, they are to control hiochic43akteria all in one effective over a wide range and they affect the taste and smell of rice wine not bad when used as preservatives for rice wine. Furthermore, they do not cause any discoloration or clouding of rice wine itself during long periods of storage. As shown in the examples, these are Compounds at a very low concentration against typical hiochic bacteria effective and they allow control of the whole range of hiochic bacteria, found in a brewery. Complete control of hiochac'akteria can be achieved; by using as a preservative for rice wine for example n-Hexyl 1,4-dihydroxybenzoate used at a concentration of 15 to 20 ppm. This proves that the compounds of the invention are superior to lysozyme as a new preservative that has attracted a lot of attention, as lysozyme against hiochec bacteria of the Lactobacillus acidophillus species is not effective, although it has properties of rice wine is not adversely affected and therefore promising as a preservative appeared.

The preservation of sake according to the present invention is described in divided into the following three procedures. The first procedure is mainly on it designed to avoid decomposition during storage in the tank. Clearer and transparent rice wine that is obtained by removing impurities from raw Rice wine is removed, warmed to approximately 55 ° C and then stored in a tank. If this heat treatment is insufficient, various yeasts and hiochic bacteria remain decomposition is caused in the rice wine and by these organisms. To the occurrence To avoid such decomposition, it is preferred to use a compound of the formulas Add I or II in an amount of 5 to 200 ppm, thereby increasing the growth during the usual storage time of microorganisms (maximum 1 year) is prevented and whereby decomposition does not occur during storage time and is fungicidal Effect is to be observed, what an effective preservation brings with it.

According to the second method, sake is made into which the preservation compound of the formulas I or IT is incorporated according to the first method above, with active Carbon or other suitable adsorbent treated before shipping, to remove substantially all of the preservative compound from the rice wine. With this procedure it is possible if one is careful in the following steps Just like bottling, sake works that essentially is free from all preservatives and has absolutely no hiochic bacteria contains.

The third method is that you can combine the formulas Add 1 or II in the amount given above to rice wine treated with activated charcoal before it was shipped. This procedure is used when There is a risk of hiochi rot even after bottling. If a rice wine bottle is opened by the consumer, it starts - especially in the Summer - the rice wine, which contains no preservatives, within a short time Time to rot through hiochi. The third method is suitable for the Prevent rot due to hiochi bacteria after opening the bottle.

Results of the antibacterial studies of the previously mentioned Species against common microorganisms which have been filtered through by a Potato dextrose medium (in the case of yeast and mold) or an agar medium (in the case of common bacteria) used are given in Table IV. the numerical values in the table are values of the minimum growth inhibition concentration (γ / ml) when cultivated at 3000 for 4 days.

Table IV Bacteria species compound 17 compound 29 Saccharomyces cerevisine 15.6 <7.81 Saccharomyces rouxii <3.91 <7.81 Asporgillus niger 62.5 62.5 Staphylococcus aureus 50 12 Bacillus subtilis 50 12 Proteus vulgaris 50 12 The main antibacterial activities of other compounds are given in Table V.

Table V Lactic acid bacil Compound no. Yeast left 16 <7.81 - 62.5 250 11 3.91 - 31.25 <25 28 7.81 - 15.63 <50 34 3.91 - 15.63 25 - 50 4 7.81 - 125 <5 The harmlessness and safety of these compounds is characterized by the fact that, when administered orally to mice, almost all of them have an LD50 value of 3 to 6 g, and the compounds are therefore characterized by very low toxicities.

The present invention is also effective for preservation used by fruit wines, such as wine made from grapes. In general, in Fruit wines, such as wines made from grapes, by @erobic bacteria, such as by Mycoderma enjoyment of movies. Pollution occurs through bacteria of the Acetobacter or Bacterium genus by acetic acid on and by bacteria the Bacterium ge - @@ occurs tartaric acid fermentation, Mannitol fermentation, the formation of bitter substances, fatty acids and lactic acids namely during the manufacturing process, or during filling @ @n bottles. This has a bad influence on the quality of the product in many cases. Particularly in the case of white wine, the use of preservatives is a control indispensable for the quality of the product. For this reason, sulfuric acid is recommended (sulfurous acid) at a concentration of 450 γ / ml or salicylic acid in a concentration of 350 γ / ml to be used, but these preservatives bring the problem of toxicity and their effect will not be enough If the present invention is used to preserve fruit wine, one can excellent preservation effects in comparison with the method according to the invention with the well-known preservation methods in which sulfuric acid is used, reach. Furthermore, it was surprisingly found that the inventive Method of taste or the smell of the one in no way be negatively influenced.

The minimum growth inhibition concentration values (r / ml) of the Compounds according to the invention which are obtained when culture experiments are carried out on yeast and acetic acid bacteria at 30 ° C for 20 days in wine to which 10 % Water added are given in Table VI. From those given in Table VI Results can be seen to be those used in the present invention Compounds especially against film formation and contamination by acetic acid are effective.

Table VI Compound yeast acetic acid compound yeast acetic acid No bacteria No bacteria 26 7.81 25 9 7.81 10 27 3.91 25 10 3.91 10 28 3.91 10 11 1.92 10 29 .1.95 5 12 1.92 5 31 15.63 50 21 15.63 50 32 7.81 50 22 7.81 25 33 7.81 25 23 7.81 25 34 3.91 10 24 3.9i 10 15 31.26 50 3 15.63 50 16 15.63 50 4 7.81 25 17 7.81 25 5 3.91 10 18 7.81 -25 6 3.91 10 The following examples illustrate the invention without, however, restricting it.

Example 1 Raw soybean oil that is free from preservatives was subjected to pasteurization treatment at 600 or 80 ° C for 30 minutes and then the impurities were subsequently removed. Each of the in table VII compounds became 20 ml of a soybean oil sample thus pasteurized admitted.

The sample to be examined was in the form of a solution in 1N aqueous Sodium hydroxide at various concentrations in 10 parts of 3 γ / ml up to 30 d '/ ml added. Each sample was yeast fully film-forming with a platinum loop infected and then the samples were kept at 3000 for 7 days and the growth the yeast was examined. The results (minimum growth inhibition concentration - γ / ml) are given in Table VII. In Table VII, the symbol means "+", that turbidity was observed in the sample of soybean oil.

Table VII Pasting at 60 ° Added preservative at 80 ° C processing agent 3 days 7 days 3 days 7 days Comparison test, nothing added + + + + Butyl para >30> 30 27 30 hydroxybenzoate -Connection 1 18 18 Compound 2 18 18 Connection 3 24 27 Connection 8 24 27 (Connection 9 24 24 Connection 14 21 24 Example 2 A solution of the test compound listed in Table VIII in 1N aqueous sodium hydroxide was added to approximately 100 ml of preservative-free vinegar and each sample was infected with a platinum loop full of a liquid containing active Saprogen bacteria and stored at 30 ° C for 20 days. Nan investigated the occurrence of cloudiness and the decrease in acid strength caused by yeast and vinegar bacteria. The results are given in Table VIII.

In Table VIII, the acidity is expressed by expressing the amount (ml) of 0.1 N aqueous sodium hydroxide indicated, which was consumed by 10 g of the Neutralize sample. The acidity of the vinegar at the time of addition was Test compound 4.21. The symbols "-" to "+++" mean the absence of haze and the degree of opacity.

Table VIII Added Turbidity acidity Preservation amount compound (γ / ml) 10days 20days 10days 20days Settlement agreement search, nothing ++ +++ 3.44 3.02 admitted Butyl para- 50 - + to ++ 4.20 3.70 hydroxybenzoate "140 - # to + 4.18 3.85 Connection 1 30 - # to + 4.22 4.06 Connection 2 30 + + - 4.18 4.10 Connection 3 30 - # 4.19 4.12 Connection 4 30 - # to + 4.18 3.98 Similar compounds were made with respect to other liquid condiments such as sauces and stick liquids, and it was confirmed that the compounds of the present invention have higher anti-putrefaction and decomposition effects at concentrations of 30 γ / ml than p-hydroxybenzoic acid esters at a concentration of 100 to 200 / ml.

Example 3 A bottle of a beverage that does not contain a preservative Contained, but was carbonated, was opened at 0 ° C and to the open Carbonated beverage (approximately 200 ml) was given as indicated in Table IX Test compounds in 1N sodium hydroxide solution. Then the drink came with Infected 1 ml of a liquid, the active yeast (the number of He- @ was approximately 105 per g) and then the bottle was closed with a cork. the Bottle was kept at 30 ° C for 21 days and the appearance of white haze was observed examined. The results are given in Table IX. The symbols "-" to "+++" mean the absence of turbidity and the degree of cloudiness.

Table IX Granted white haze Preservation (γ / ml) middle 7 days 14 days 21 days Comparative experiment nothing added + ++ +++ Benzoic acid 600 - # to + + to ++ Dehydracetic acid 50 - # to + + to ++ Butyl para 70 # + ++ hydroxybenzoate Connection 8 30 - # to + Connection 9 30 - # to + From the results given in Table VIII it can be seen that the compounds of the present invention are much more effective at inhibiting the growth of yeast and / or the appearance of white turbidity in carbonated ones, unlike known preservatives such as benzoic acid, dehydroacetic acid and p-hydroxybenzoic acid esters Connect drinks.

Have similar studies been made with respect to non-carbon Drinks, it was confirmed that the compounds of the present invention were excellent Deliver preservation results.

Example 4 A platinum loop full of putrefactive bacterial liquid (containing active yeast, mold, acid-resistant lactic acid bacteria and other bacteria) was added to 50 ml of fruit juice prepared by squeezing an orange (Onshyu quality), and then added sugar in such an amount as that a sugar content of 10% was obtained. A solution of the compound given in Table X in 1N aqueous sodium hydroxide was then added to the juice and the juice was stored at 30.degree. The growth of mold and the appearance of turbidity in the juice were examined. The results are given in Table X. The symbols "-" to "+++++" appearing in the table mean the absence of mold or turbidity and the degree of intensity of mold growth or turbidity in the juice. Table 1 Granted Preserved cloudiness mold growth material (γ / ml) 3 days 7 days 10 days 3 days 7 days 10 days Comparative try + ++ +++ + +++ +++++ nothing to- given Benzoic acid 500 - # to + ++ - -to + + Btityl-para- hydroxy- 30 - - -to # - - - benzoate Connection 2 30 - -to # # to + - - # Connection 3 30 - -to # #to + - - -to # Connection 90 30 - - - - - - Connection 15 30 - - - - - - Example 5 Raw soybean oil free from preservatives was subjected to pasteurization treatment for 30 minutes at 60 ° O or 80 ° C, and then the impurities were removed. Each of the compounds listed in Table XI was added to 20 ml of a pasteurized sample of soybean oil.

The compound to be investigated was in the form of a solution in 1N aqueous Sodium hydroxide at concentrations ranging in 10 parts from 3 γ / ml to 30 Vml varied, admittedly. A platinum loop of fully active film-forming yeast became with each Sample given and then the sample was kept for 7 days at 3000 and that Heart growth was examined. The results (minimum growth inhibiting concentration - S / ml) are given in Table XI. Compound A is an ethyl ketone that corresponds to compound 25, compound B is a hexyl ketone, which corresponds to compound 25, compound a is an ethyl ketone, which corresponds to compound 30 and Compound D is an ilexyl ketone which corresponds to Compound 30. That Symbol "+" in the table means that in the simple soybean oil sample, turbidity occurred.

Table XI 60 ° C pasteurization 80 ° C pasteurization Preservative 3 days 7 days 3 days 7 days Comparative experiment + + + + nothing admitted Butyl-para>30> 30 27 30 hydroxybenzoate ......................... | ............ | ........... . | ........... | ............. | Connection A 18 21 18 21 Connection 25 12 15 15 15 Connection 26 12 15 12 15 Connection 27 .12 12 12 15 Connection B 24 24?>30> 30 Connection C | > 30 | > 30 | > 30 | > 30 Connection 32 12 15 12 15 Connection D | > 30 | > 30 | > 30 | > 30 Example 6 A solution of the compound shown in Table XII in 1N aqueous sodium hydroxide was added to about 100 ml of vinegar containing no preservatives, and the vinegar sample was infected with a platinum loop full of putrefactive bacterial fluid containing active Saprogenus bacteria and infected for 30 days kept at 3000. The occurrence of cloudiness and the decrease in acidity caused by acetic acid bacteria and yeasts were investigated. The results are given in Table XII. In the table, the acid content is given in the form of the amount (ml) of 0.1 N aqueous sodium hydroxide which is used to neutralize 10 g of the sample. The acidity of the vinegar at the time of adding the test compound was 4.21. The symbols "-" to "+++" mean the absence of turbidity and the degree of intensity of the turbidity.

Table XII Granted Turbidity acidity lot Preservation (γ / ml) fabric 10 days 20 days 10 days 20 days Settlement agreement search, nothing ++ +++ 3.44 3.02 Butyl para- 50 - + to ++ 4.20 3.70 hydroxybenzoate "140 - # to + 4.18 3.85 Connection 25 30 - # to + 4.19 4.01 Connection 26 30 - - 4.18 4.17 Connection 27 30 - - 4.20 4.19 Connection B 30 - # to + 4.23 4.10 Connection 31 30 - # 4.19 4.12 Connection 32 30 - # 4.22 4.11 Connection 36 30 - # 4.19 4.08 Connection 37 30 - @ to # 4.18 4.16 Similar studies were carried out with other liquid condiments such as sauces and stock liquids, and it was confirmed that 2,4-dihydroxyphenylalkyl ketones containing a butyl or pentyl group as the alkyl group R in the formula II have a better effect in preserving against putrefaction and decomposition at concentrations of 30 γ / ml, compare with butyl hydroxybenzoate at a concentration of 100 to 200 γ / ml.

Example 7 A bottle of carbonated beverage that is free of preservatives and was kept at 0 ° C was uncorked and a Solution of the test compounds given in Table XIII in 1N aqueous nytrium hydroxide anode to the open carbonated drink (approx. @ @ ml) not given. That drink was infected with 1 ml of a liquid, the active one Yeast contained (the number of yeast was about 105 per g) and then the bottle closed with a cork. The bottle was stored at 30 ° C for 21 days and the occurrence of haze was examined. The results are shown in Table XIII specified. The symbols "-" to "+++" mean the absence of haze and the Degree of intensity of the turbidity.

Table XIII Granted white haze Preservation amount substance (γ / ml) 7 days 14 days 21 days Settlement agreement search, nothing + 4+ +4+ admitted ........ | ............... | ............... | ........ .... | ............ Benzoic acid 600 - | #to + to Dehydroacetic acid @ 50 | - | # to + | + to ++ Butyl-para-hydroxy- 70 f ++ benzoate ................... | ............... | ............ |. ........... | ............ Para-hydroxyphenyl 30. + butyl ketone ................... | ............... | ............ |. ........... | ............ Connection 26 30 - - | # Connection 27 30 w - t From the results given in Table XIII it can be seen that the compounds used in the present invention are significantly more effective in inhibiting yeast growth and preventing the occurrence of cloudiness in the carbonated beverage as compared to known preservatives such as Benzoic acid, dehydracetic acid and p-hydroxybenzoic acid esters.

Similar experiments have been carried out with beverages that are none Contained carbonic acid, it was confirmed that the according to the invention Compounds provide excellent preservation results.

Example 8 A platinum loop full of putrefactive bacterial fluid (the active Yeast molds, acid-resistant lactic acid bacteria and other bacteria contained) was added to 50 ml of fruit juice, which was obtained by squeezing an orange (Onshyu quality) and added sugar in an amount up to a sugar content of 10% was. Then a solution of the compound shown in Table XIV in 1 N aqueous Sodium hydroxide was added to the juice and the juice was stored at 30 ° C. That Mold growth and the occurrence of turbidity were examined. the Results are given in Table XIV. The symbols "-" to "+++++" that appear in the Occur in the table indicate the unit of absence of mold growth or turbidity and the degree of intensity of mold growth or turbidity in the juice sample.

table XIV Admitted Preservative cloudiness mold growth material lot 3 days 7 days 10 days 3 days 7 days 10 days (γ / ml) Comparative try + ++ +++ + +++ +++++ no encore Benzoic acid 500 - # to + ++ - -to # + Butyi-para- hydroxy- 30 - - to i - | - | - ben zoat ............... | ........ | ........ | ........ | ....... . | ........ | ........ | ........ Connect 2 30 - | - | # | - | - | - Connection 27 30 - - # - - -to Connection 37 150 - - # - - -to From the results given in Table XIV, it can be seen that the compounds of the present invention are very effective in inhibiting the growth of mold and preventing the occurrence of cloudiness in the break juice compared to benzoic acid.

Example 9 An alcoholic solution of one given in Table XV Compound was added to rice wine peptone medium. The content of the compound in the alcoholic solution was less than 1.

Water was then added to the medium to adjust the alcohol concentration set to 13 / o. Each of the following four bacteria are often found in trials used as standard hiochc bacteria were separated in an amount of 105 cells per ml added to the medium. The medium was stored at 30 ° C and after culturing for 20 days, it became the minimum growth inhibiting concentration (γ / ml) determined Similar experiments were used for comparison carried out by salicylic acid and lysozyme. The results obtained are in the Table XV given.

HiochS bacteria used Lactobacillus homohiochi (H 42) Lactobacillus heterohiochi (H 1) Lactobacillus fermentum (H 34) Lactobacillus acidophilus (H 7) Table XV Conservation - Minimum Growth Inhibition Concentration (γ / ml) material Lactobacillus Lactobacillus Lactobacillus Lactobacillus homohiochi heterochiochi fermentum acidophilus Salic, ylic acid | 400 200 200 400 Lysozyme 20 10 <1> 100 Connection 26 100 75 100 100 Connection 27 50 50 50 50 Connection 28 25 10 25 25 Connection 29 10 10 10 10 Connection 31 100 100 100 100 Connection 32 50 50 50 50 Connection 33 25 10 25 25 Connection 34 10 10 10 '10 Connection 38 100 100 50 50 Example 10 A rice wine which contained no preservatives and had an alcohol concentration of 16.0% was infected with 2 × 10 5 cells per ml of hiochic lactobacilli which had been obtained in a brewery in Nada, Probe, Japan. A solution of a compound indicated in Table XVI in alcohol, with the concentration indicated in Table XVI, was added to the infected rice wine. By adding water, the increase in the alcohol content in the sample, which was caused by the addition of the alcoholic solution of the preservative, was adjusted to the original concentration and then the sample was filled into blue glass bottles and the bottle was closed with a cork. For comparison, similar experiments were carried out using lysozyme at 40 γ / ml and using salicylic acid.

The bottle was then stored at 30 ° C and the appearance of turbidity, caused by hiochic bacteria was investigated. The results are in the table XVI specified. In Table XVI, the symbol "+" means that putrefaction by hiochic bacteria occurred and the symbol "-" means that there is no putrefaction caused by high bacteria was observed. In the table, "white haze" means that white haze causes by precipitation of crystals, occurred when the sample was kept at 0 ° C for 48 hours became. From the results shown in Table XVI it can be seen that the present invention Compounds have excellent activity at low concentrations, to prevent the growth of hiochic bacteria and make them much more effective are considered salicylic acid when used at a concentration of 500 ppm will. This concentration is twice as high as the permitted upper limit of the Salicylic acid concentration.

Table XVI Trains- Storage time Storage at Preserved added material amount 0 ° C during 7 days 14 days 21 days 70 days (/ ml) 48 hours Settlement agreement search, nothing + + + + admitted Salicylic Acid 500 - - - + "250 - + + + Lysozyme 40th to | + + + + Compound 28 50 - - - - white turbidity tr 25 - - - - "10 - - - + Compound 34 25 - - - - white haze "10 - - - - "5 - - - + Samples from rice wine which contained the compounds according to the invention in concentrations which were above the effective concentrations, ie samples which contained 50 γ / ml of compound 28 or 25 γ / ml of compound 34, tasted before infection with hiochic bacteria investigated, it was found that the addition of these compounds did not affect the taste or smell of the rice wine in any way. Samples in which the above compounds were incorporated above the effective concentration showed no visible changes, such as a color change, even after being stored for 70 days.

Example 11 A commercially available rice wine that is free from preservatives was was mixed with 10 koji, specially prepared, and then carried out at 3000 during 4 hours and filtered.

Alcohol was added to the filtrate to increase the alcohol concentration set to 200. Active carbon was added to the medium in an amount of 200 ppm was added, then the medium was filtered and in one for 20 minutes Water bath held at 56 ° C with the medium in a reaction vessel, the one Contained reflux condenser. then the medium was increased with 1.2 x 10 2 cells per ml hiochic bacteria infected or infected that are collected in a brewery in Nada, Kobe, Japan and alcoholic solutions of the compounds were added to the infected sample 28 or 34 given. The final concentration of the added compound was reduced to 25% ppm or 10 ppm. For comparison purposes, salicylic acid was used at concentrations of 250 ppm and 500 ppm were added. The increased alcohol content caused by the addition the solution of the preservatives was caused by adding water reduced to 20 0. Each sample was transferred to a 200 ml beaker and with sealed with a polyethylene film. In this condition, the samples were at 3000 and then the condition of the sample was examined. The results are given in Table XVII.

Table XVII Granted Storage time Preservation amount substance (γ / ml) 7 days 14 days 21 days 70 days Comparative + + + + search, nothing added ......... | .............. | .......... | .......... | .. ........ | .......... Salicylic Acid 250 - | + + + + 11 500 - - - - ................... | .............. | .......... | .... ...... | .......... | .......... Connection 28 25 - - - - Connection 34 | 10 | - | - | - | - In Table XVII, the symbol "-" means that no hiochi rot was observed and the symbol "+" means that hiochi rot was observed.

If the above experiment was carried out with hiochi putrefactive bacteria in a barrel, so the sample showed the salicylic acid with a concentration of 250 γ / ml healed, hiochi rot.

after 70 days of storage, each sample of rice wine was tit 400 ppm active carbon mixed and filtered. The filtrate was then pasteurized with Water diluted so that the alcohol concentration was 16%. The sample was then Carefully overflowed into a pasteurized bottle and the bottle was filled with a Cork closed and stored at 30 ° C.

The results are given in Table XVIII, where the symbol "@" means that no hiochi rot has been observed and the symbol "+" means that hiochi rot was observed.

Table XVIII Allowed storage time Preservation Amount (/ ml) fabric 7 days 14 days 21 days 70 days Salicylic acid 500 Connection 28 25 Connection 34 10 The amount of preservative remaining in the samples was determined by ultraviolet absorption analysis. The results are given in Table XIX. In the samples that had been treated with active carbon, the alcohol content, which had been lowered by evaporation of water, was readjusted, Table XIX Conservation - Remaining Ronservii "Dirty Rat - rungsstoll! nia ('e) 0. . erade to Zu- Iliachdom m - Ln 70 h CI YCI rh ~ Ir? - ^ -celaeis- - hn 117 mi ~ t Salicylic acid had 100 too active carbon atoms (Sso6 / iL) Connection 2E 100 100 C l (2sK Connection 34 100 100 <l {so r / wl Example 12 20 ltr. Mirin (sweet rice wine), which contained 17% alcohol, 0.01% acids (identified as lactic acid) and 41.2% sugar, were tested in four samples with 5 ltr. divided. Compounds 28 and 34 were added to two samples in concentrations of 25 g / ml and 10 / ml. For comparison purposes, salicylic acid was added to another sample at a concentration of 250 µg / ml. The compounds were added in the form of alcoholic solutions. The increase in alcohol content was regulated by adding water. Each sample was dispensed into 25 200 ml bottles and a platinum loop of fully active Lactobacillus acidophilus was added to each bottle, then the bottle was closed with a cork. Each bottle was stored at 30 ° C and the condition of the sample was examined.

The samples that incorporated compounds 28 and 34 of the invention did not show any changes after 3 months. But all samples that contain salicylic acid contained were rotten within 30 days.

Example 13 Experiments were carried out in a (lever piece) rice wine peptone culture medium carried out for 20 days in the same way as in Example 9, but the dihydroxybenzoic acid esters given in Table XX were used. The results (minimum growth inhibition concentration - γ / ml) are given in Table XX.

Table XX Preservation Minimum Growth Inhibition Concentration (γ / ml) material Lactobacillus Lactobacillus Lactobacillus Lactobacillus homohiochi heterohiochi fermentum acidiphilus Salicylic acid 400 200 200 400 Lysozyme 20 10 <1> 100 Link 15 200 150 200 200 16 16 100 75 100 100 "17 | 30 | 20 | 30 | 30 18 10 3.0 10 10 "9 300 250 250 250 10 10 150 100 100 150 11 | 25 | 25 | 25 | 25th 12 10 10 10 10 "21 400 200 200 400 "22 300 100 300 100 "23 200 50 50 200 "24 50 30 30 50 "3 60 45 45 50 "- 4 20 8 15 15 18 "5 8 5 <5 <5 "6 <5 <5 <5 <5 Example 14 Rice wine which was free of preservatives and had an alcohol content of 16,54 was infected with 2 × 10 5 cells per ml hiochi bacteria and then transferred to a 300 ml blue glass bottle. The compound indicated in Table EI was added to the bottle in the amounts also indicated in the table.

For comparison purposes, salicylic acid was also tested.

The bottles were closed with corks and stored at 30 ° C. The occurrence of turbidity caused by hiochi bacteria was checked. the Results are given in Table XXI, where the symbol "-" means none Haze was observed and the symbol "+" means that haze was observed. Each preservative was added in the form of an alcoholic solution and the increase in alcohol content was due to the addition of the preservative adjusted to the original alcohol content of 16% by adding water.

Table XXI Storage time Storage at Preservation level 0 ° C during 7 days 14 days 21 days 70 days Amount 48 hours (/ ml) Comparative + + + + search, nothing admitted 500 - - + + Salicylic acid "250 - + + + Connection 17 50 - - - - white haze "30 - - - - "20 - - + + Connection 11 50 - - - - white haze "25 - - - - "10 - - + + Connection 4 20 - - - - "10 - - - - "5 - - - + When samples in which the above compounds were incorporated at concentrations higher than the effective concentrations were tasted, it was found that these compounds had no bad influence on the taste or smell of the rice wine. No color change was observed in any of the samples which contained the compounds according to the invention, even after storage for 70 days.

Example 15 20 ltr. Mirin (sweet rice wine) ,. the 17.0% alcohol, 0.01% acids (determined as lactic acid) and 41.2% sugars was divided into four parts to each 5 ltr. divided. Compounds 17, 11 and 5 were in alcoholic Solution in concentrations of 30 Wml, 25 </ ml and 5 5 γ / ml to the three Added to parts.

The remaining one part was used as a comparative sample with no preservative examined. Each compound was added in the form of an ethanol solution and the increase in alcohol was due to the addition of the preservative Equalize by adding water to the same alcohol content of 17%. Each portion was filled into 25 200 ml bottles and each bottle was filled with one Platinous fully active Lactobacillus acidophilus infected. Then every bottle stored at 30 ° C and the condition of the sample was examined. The samples containing the Compounds according to the invention contained arene after 3 months after unchanged, whereas all comparison samples were moldy within 10 to 20 days.

Example 16 An ethanol solution of the preservative given in Table XXII was added to red wine that did not contain a preservative and then became the wine each with a platinum loop full of film-forming yeast and acetic acid bacteria infected and stored at 3000 for 70 days. The change in the quality of the Wine was examined. No decomposition was found in any sample that was recognizable by the taste or smell after you had the Preservatives had been added. Furthermore, after 70 days of storage in none Sample observed a color change. The results of the conservation studies are given in Table XXII, where the symbol "+" means that white haze, caused by the growth of microorganisms has been observed.

Table XXII Granted Preservation storage time 7 days 14 days 21 days 70 days Salycylic acid 250 - - + + SO2 400 - - + + connection 28 25 - - - - Connection 17 | 30 | - | - | - | - Connection 6 5 - | - | - | - Example 17 An ethanol solution of the preservative shown in Table XXIII was added to white wine containing no preservative, and then the wine was infected with active film-forming yeast and acetic acid bacteria (the contamination level of bacteria being 2 x 10² cells per ml) and then the samples were taken stored in bottles at approx. 30 ° C.

The difference in quality was checked. In no sample could Any pollution can be detected by means of odor after watching the preservatives had been added, in no sample was there a color change found after the sample was stored for 70 days. The results of the conservation studies are given in Table XXIII, where the symbol "+" means that by growth white turbidity occurs from microorganisms.

Table XXIII Granted Storage time Preservation amount substance (γ / ml) 7 days 14 days 21 days 70 days Salicylic Acid 250 - - + + SO2 400 - - + + Connection 28 25 - - - - Connection 17 30 - - - - Connection 6 5 - - - - an additive equalization + + + +

Claims (5)

Patent claims 1. A process for the preservation of liquid foodstuffs, characterized in that a compound of the formula is selected for the liquid food which is selected from the group consisting of liquid condiments, non-alcoholic beverages, fruit wines and sake wherein n is 2, R is an alkyl group having 3 to 8 carbon atoms and M is a hydrogen atom, an alkali metal or 1/2 nol of an alkaline earth metal, added in an amount of 5 to 300 ppm. 2. The method according to claim 1, characterized in that the connection is added in an amount of 5 to 60 ppm. 3. The method according to claim 1, characterized in that the connection is added in the form of a solution in an edible safe solvent. 4. The method according to claim 1, characterized in that d the liquid Food is soybean oil and that R in the formula is an alkyl group of 3 to 5 denotes alkyl groups. 5. The method according to claim 1, characterized in that the liquid food is rice wine and that the compound which is added is expressed by the formula: where M and n have the meaning given above, R is an A1-alkyl group having 5 to 8 carbon atoms, and two MO groups are bonded to the benzene nucleus in 2,4- or 3,4-positions to the group COOR1 or COR1 .