FI100376B - New preservative composition - Google Patents

Description

100376

New preservative composition

The invention relates to e.g. compositions for preserving grass material and fresh cut, cereals, etc. 5 organic material and for controlling harmful microorganisms, which contain an ester of unsubstituted or substituted benzoic acid.

10 The AlV method is commonly used in the preservation of fresh fodder, in which the pH of the fodder to be preserved is reduced to about 4 or less by the addition of acidic compounds and lactic acid fermentation. Mineral acids, organic acids, in particular other monetary, acetic and propionic acids, and acid salts are used for this purpose.

The use of benzoic acid as an additive to reduce unfavorable fermentation and improve the sugar content of fresh feed and the like in acidic preservatives is known from 20 FI patent publication 63328 (Lampila). The preservatives according to the publication contain 2-60% of benzoic acid or its derivative, calculated as benzoic acid.

In practice, it has been found that the benzoic acid content of the preservative of the AIV method should be at least 5% by weight; ; no-% before it has sufficient inhibitory effect on harmful microbes. However, at such high concentrations, benzoic acid is difficult to use in liquid preservatives. As sparingly soluble, it causes severe crystallization problems in storage containers, resulting in clogging of the • nozzles of the dosing syringes. FI patent application 920887 • · · · proposes stabilizing and compositions containing 5-30% by weight of benzoic acid, e.g. formic acid and an aliphatic carboxylic acid having at least 2 carbon atoms.

According to PCT / FI93 / 00068, stable compositions containing 5-25% by weight of benzoic acid or p-hydroxybenzoic acid or a salt or ester thereof are known, in which, in addition to possible other components, there are ants, vinegar and / or propionic acid or their esters.

5 FI patent application 920886 discloses preservatives containing benzoic acid or its salts and ethyl formate as well as possibly C 1 -C 3 carboxylic acids.

GB Patent 2,193,078 discloses compositions for the preservation of moist grass 10 comprising acetic, propionic or preferably sorbic acid and magnesium oxide, zinc oxide and soluble Cu (II) preferably in a ratio of 100: 10 to 20: 1.

15 In J.Am.Soc.Brew.Chem. 37. (1979): 3, pp. 140-144 discloses acetic acid / propionic acid, isobutyric acid / propionic acid, formaldehyde / propionic acid, formaldehyde / other acid / propionic acid / formaldehyde / acetic acid / acetic acid / propionic acid, combinations 20 for the preservation of spent brewer's yeast.

The possibility of using formic acid esters of 1,2-propanediol in the preservation of animal feed and in the treatment of drinking water is known from DE patent 3,540,771. The esters have a particular effect on coliform bacteria.

According to JP 57 018 601, the use of carboxylic acids and their derivatives (e.g. chlorides, esters, anhydrides, amides and nitriles) and salts is known. 10'3 - 10 "1 M solutions Tor as a pesticide against various plant diseases • ·:::.

U.S. Pat. No. 3,745,027 discloses the preservation of foods such as meat, fruits and vegetables against mold and bacterial spores by boiling them in a solution containing 25 to 90% by weight of polyalcohols. and 0.5-1% by weight of an antifungal agent. As fungicides li 3 100376 are mentioned sorbic acid, propionic acid and benzoic acid and their salts and esters.

Propionic acid, sorbic acid, benzoic acid, methyl benzoate, ethyl benzoate and the edible alkali and alkaline earth salts of said acids are also known from US-3,404,987 for the protection of foodstuffs against microorganisms.

The efficacy of ethyl and methyl benzoate in inhibiting the growth of Aspergillus flavus and A. parasiticus and in reducing the amount of aflatoxin produced by these organisms is known from Applied and Environmental Microbiology, Aug.

1980, pp. 352-357.

15

From Food Microbiology, 5. (1988): 3, pp. 135-139, 1% acetic acid, 1% lactic acid, malic acid, tartaric acid or citric acid, 0.05% sorbic acid, 0.05% benzoic acid and 3.5% salt are known The composition comprising a salivella blockley, Escherichia coli and Staphylococcus aureus in a salad buffered to pH 4.8 is bactericidal and is bacteriostatic Streptococcus. faecalis.

25 From the International Journal of Food Microbiology 22.

• · (1994): 2-3, pp. 127-140, the combination of potassium sorbate and sodium «· · •« * · .. * umbenzoate is known to slow or inhibit the growth of Salmo- • «nella in milk or cheese when its pH is regulated with · propionic acid.

30: According to Poultry International, July 1994, pp. 40-42, • · · ·: 'j *; In the control of Salmonella in poultry feed, mixtures of • organic, *, organic acids, in particular propionic and formic acid, or mixtures of organic acids and their ammonium salts or salts of organic acids are used. The products are either solutions or solids.

According to EP-A-275 958, solid feed containing up to 20% by weight of moisture for chickens, cows, pigs, etc. can be preserved without drying by means of a preservative containing sorbic acid or sorbates together with a physiologically harmless organic or inorganic acid or its salt. with.

According to U.S. Pat. No. 5,234,703, carcasses of dead animals, such as chickens, are disinfected by treatment with solutions containing medium-chain fatty acids, e.g., CI0, in addition to acetic, propionic, citric and hydrochloric acids. The mixture is reported to affect e.g. Salmonella typhirium and Escherichia coli.

15 According to JAOCS 61 (1984): 2, pp. 397-403, lauryl monoglyceride, or monolaurin, is an effective and food-grade antimicrobial agent. A combination of monolaurin, methyl, propyl paraben and EDTA is known for preserving a protein-containing cosmetic emulsion.

20

A fresh feed preservative impregnated in natural zeolite or synthetic zeolite is known from SU patent 1,461,398.

It contains 10 to 50% by weight of organic acids, such as formic, acetic and propionic acid, and 10 to 60% by weight of zeolite, the remainder being salts of inorganic acids or aqueous; salts of soluble organic acids such as Na-benzoate, salicylate or acetyl salicylate.

* · «« · • «· ♦ · · · ί, · * · According to PCT publication 91/11192, an acid-containing solid product for preserving fresh feed or as an additive in animal feed is known in which the acid is absorbed into the diatomaceous earth, · · Preferably granular clay-containing diatomaceous earth, "moler".

There is still room for improvement in the above feed preservatives, especially when storing pre-dried fresh fodder, leaving the grass cut on the ground to pre-dry before baling or silage. In this case, molds, bacteria, yeasts and their spores are easily introduced into the feed, which can easily spoil the feed lot.

Although the compositions containing about 5-25% by weight of the benzoic acid component disclosed in FI-920887 and PCT / FI93 / 00068 generally give a good preservation result of pre-dried fresh feed, they still have shortcomings. If expensive stabilizers are not used sufficiently, some kilos of deposits may still be formed in the preservative during long-term cold storage. It would also be desirable to reduce the amount of the benzoic acid component, in part because of its high cost, and in part because it contaminates work machines at these concentrations when the material exposed to them forms a difficult to wash, light benzoic acid-containing dirt layer.

15

Another shortcoming of existing preservatives is that, even after the feed bale or silo has been opened, the fodder that has remained good in it can spoil quickly when the sugars it contains start to ferment. It is desirable to preserve the feed in such a way that 20 sugars remain in it, but post-fermentation is still negligible.

The grain grain is preserved when it is not dried, either as crushed grain or whole grain. In the former case, the moisture content of the grain is about 30-35% and the preservation is generally carried out with the same preservatives according to the VAT method as the product; rerehunkin. In whole grain preservation, the usual * · · preservatives for fresh fodder are not effective enough, but • ·:, · · mm are used. propionic acid, which is expensive. It would therefore be desirable * | t ::: also finds more preservative compositions for preserving cereals.

* · ·

It is further desirable that the same preservative compositions could be used for other purposes, e.g.

For the control of Salmonella and other microbes in agriculture and 35 feed production.

It would still be desirable to be able to achieve a preservation result according to the AlV method without having to use the same amount of 6,100376 or strong acids, but could be content with a higher initial pH.

It is also desirable to have e.g. 5 reduce the corrosivity of formic acid-containing preservatives to the skin, clothing and machinery and alleviate their pungent odor.

It has now surprisingly been found that the above-mentioned drawbacks can be considerably reduced by using as a preservative a preservative composition containing esters of unsubstituted or substituted benzoic acid comprising an ester component 1) which is an ester of unsubstituted or substituted benzoic acid C or -C9 of such esters mixture, and an ester component 2) synergistically with said ester component 1), which is an ester of a non-aromatic C 1 -C 20 carboxylic acid with a C 1 -C 9 alcohol, the relative proportions by weight of the ester component 1) and the ester component 2) being 10: 1 to 1: 5. Although the above-mentioned references disclose the use of these component-20 pathways per se, it has not been realized that they have a surprising, synergistic interaction that was found by reliable comparative experiments (see examples in this application).

The acid of the ester component 1) is thus an unsubstituted or substituted benzoic acid.

• · • · ·

Particularly preferred are benzoic acid and hydroxybenzoic acid. The C1-C9 alcohols of the ester component 1) or 2) are e.g.

primary and secondary, saturated or unsaturated alcohols, optionally containing more than one hydroxyl group, with a straight or branched chain.

Saturated alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, butanols, in particular n-butanol and isobutanol, pentanols, hexanols, heptanols, octanols, V 35 in particular n-octanol and 2-ethylhexanol, and nonanols.

:: Alcohols containing more than one hydroxyl group are e.g.

glycols such as 1,2-propanediol, and triols such as glycerol. Preferred alcohols are C 1 -C 4 alcohols such as ethanol 7 100376 nol, propanol and butanol. Of the aromatic alcohols, e.g. benzyl alcohol.

Of the esters of the ester component 1), methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-amyl, isoamyl, n-octyl or 2-p-hydroxybenzoic acid are preferred. -etyyliheksyyliesterit. Even more preferred are methyl, ethyl, propyl, isopropyl, butyl and isobutyl benzoates, with ethyl 10, propyl and isopropyl benzoate being particularly preferred.

The non-aromatic C 1 -C 20 carboxylic acids of the ester component 2) are saturated or unsaturated mono-, di- or tricarboxylic acids optionally having hydroxyl groups.

Such saturated monocarboxylic acids include e.g. non-monetary, acetic, propionic, butyric, butyric, valeric, isovaleric, caproic, caprylic, 2-ethylhexanoic, capric, lauric and myristic acids and dicarboxylic acids are oxalic, malonic, succinic, glutaric, adipic, pimelic and suberic acids with their alkyl and hydroxy derivatives. Hydroxycarboxylic acids include e.g. glycolic and lactic acids, sugar acids, tartaric, malic and citric acids. Unsaturated acids include e.g. fumaric, maleic, sorbic, oleic, linoleic, linolenic and castoric acids.

25 The esters of the ester component «· * ♦ ·· '2) which are advantageous from the point of view of preservative action are those which, in the field of application, hydroly- • · * · M .. ....

When taken together, they form preservative acids such as formic, acetic, propionic, lactic, octanoic, 2-ethylhexyl or sorbic acid, or preservative alcohols such as octyl alcohol.

• · · 9 • »* I I« * I <'. Particularly preferred esters of the ester component 2) are the other propyl, isopropyl, butyl and isobutyl esters of formic acid, propionic acid and lactic acid, the most preferred being propyl propionate.

8 100376

The ester component 2) alone may have poor preservative performance. Therefore, synergies are expected e.g. based on the fact that this ester, depending on the application, improves the adhesion, migration and absorption of the ester component 1) on the surfaces of the preservative material and the bacterium, yeast or the like to be controlled. No such interaction has been observed in the past.

The synergy of the preservative according to the invention is realized whenever both the ester component 1), i.e. the ester of unsubstituted or substituted benzoic acid with C 1 -C 9 alcohols, and the ester component 2), i.e. the ester C of the non-aromatic C 1 -C 10 carboxylic acid, are present. With C9 alcohol. According to one embodiment, the relative weight proportions of the ester component 1) and the ester component 2 2) in the composition are between n.

4: 1-1: 2, preferably between about 2: 1-1: 1.5.

It is, of course, understood that the preservative composition of the invention may also contain other preservative components.

20 Such are e.g. the preservatives listed in the previous literature review, so the publications mentioned in the review and their English equivalents are incorporated herein by reference.

25 In particular, for the preservation according to the AIV method. The application of the preservative mixture according to the invention also contains an acid component 3). Its purpose is to lower the pH of the treatment object to, for example, about 4 or below. The quality of the acid is not critical to the invention. The component "30" may be an organic or inorganic acid or a polyacid or an acid-forming compound in solution. In one embodiment, the acid component comprises an organic C1-C20 acid and most preferably a C1-C20 acid. organic acids are, in particular, formic acid, acetic acid, propionic acid and lactic acid, preferably formic acid, but other carboxylic or polycarboxylic acids, such as citric acid, may also be used Inorganic acids, hydrochloric acid, sulfuric acid or phosphoric acid They may also be partially neutralized. Acid-forming compounds include acid-reactive ep inorganic or organic salts or acid anhydrides.

The acid component can also be produced chemically during the storage according to the invention, for example by means of lactic acid fermentation controlled by enzymes and / or bacteria. The acid component is about 10-100, preferably about 30-100 and even more preferably 60-100% by weight of formic, acetic, lactic and / or propionic acid, optionally neutralized, most preferably formic acid. According to a preferred embodiment, the preservative mixture according to the invention contains about 70-90% by weight of formic acid, about 0-10% by weight of orthophosphoric acid and about 1.5-3% by weight of the ester mixture according to the invention and hydrogen.

The preservative composition according to the invention may contain very varying total amounts of said ester components 1) and 2). According to one embodiment, the minimum content of the ester component 1) in the preservative composition is about 0.25% by weight, preferably about 0.5% by weight, most preferably about 1% by weight. Nevertheless, the maximum content of the ester component 1) is about 10% by weight, preferably about 5% by weight and most preferably n.

2.5% by weight. The weight% is expressed as benzoic acid 25 and the proportions are preferred in the presence of the acid component 3).

♦ ♦ »· t · • · * *« ** ·; ' In addition to the above ingredients, the mixture may contain other M: preservative enhancing compounds, e.g. C4-C14 carboxyl-.

* f * 30 acids, e.g. free benzoic acid, isobutyric acid or octanoic acid, or similar alcohols; Cg-C16 carboxylic acid monoglycerides or other bactericidal or static surfactants; dicarboxylic acids and, for example, oxalic, malonic, succinic, adipic, pimelic, capic, fumaric or maleic acids; polycarboxylic acids such as polyacrylic acid or copolymeric acids formed between acrylic acid and unsaturated compounds polymerizable therewith; hydroxycarboxylic, dicarboxylic or polycarboxylic acids, e.g. sorbic, ascorbic, cinnamic, salicylic, tartaric or malic acid; complexing agents, e.g. EDTA, DTPA; or derivatives of all said acids such as salts or esters. Furthermore, depending on its application, the mixture may contain e.g. metal salts which act as preservatives, e.g. salts of magnesium, zinc and copper, animal nutrients or compounds which adjust the salinity of the mixture or buffer it, e.g. ammonium phosphate 10 or potassium sulphate; imidiazolindylurea, phenolic compounds and sulfonic acids, e.g. lignosulfonates, or aldehydes, e.g. formaldehyde. Furthermore, components acting as antioxidants, e.g. butylated hydroxyanisole or toluene or gallusha-15 esters, can be added to the mixture.

The preservative compositions according to the invention are prepared simply by mixing the ester components 1) and 2) and any other components, such as the acid component, in the center.

The preservative mixture is generally in the form of a solution at conventional temperatures. It can also be solidified by impregnation with a large surface area clay mineral, silica or other absorbent.

«9 I t«

In addition to the preservation of grass fodder and fresh cut or cereals, the composition according to the invention can also be used for the treatment and preservation of other living materials, such as beet by-products, broth feed, mash, grits, food industry by-products. Uotteet \ \; by-products, feed or feed additives used as animal feed, as well as organic products for human consumption, and can also be used to improve the hygiene of livestock shelters and other structures, plants and equipment used to control harmful micro-organisms. 11 100376 can be used not only as food but also as a raw material in industrial processes, For example, cereals preserved with the composition according to the invention lead to an improved sugar content, whereby its use starts with as a raw material for the production of ool, mer-5 cuts the increased alcohol yield. At the same time, grain drying, which is an energy-consuming process, is avoided.

When the compositions are used in products intended for human or animal consumption, their components must be selected from among the compounds acceptable as re-10 or food additives.

The ester mixtures according to the invention are neither corrosive nor pungent. Acid solutions 15 containing them are also better in these respects than those without them.

The invention also relates to a process for preparing a composition for preserving grass fodder, fresh cut, cereals or other such material. In the process, the ester component 20) which is an ester of an unsubstituted or substituted benzoic acid with a C 1 -C 9 alcohol or a mixture of such esters, and a second ester component 2) synergistically active with said ester component 1), which is a non-aromatic CVCl 3 carboxylic acid ester with a C 1 -C 9 alcohol, is added in a weight ratio of 1): 2) = 10: 1-1: 5 acid. . to a preservative containing component 3) on a farm or other place of use for a relatively short period before use or during use, so that a synergistically active composition of the type mentioned above is formed into an active mixture.

: '30 * ·. · · Examples

The invention will now be illustrated by the following examples, in which: Figure 1 shows the amounts of acetic acid and lactic acid in the feed; : when the preservative contains different amounts of ethyl benzoate, propyl formate or a mixture thereof (Example 5), 12 100376 Figure 2 shows the after-fermentation of feed samples unloaded from the tank in degrees (Example 6), 5 Figure 3 shows how the effectiveness of acetic acid in controlling salmonella improves ethyl benzoatex and a combination of propyl formate.

Example 1 (Solution Culture / Yeast) Laboratory experiments were performed on the effect of esters of benzoic acid, formic acid and propionic acid on yeast growth. YPE broth medium containing yeast extract was used as the medium. 2% glucose was added to the medium. Cultures were performed in Klett tubes. Yeast growth was monitored by measuring solution turbidity due to microbial growth

With Klett analyzer after 3 days of culture.

The result is the absorbance reading. The better the inhibitory effect, the brighter the medium and the lower the absorbance reading.

20 Preservative amount: 0% 0.1% 0.5% 1.0% EB, Ethyl benzoate 280 40 20 20 PB, Propyl benzoate 260 90 25 25 EF, Ethyl formate 280 280 250 240 PF, Propyl formate 220 220 160 110 25 EP, Ethyl propionate 280 280 180 180. . PP, Propyl propionate 260 260 130 140 EB + PB 1: 1 270 100 25 25 EB + EF 1: 1 270 190 15 15 EB + PF 1: 1 270 40 15 15 3 0 EB + EP 1: 1 270 90 15 15 EB + PP 1: 1 270 45 15 15 PB + PF 1: 1 270 15 15 15: PB + EP 1: 1 270 10 10 10 PB + PP 1: 1 270 10 10 10 35. . Of the individual preservatives tested, the ethyl and propyl esters of benzoic acid acted as the best-tested preservatives, giving a clear effect even at the 0.1% dosage level. The combination of these two averages did not provide additional power. The ethyl and propyl esters of muurc and propionic acid alone did not provide adequate yeast control under the experimental conditions, even at a dose of 1.0%. Surprising synergies are shown by the fact that

II

13 100376 by including a low-potency ester among the benzoates per se, the resulting combination performed even better than the benzoate alone, although in these combinations the benzoate content is half that.

5

Example 2 (solution culture / colony)

Laboratory experiments were performed on the effect of benzoic acid, formic acid and propionic acid esters on the growth of coliform bacteria. Luria-Bertani vessel 10, adjusted to pH 7.5, was used for testing. A colony containing E. coli was added at 1%. Otherwise, the procedure was as in Example 1 (solution culture / yeast). The following results were obtained: Preservative amount: 0% 0.1% 0.5% 1.0% 15 EB, Ethyl benzoate 105 55 25 30 PB, Propyl benzoate 90 60 80 80 EF, Ethyl formate 105 105 105 100 PF, Propyl formate 105 105 90 80 EP, Ethyl propionate 105 105 85 80 20 PP, Propyl propionate 90 90 70 65 EB + PB 1: 1 100 60 55 70 EB + EF 1: 1 100 60 15 15 EB + PF 1: 1 105 65 10 10 EB + EP 1: 1 100 65 15 15 25 EB + PP 1: 1 100 25 10 10

Of the individual preservatives, ethyl benzoate was the most effective. When ineffective or ineffective esters of formic acid and propionic acid were mixed with it, pa-. ·. rani result compared to ethyl benzoate alone. The best result was obtained with a mixture of ethyl benzoate and propyl formate.

«» · 1 35 Example 3 {solution culture / propionic and lactic acid / yeast)

The experiments according to Example 1 were carried out using 80% by weight of propionic acid or 80% by weight of lactic acid as preservatives, containing a total of 5% by weight of ethyl benzoate (EB) and / or propyl formate (PF). Dosage of the preservative, "40 in solution was 0.5% by weight. The following results were obtained: 14 100376

Acid Ester Yeasts (Klett reading)

Time: 1 day 2 days 3 days

Propionic acid 3A no esters 30 - 140 5 3B EB 30 - 60 3C EB + PF 1: 1 10 - 15 3D PF 10 - 95

Lactic acid 10 3E no esters 85 230 300 1) 3F EB 50 70 90 2 3 4) 3G EB + PF 1: 1 55 55 55 1) 3H PF 90 210 270 1) 15 Note! *) Reading after lactic acid addition (0 days) = 55 **) Reading after lactic acid addition (0 days) = 40 In the sample containing propionic acid and a synergistic ester mixture according to the invention, 3C yeast growth is hardly detectable after another 3 days, but in contrast only another in the ester-containing samples 3B and 3D and especially in the non-ester-containing sample 3A, the increase is remarkably -25 vaa.

Sample 3F containing ethyl benzoate has given a moderate result at a dosage level of 0.5% by weight, although growth has clearly started at 2 days. In the sample 3G containing 30 lactic acid and a synergistic ester mixture according to the invention, in which there is half as much ethyl benzoate as in the sample 3F, the yeast has not grown so much in 3 days that the turbidity reading has changed from the initial situation.

• · * ··. ' At 2 days in the non-ester-containing sample 3E and • ·: 35 in the sample containing propyl formate 3H, the increase is already very marked »· · V’.

II

2

Example 4 (solution culture / acetic acid / colifties) 3 • · «· 4

The experiment according to Example 2 was carried out using 80% by weight of acetic acid with esters of ethyl benzoate (EB) and / or propyl formate (PF) as a preservative solution. At 0.5 and 0.2% w / w preservative dosage, no increase was observed in any of the samples. Dosing with 0.1% by weight gave the following results, which show that E. coli growth starts to slow down in 100376 min in the solution containing the synergistic ester mixture 4C:

Acid Ester Yeasts (Klett reading) 5

Acetic acid Time: 1 day 2 days 3 days 4A no esters 65 80 80 4B EB 65 75 75 4C EB + PF 1: 1 30 65 65 10 4D PF 65 80 80

Example 5 (bag test)

Timothy grass was cut and weighed into 1 batches of 1 kg and treated with various formic acid-based preservatives. The samples were sealed in airtight plastic bags. Five parallel bag experiments were performed with each preservative. The dosing of preservatives corresponded to the level of 5 1 / tonne of feed.

20

The following preservative mixtures were tested (amounts of recipes in% by weight):

Ingredient Mixture: 5/1 5/2 5/3 5/4 25 Formic acid 80 78 76 74

Phosphoric acid 2222

Water 18 18 18 18

Esters 0246 30. Feeds were analyzed after 48 days of storage. The dry matter contents of the samples ranged from 15.8 to 17.0% by weight and the pHs ranged from 3.6 to 3.9. Acetic acid is formed during harmful fermentation in feed, while fermentation leading to lactic acid is desirable. The concentrations of these acids are shown in the table below and in Figures IA and IB: »· • ·« «·« • · · · 16 100376 No. 5/2 EB 55.6 7.0 5C 5/2 EB + PF 81.4 5.0 5D 5/2 PF 71.8 11.2 5E 5/3 EB 62.8 7.4 10 5F 5/3 EB + PF 73.8 5.0 5G 5/3 PF 72.4 7.2 5H 5/4 EB 64.2 10.0 51 5/4 EB + PF 56.0 5.6 15 5J 5/4 PF 81.2 12.2

It can be seen from the table and the figures that preservatives containing ethyl benzoate + propyl formate in the ester mixture according to the invention gave a clearly better result than those containing only one of the esters. At low dosage levels, the ester mixture mainly prevents adverse fermentation, only at higher dosage levels does lactic acid fermentation slow down.

25 Example 6 (post-fermentation)

The feed samples according to the previous example were opened and their temperature and room temperature were then monitored for 10 days. The area between the temperature curves, the so-called degree day number, describes the intensity of post-fermentation. The lower the degree-30 day number, the less post-fermentation in the sample has been. The results obtained as the averages of 5 samples are shown in Figure 2. It can be seen that a preservative containing a combination of ethyl benzoate and propyl formate gave a significantly lower residual fermentation than a preservative containing only one of the esters. .

m «

Example 7 (cereal preservation test) ♦ · * M · Barley grains were preserved with various acid-containing preservative solutions. The moisture level of the barley was 43% by weight. The fiber 40 was dispensed by killing on a screw conveyor. Two dosage levels, 1.8 L and 1.44 1/100 kg of grains, were used.

17 100376 Of these, the former corresponds to the recommended dosage of propionic acid for such wet grains, the latter being 20% less. The grains were stored in barrels.

The following preservatives were used in the experiment: 1: 100% by weight of propionic acid 2: 61% by weight of formic acid + 30% by weight of propionic acid + 9% by weight of benzoic acid 3: 70% by weight of formic acid + 20% by weight of propionic acid + 10% by weight % ethyl benzoate + 5% by weight propyl formate.

After 11 weeks, the condition of the barley was checked. The following observations were made, in which nume-15 rot, which describes the presence of mold, refers to the width, length and depth in centimeters of the moldy spot: Preservative 1.8 1/100 kg 1.44 1/100 kg 1 (comparison 1) no mold 5x10x10 20 2 (comparison 2) mold 5x10x10 mold 8x20x15 3 (according to the invention) no mold no mold.

It is found that propionic acid gave good results at the recommended dosage, but the underdosing level was insufficient.

In preservative 2, a large part of the propionic acid has been replaced by cheaper formic acid and attempts have been made to compensate for the loss of storage power with benzoic acid. The result was poor. In the preservative 4 according to the invention, even more propionic acid has been replaced by formic acid and the amount of benzoic acid; , -β0 (calculated as acid) has been reduced to less than half. This combination of ethyl benzoate and propyl formate has still improved the preservation performance even better than that obtained with propionic acid alone.

I * I «· · • · ♦ · 35 Example 9: Salmonella

The Salmonella infantis used in the experiment was originally isolated from chickens and cultured in buffered peptone water.

For the experiment, dilution series were made in peptone water using different amounts of preservatives. Bacterial growth was monitored at 18,100376

With Bioscreen (Labsystems, Finland). The instrument automatically measures the turbidity of bacterial growth from the sample set as a function of time. The results are shown in Figures 3A (acetic acid) and 3B (acetic acid with 2.5% by weight EB and 2.5% by weight PF).

It is found that the growth of Salmonella is inhibited at an acetic acid content of 0.5% by weight, but when 5% by weight of a 1: 1 ester mixture of ethyl benzoate + propyl formate according to the invention was mixed with acetic acid, the growth was already inhibited by 0.3% by weight: n amount of preservative.

10

Example 10 (solid preservative)

A solution was made containing 78% by weight of formic acid, 2% by weight of phosphoric acid, 1.25% by weight of ethyl benzoate, 1.25% by weight of propyl formate and 17.5% by weight of water. 45 parts by weight of 15 parts of the solution were absorbed in 55 parts by weight of moler (Damolin K 0.5-1 mm). An easily administrable solid preservative was obtained.

• · • · · •: • · • · 1 • 1 · • · · tl · • · ·

Claims (20)

1. Composition for the preservation of grass fodder, fresh cutting, cereals and the like. organic material and the control of microorganisms, which composition contains an ester of an unsubstituted or substituted benzoic acid, characterized in that it comprises at least one ester component 1) which is an ester of an unsubstituted or substituted benzoic acid and a C, -C9 alcohol or a mixture of such esters and one having said ester component 1) synergistically acting second ester component 2) which is an ester of a non-aromatic C1-C20 carboxylic acid and a C1-C9 alcohol, wherein the relative the weight proportions between the ester component 1) and the ester component 2) is 10: 1-1: 5. Composition according to claim 1, characterized in that. ester's unsubstituted or substituted benzoic acid is unsubstituted benzoic acid and / or parahydroxybenzoic acid, preferably unsubstituted benzoic acid. Composition according to claim 1 or 2, characterized in that the ester component of the ester C) -C9 alcohol is a C, -C4 alcohol, preferably ethanol or propanol. · «« · 4. A composition according to claims 1, 2 or 3. Characterized in that the ester component 1) is ethyl benzoate, propyl benzoate, isopropyl benzoate or a mixture thereof. 100376 Composition according to any one of the preceding claims, characterized in that the non-aromatic C 1 -C 20 carboxylic acid of the ester component 2 is a C 1 -C 2 carboxylic acid, preferably a C 1 -C 8 carboxylic acid, heic formic acid, propionic acid. or lactic acid. Composition according to any of the preceding claims, characterized in that the ester component of the 2) C 1 -C 9 alcohol is a C 1 -C 4 alcohol, preferably ethanol, propanol or butanol. Composition according to any of the preceding claims, characterized in that the ester component 2) is propyl formated; ethyl propionate, propyl propionate or a mixture thereof. 15 Composition according to any of the preceding claims, characterized in that the relative weight proportions of the preservative composition between the ester component 1) and the ester component 2) are between about 4: 1-1: 2, heist about 2: 1-1: 1.5. Composition according to any of the preceding claims, characterized in that it further comprises an acid component 3) which is an organic or inorganic acid or a mixture thereof, possibly at least partially neutralized. a compound forming these, or a mixture thereof. : "30 Composition according to claim 9, characterized in that the acid component 3) contains an organic C 1 -C 20 acid, preferably: preferably a C ^-C ^ acid, more preferably C1-C4 acid, such as formic acid, ···. acetic acid, propionic acid, lactic acid or a mixture thereof, heist formic acid. : 35 The composition according to claim 10, characterized in that the acid component 3) is 10-100-, preferably 30-100-, heist a 60-100% by weight aqueous solution. 100376 12. A composition according to claim 9, 10 or 11, characterized in that the acid component 3) contains phosphoric acid or a derivative or mixture thereof. Composition according to any of the preceding claims, characterized in that the minimum amount of the ester component 1) in the preservative composition is, calculated as benzoic acid, about 0.25 wt%, preferably about 0.5 wt%, heist about 1% by weight. 10 Composition according to any of the preceding claims, characterized in that the maximum content of the ester component 1) in the preservative composition is, as benzoic acid, about 10% by weight, preferably about 4% by weight, preferably about 2%. 5% by weight. Composition according to any one of the preceding claims, characterized in that it contains about 1.5-3.0% by weight of a mixture of the ester component 1) and the ester component 2), about 70-90% by weight of formic acid. and about 0-10% by weight of orthophosphoric acid as the acid component 3) and water. Composition according to any of the preceding claims, characterized in that it is in the form of a solution. ! 25 17. Composition according to any of the foregoing patent claims. also characterized in that it is solidified, preferably by suction in a support such as a large surface clay mineral. ; 1 · 30 * 18. Process for preparing a composition for preserving grass fodder, fresh cuts, cereals and the like. organic material, characterized in that an ester component 1) which is an ester of an unsubstituted or substituted benzoic acid and a C, -C9 alcohol or a mixture of such esters, and one having said ester component 1 2) which is an ester of a non-aromatic C, -C20 carboxylic acid and a C1-C9 alcohol, additives in the weight ratio 1): 2) = 10: 1 -1: 5 in a suitable gaseous, liquid or solid medium, preferably to a liquid preservative composition, optionally containing an acid component 3), in a home or at a different use just before or in connection with these uses, so that said synergistic acting composition forms an acting mixture. Use of a composition according to any one of claims 1-17 or a composition prepared according to patent claim 18 as additive in feed. Use of a composition according to any of claims 1-17 or a composition prepared according to patent claim 18 for improving livestock spaces and the like. spaces and / or for disinfecting the apparatus or apparatus. i:: «·· · * · ·» · • · «·« 1 · · ·