DE19831288A1 - Antimicrobial composition containing a mixture of hydrophilic and hydrophobic GRAS flavorings, useful for protecting foodstuffs, pharmaceuticals, cosmetics, dyes, paper and/or celluloses - Google Patents

Abstract

An antimicrobial composition contains a mixture of hydrophilic and hydrophobic GRAS flavorings. An antimicrobial composition comprises either: (1) a mixture of two or more GRAS (generally recognized as safe) flavorings (except polyphenol compounds or benzyl alcohol) and one or more hydrophilic, alcoholic and/or non-alcoholic GRAS flavorings; or (2) a mixture of benzyl alcohol or polyphenol compounds and one or more hydrophilic, non-alcoholic GRAS flavorings without any GRAS alcohols. The alcoholic GRAS flavoring is a mono- or polyvalent 2-10C alcohol. The non-alcoholic GRAS flavoring is a 1-15C organic acid or a physiological salt, a hydrophilic acetate and/or a hydrophilic aldehyde.

Description

The present invention relates to a method and an additive as well its use to improve durability and / or Stabilization of microbially perishable products by adding Additives.

Industrially processed food and feed, cosmetics, Pharmaceuticals and other products susceptible to microbial corruption have to be stable for a certain amount of time, not too short, to be able to find a Transport and distribution through the usual channels unspoiled To reach consumers. The consumer also expects that the purchased product does not spoil immediately after purchase, but, depending on the product, kept in stock for a few days or weeks can be.

Most food and feed would be left untreated within spoil fewer days because fungi and / or bacteria at most impaired by cooling, on an ideal one for them Could proliferate. Typical examples are the spoilage of Bread through mold, e.g. B. Aspergillus niger, of meat products (e.g. sausage) by enterobacteria or lactobacilli, the contamination from poultry through salmonella and much more. Because mushrooms including yeasts or their spores, gram positives and gram negatives Bacteria are present everywhere, if not through special, expensive ones and cannot be used industrially for economic reasons Measures to create a sterile environment must be appropriate Countermeasures are taken.  

Traditionally, food and feed, Cosmetics, pharmaceuticals, paints, paper and cellulose and others perishable products preserved with preservatives that are loud the Codex Alimentarius List of the Food and Agriculture Organization (FAO / WHO Food Standard Program) in Division 3 Food Additives Preservatives 3.73 listed as a "synthetic preservative" and mostly in the form of chemical monosubstances or their Combinations can be used.

A large number of additives are known from the prior art Preservation of perishable products known. These include e.g. B. Additives based on flavorings, alcohols, organic acids, Aldehydes, phenolic substances and essential oils. Such Compositions are, for example, in the US patent 4,446,161, US 4927651, WO 94/14414 of GB 172993 and DE-OS 31 38 277 and in E. Lück (chemical food preservation, page 1977, 1986 Springer-Verlag).

The preservatives listed in the list are bacteriostatic and / or fungistatic and significantly improve their shelf life. However, they are rejected by many consumers because their effects on the health of the consumer are not known, or harmful effects, especially if they are repeated over a long period of time, cannot be excluded. It is also disadvantageous that all previously known methods are based on changing the pH or a _w value.

A particular disadvantage of these preservatives is that they regularly added high concentrations to the food will. As a result, relatively large amounts of these funds reach Consume also in the human body. The consequence is today Frequently occurring reactions in the form of allergic Diseases.

An alternative to preservation by adding synthetic Preservatives are the thermal inactivation of germs, e.g. B. by pasteurization. Pasteurization is thermal Treatment of 30 to 120 minutes exposure time at 70 to 85 ° C.

Pasteurization improves the durability of such treated Products considerable, but is technically complex and consumes a lot much energy. In addition, the viability of spores is often not affected or only incompletely affected. Pasteurization is also not applicable to temperature sensitive products or leads to a not inconsiderable loss of quality, since at the latest the often necessary second thermization (up to 85 ° C) of the The "freshness" of the pasteurized product decreases. Also are especially valuable components of food, cosmetics or Pharmaceuticals, e.g. B. vitamins, amino acids and many pharmaceuticals Active ingredients, thermolabile, so that a thermal treatment under forbids the usual pasteurization conditions.

A further possibility for improving the durability is to pack the endangered product in an airtight manner under nitrogen or CO ₂ or to provide it in vacuum packaging, as it is e.g. B. is handled with ground coffee. However, these processes are expensive and complex and therefore cannot be used for many foods.

Accordingly, it is an object of the present invention to provide an additive for Improved shelf life and / or stabilization of microbial perishable products by adding additives do not have the disadvantages of the prior art having.

This object is achieved in that the additive is a mixture that

• a) at least 2 GRAS aroma alcohols, except benzyl alcohol
• b) and at least one non-alcoholic, preferably hydrophilic GRAS flavoring, except polyphenol

contains
wherein the mixing ratio of components a) to b) is between 1: 1 to 1: 10,000 and 10,000: 1 to 1: 1, preferably between 1: 1 to 1: 1000 and 1000: 1 to 1: 1. A mixing ratio between 1: 1 to 1: 100 and 100: 1 to 1: 1 is particularly preferred.

The following are those which can preferably be used according to the invention Substances described in more detail:

The named GRAS aroma alcohols are approved by the FDA Food use recognized as commercially safe (G.R.A.S = Generaly Recongnized As Safe In Food). This differs the alcohols according to the invention in particular from those in the US 4,446,161 can be used.

The GRAS aroma alcohols mentioned are such Alcohols listed in FEMA / FDA GRAS Flavor Substances Lists GRAS 3-15  No. 2001-3815 (status 1997). In this list there are natural ones and nature-identical flavorings listed by the American FDA for Food Use are approved (FDA Regulation 21 CFR 172.515 for nature-identical Flavorings (Synthetic Flavoring Substances and Adjuvants) and FDA Regulation 21 CFR 182.20 for natural flavorings (natural flavoring Substances and Adjuvants).

According to the invention, component a) can contain two or more GRAS Aroma alcohols can be used. It is preferred according to the invention the use of two GRAS aroma alcohols. Is particularly preferred the use of three or more GRAS aroma alcohols.

In particular, the following GRAS aroma alcohols can be used:
Acetoin (acetylmethylcarbinol), ethyl alcohol (ethanol), propyl alcohol (1-propanol), iso-propyl alcohol (2-propanol, isopropanol), propylene glycol, glycerin, n-butyl alcohol (n-propyl carbinol), iso-butyl alcohol (2-methyl-1 - propanol), hexyl alcohol (hexanol), L-menthol, octyl alcohol (n-octanol), cinnamon alcohol (3-phenyl-2-propene-1-01), α-methylbenzyl alcohol (1-phenylethanol), heptyl alcohol (heptanol), n -Amyl alcohol (1-pentanol), iso-amyl alcohol (3-methyl-1-butanol), anise alcohol (4-methoxybenzyl alcohol, p-anise alcohol), citronellol, n-decyl alcohol (n-decanol), geraniol, β-γ-hexenol (3-hexenol), lauryl alcohol (dodecanol), linalool, nerolidol, nonadienol (2,6-nonadien-1-ol), nonyl alcohol (nonanol-1), rhodinol, terpineol, borneol, clineol (eucalyptol), anisole, cuminyl alcohol ( Cuminol), 10-undecen-1-ol, 1-hexadecanol.

According to the invention, benzyl alcohol is an exception.  

The mixing ratio of component a) to component b) is preferably between 1: 1 and 1: 10,000 or 10,000: 1 and 1: 1, particularly preferably between 1: 1,000 and 1: 1 or 1: 1 and 1: 1,000, very particularly preferably between 1: 1 to 1: 100 and 100: 1 to 1: 1.

In components a) and b), however, different can additionally Alcohols are used. These are preferably monohydric or polyhydric alcohols with 2 to 10 carbon atoms preferably 2 to 7 carbon atoms.

Such amounts of GRAS aroma alcohols and other alcohols used that their mixing ratio between 1: 1 and 1: 1,000, in particular 1: 1 to 1: 100 and 100: 1 to 1: 1.

The components which can be used according to the invention and are described as follows Component b) are flavoring substances that are included in FEMA / FDA GRAS Flavor Substances List as G.R.A.S (Generally Recognized As Safe in Food) 3-15 No. 2001-3815 (status 1997) are recognized.

So z. B. in the additive according to the invention acids and / or their physiologically acceptable salts can be used. Preferably come organic acid and / or salts thereof. This is what it is about are preferably those compounds which have 1 to 15 carbon atoms, preferably contain 2 to 10 carbon atoms.

The following acids, for example, can be used:
Acetic acid, aconitic acid, adipic acid, formic acid, malic acid (1-hydroxy succinic acid), caproic acid, hydrocinnamic acid (3-phenyl-1-propionic acid), pelagonic acid (nonanoic acid), lactic acid (2-hydroxypropionic acid), phenoxyacetic acid (glycolic acid phenyl ether), phenylacetic acid ( ), Valeric acid (pentanoic acid), iso- valeric acid (3-methylbutanoic acid), cinnamic acid (3-phenylpropensic acid), citric acid, mandelic acid (hydroxyphenylacetic acid) tartaric acid (2,3-dihydroxybutanedioic acid; 2,3-dihydroxysuccinic acid), fumaric acid, e.g. B. lactic acid, preferred.

The following compounds can also be used in component b):
As phenols such. B. thymol, methyleugenol, acetyleugenol, safrol, eugenol, isoeugenol, anethole, phenol, methylchavicol (estragole; 3-4-methoxyphenyl-1-propene), carvacrol, cc-bisabolol, fornesol, anisole (methoxybenzene), propenylguaethol (5- Prophenyl-2-ethoxyphenol) can be used.

As acetates such. B. iso-amyl acetate (3-methyl-1-butyl acetate), Benzyl acetate, benzylphenylacetate, n-butyl acetate, cinnamyl acetate (3- Phenylpropenylacetate), citronellylacetate, ethyl acetate (ethyl acetate), Eugenol acetate (acetyleugenol), geranyl acetate, hexyl acetate (Hexanylethanoate), hydrocinnamyl acetate (3-phenyl-propyl acetate), Linalyl acetate, octyl acetate, phenylethyl acetate, terpinylacetate, triacetin (Glyceryl triacetate), potassium acetate, sodium acetate, sodium diacetate, Calcium acetate used.

As an ester z. B. Allicin usable.  

As terpenes come e.g. B. camphor, limonene, β-caryophyllene in Consider.

The acetals that can be used include, for. B. acetal, AcetaIdehydibutylacetal, Acetaldehyddipropylacetal, Acetaldehyde phenethylpropylacetal, cinnamaldehyde ethylene glycol acetal, Decanal dimethyl acetal, heptanal dimethyl acetal, heptanal glycery acetal, Benzaldehyde propylene glycol acetal.

Aldehydes, e.g. B. acetaldehyde, anisaldehyde, Benzaldehyde, iso-butyl aldehyde (methyl-1-propanal), citral, citronellal, n- Caprinaldehyde (n-decanal), ethyl vanillin, fufurol, heliotropin (piperonal), Heptylaldehyde (heptanal), hexylaldehyde (hexanal), 2-hexenal (β- Propylacrolein), hydrocinnamaldehyde (3-phenyl-1-propanal), lauryl aldehyde (Dodecanal), nonylaldehyde (n-nonanal), octylaldehyde (n-octanal), Phenylacetaldehyde (1-oxo-2-phenylethane), propionaldehyde (propanal), Vanillin, cinnamaldehyde (3-phenylpropenal), perilla aldehyde, cuminaldehyde.

Most of the flavorings on the GRAS FEMA list are not water soluble, d. H. hydrophobic. They are mainly in fatty foods are used because of their lipophilic character usable directly without solvent. The amount However, lipophilic foods are relatively low. According to the invention then hydrophilic GRAS aroma substances are preferably used or through combination with hydrophilic GRAS aroma substances (e.g. Solvent) achieved hydrophobic properties.

So that the additives according to the invention in most hydrophilic Food or feed, cosmetics or pharmaceuticals their  Can also have an effect in conjunction with a water-soluble solubilizers are used. This is what it is about preferably glycerin, propylene glycol, water or cooking oils Fats. In this case, hydrophilic flavorings can be found in food used with little or no content of hydrophilic substances will.

The essential oils and / or alcoholic, glycolic or plant extracts obtained by CO ₂ high-pressure processes can also be used according to the invention, for example:

• a) Oils or extracts with a high proportion of alcohols:
  Melissa, coriander, cardamom, eucalyptus;
• b) Oils or extracts with a high proportion of aldehydes:
  Eucalyptus citriodora, cinnamon, lemon, lemongrass, lemon balm, citronella, lime, orange;
• c) Oils or extracts with a high proportion of phenols:
  Oregano, thyme, rosemary, orange, clove, fennel, camphor, mandarin, anise, cascarille, tarragon and allspice;
• d) Oils or extracts with a high proportion of acetates:
  Lavender;
• e) Oils or extracts with a high proportion of esters:
  Mustard, onion, garlic;
• f) Oils or extracts with a high proportion of terpenes:
  Pepper, bitter orange, caraway, dill, lemon, peppermint, nutmeg.

The mixing ratio of components a) and b), the described Acids, phenols, acetals, aldehydes, esters, terpenes, acetates, essential oils and / or solubilizers can each between 1: 1 to 1: 10,000 and 10,000: 1 to 1: 1, preferably between 1: 1 to 1: 1000 and 1000: 1 to 1: 1.

The additives described are preferably used to improve the shelf life and stabilize the following groups of foods:
Bread, baked goods, baking agents, baking powder, pudding powder, beverages, dietetic foods, essences, delicatessen, fish and fish products, potatoes and products based on potatoes, spices, flour, margarine, fruits and vegetables and products based on fruits and vegetables, pickled foods, starch products , Confectionery, soups, pasta, meat and meat products, milk, dairy and cheese products, poultry and poultry products, oils, fats and products containing oil or fat.

The additives according to the invention are in particular against Molds, yeasts and bacteria (gram-positive and gram-negative) effective. Especially against pathogenic agents (Enterobacteriaceaen, e.g. E. coli, salmonella, enterococci, listersen, e.g. B. staphylococci, Streptococci, as well as against spoilage pathogens such. B. Lactic acid bacteria e.g. B. Lactobacillus vulgaris, molds, e.g. B. Aspergillus niger, yeasts, e.g. B. Endomyces tibuliger, they act outstanding. The additives according to the invention also act on viruses and reducing against microbial toxins, e.g. B. aflatoxins, enterotoxins.  

The additives are preferably used in amounts of 1 ppm to 10% by weight, preferably 1 ppm to 1.0% by weight of the microbially perishable product added. Particularly preferred amounts are 0.001% by weight to 0.5 % By weight. 0.002% by weight to 0.25% by weight are very particularly preferred.

It is surprising according to the invention that the effect of additives according to the invention already when using the aforementioned low concentrations occur. This is all the more surprising than that food treated with the additives of the invention have a significantly longer shelf life than conventional ones Preservatives treated perishable products.

It is also surprising that the advantages already described Microbial exposure times of less than 24 hours, especially 60 Minutes, preferably 1-60 minutes, most preferably 5-15 minutes occur.

The additives according to the invention surprisingly do not lead to any disadvantages in taste, smell or color in the treated food. A particular advantage over the prior art is that there are no shifts in the pH or a _w value. Ie, the effect of the additives used is surprisingly independent of the pH value and a _w value. It is also surprising that the additives can be used regardless of the moisture, the fat, protein and carbohydrate content. Finally, the combinations according to the invention are insensitive to temperature fluctuations in the range between -30.degree. C. and 200.degree. C., ie they are insensitive to both cold and heat.

In addition to the additives described, before, during or after completion of the manufacturing, processing or Packaging of the products, their surfaces and / or their surroundings, in particular the ambient air and / or the surfaces of the coming into direct or indirect contact with the products Devices or other materials with one or more Process aids are applied, the at least two Flavorings. That is, in addition to using the additives according to the invention also an external treatment with process aids respectively.

The flavorings contained in the processing aids are exclusive Natural substances Natural or nature-identical aroma substances, which according to FEMA are recognized as safe (GRAS - Generally Recognized As Safe). At The list mentioned is FEMA / FDA GRAS Flavor Substances Lists GRAS 3-15 No. 2001-3815 (status 1997), the natural and nature-identical flavorings by American FDA for Food Use are approved (FDA Regulation 21 CFR 172.515 for nature-identical Flavorings (Synthetic Flavoring Substances and Adjuvants) and FDA Regulation 21 CFR 182.20 for natural flavorings (natural flavoring Substances and Adjuvants). Those that meet these FDA standards Flavorings may be used "quantum satis", i. H. they are allowed to to the maximum concentration in the food they contain no odor or taste impairment of the Food to which they are added. According to FEMA Flavorings listed largely coincide with those in the substances contained in the corresponding European standard COE.  

According to the invention may also according to Article V European Community Directive Flavors (22.06.88) classified as "NAT4" Flavorings are used, provided they apply according to the previously mentioned FEMA GRAS list as safe. Are NAT4 substances Substances that are identical to nature under certain conditions are declared, e.g. B. when these substances in combination and as Ingredient with a natural or nature-identical aroma be used.

The particular advantage of process aids is that, due to its in listed on the FEMA GRAS list and by the United States Department of Health FDA, arguably the most critical health agency ever components recognized in the "quantum satis" - Concentration range can be added without further food can.

Another particular advantage is that the process aids Do not affect the taste and smell of the treated products.

The process aids according to the invention are, for example, in the form of lubricants, emulsifiers and cleaning agents, spray agents, Nebulizers, gas phase active agents, Heat transfer agents as well as cutting or separating agents are used. The process aids can also be used as additives to the above Funds are used.

It is essential that the process aid not the food be added or mixed with these. Rather be  only the surfaces or cut surfaces of the food with the Process aids applied. This can be done in that the Food surfaces or cut surfaces directly with the Process aids are applied. But it is also possible the surfaces of devices, production machines, Packaging equipment, transport equipment, packaging materials rialien and the ambient air with the processing aid.

It is surprising that the microbicidal action of the processing aids occurs even when low concentrations are used. Only 0.01 to 5 g / kg, preferably 0.05 to 2g / kg, particularly preferably 0.05 to 1g / kg of food are used when they are applied. When used for the ambient air, only 0.001 to 10 g / m ^{3 of} air are used, for example. Only 0.000001g to 0.1 g / cm ² surface is used for the surfaces of devices.

If these concentrations are adhered to, they are in the food detectable amounts only at 0.001% by weight. In contrast, will the prior art regularly 0.1 to 3 wt .-% preservative be present in the food. Despite this extremely low Concentrations, it is surprising according to the invention that conventionally preserved foods Shelf life extension of up to 50% can be achieved.

It is particularly noteworthy and astonishing that already through Process aids that are applied indirectly to food, 0.001% by weight is sufficient to stabilize the shelf life or -to achieve improvement with increased product quality.  

This effect is all the more surprising than the microbicide Effect time of the flavoring substances used according to the invention under 24 Hours, preferably less than 12 hours. Most notably it is preferred to select process aids and concentrations in such a way that the microbicidal time is less than 1 hour, preferably less than 15 Minutes.

In contrast, it is the goal of the conventional Preservatives, as long as possible, d. H. over weeks and months, in to be effective on the food. Despite the very short effects The process aid used according to the invention is the durability compared to the prior art with conventional Preservatives or preservation processes treated Food significantly increased. According to the invention is accordingly at Combination of the additives described above and the processing aid it is surprisingly possible to work with considerably smaller quantities, than this when using the hitherto customary according to the prior art Preservatives were required.

The process aid which can be used according to the invention comprises flavorings, which are selected from the group of alcohols, aldehydes, phenols, Acetates, acids, esters, terpenes, acetals and their physiological compatible salts, essential oils and plant extracts.

Preferred embodiments of the process aids according to the invention include one or more flavoring agents that consist of one or more of the following groups are selected:

I. Alcohols

Acetoin (acetylmethylcarbinol), ethyl alcohol (ethanol), propyl alcohol (1- Propanol), isopropyl alcohol (2-propanol, isopropanol), propylene glycol, Glycerin, benzyl alcohol, n-butyl alcohol (n-propyl carbinol), iso- Butyl alcohol (2-methyl-1-propanol), hexyl alcohol (hexanol), L-menthol, Octyl alcohol (n-octanol), cinnamon alcohol (3-phenyl-2-propene-1-01), α- Methylbenzyl alcohol (1-phenylethanol), heptyl alcohol (heptanol), n- Amyl alcohol (1-pentanol), iso-amyl alcohol (3-methyl-1-butanol), Anise alcohol (4-methoxybenzyl alcohol, p-anise alcohol), citronellol, n- Decyl alcohol (n-decanol), geraniol, β-γ-hexenol (3-hexenol), Lauryl alcohol (dodecanol), linalool, nerolidol, nonadienol (2,6- Nonadien-1-ol), nonyl alcohol (nonanol-1), rhodinol, terpineol, borneol, Clineol (eucalyptol), anisole, cuminyl alcohol (cuminol), 10-undecen-1-ol, 1-hexadecanol.

II. Aldehydes

Acetaldehyde, anisaldehyde, benzaldehyde, isobutylaldehyde (methyl 1- propanal), citral, citronellal, n-caprinaldehyde (n-decanal), ethylvanillin, Fufurol, heliotropin (piperonal), heptylaldehyde (heptanal), hexylaldehyde (Hexanal), 2-hexenal (β-propylacrolein), hydrocinnamaldehyde (3-phenyl-1- propanal), lauryl aldehyde (dodecanal), nonyl aldehyde (n-nonanal), Octylaldehyde (n-octanal), phenylacetaldehyde (1-oxo-2-phenylethane), Propionaldehyde (propanal), vanillin, cinnamaldehyde (3-phenylpropenal), Perilla aldehyde, cuminal aldehyde.

III. Phenols

Thymol, methyleugenol, acetyleugenol, safrol, eugenol, isoeugenol, Anethole, phenol, methylchavicol (estragole; 3-4-methoxyphenyl-1-propene), Carvacrol, oc-bisabolol, fornesol, anisole (methoxybenzene), Propenylguaethol (5-propenyl-2-ethoxyphenol).

IV. Acetates

iso-amyl acetate (3-methyl-1-butyl acetate), benzyl acetate, Benzylphenylacetate, n-butyl acetate, cinnamyl acetate (3- Phenylpropenylacetate), citronellylacetate, ethyl acetate (ethyl acetate), Eugenol acetate (acetyleugenol), geranyl acetate, hexyl acetate (Hexanylethanoate), hydrocinnamyl acetate (3-phenyl-propyl acetate), Linalyl acetate, octyl acetate, phenylethyl acetate, terpinylacetate, triacetin (Glyceryl triacetate), potassium acetate, sodium acetate, sodium diacetate, Calcium acetate.

V. acids and / or their physiologically tolerable salts

Acetic acid, aconitic acid, adipic acid, formic acid, malic acid (1- Hydroxy succinic acid), caproic acid, hydrocinnamic acid (3-phenyl-1- propionic acid), pelagonic acid (nonanoic acid), lactic acid (2- Hydroxypropionic acid), phenoxyacetic acid (glycolic acid phenyl ether), Phenylacetic acid (α-toluenic acid), valeric acid (pentanoic acid), iso- Valeric acid (3-methylbutanoic acid), cinnamic acid (3-phenylpropenoic acid), Citric acid, mandelic acid (hydroxyphenylacetic acid) tartaric acid (2,3- Dihydroxybutanedioic acid; 2,3-dihydroxysuccinic acid), fumaric acid, Tannic acid.

VI. Esters

Allicin.

VII. Terpenes

Camphor, limonene, β-caryophyllene.

VIII. Acetals

Acetal, acetaldehyde butyl acetal, acetaldehyde dipropylacetal, acetaldehyde phenethylpropylacetal, cinnamaldehyde ethylene glycol acetal, Decanal dimethyl acetal, heptanal dimethyl acetal, heptanal glycery acetal, Benzaldehyde propylene glycol acetal.

IX. Polyphenol X. Essential oils and / or alcoholic glycolic extracts or extracts obtained by the high-pressure CO _{2 process} from the plants listed below

• a) Oils or extracts with a high proportion of alcohols:
  Melissa, coriander, cardamom, eucalyptus;
• b) Oils or extracts with a high proportion of aldehydes:
  Eucalyptus citriodora, cinnamon, lemon, lemongrass, lemon balm, citronella, lime, orange;
• c) Oils or extracts with a high proportion of phenols:
  Oregano, thyme, rosemary, orange, clove, fennel, camphor, mandarin, anise, cascarille, tarragon and allspice;
• d) Oils or extracts with a high proportion of acetates:
  Lavender;
• e) Oils or extracts with a high proportion of esters:
  Mustard, onion, garlic;
• f) Oils or extracts with a high proportion of terpenes:
  Pepper, bitter orange, caraway, dill, lemon, peppermint, nutmeg.

If the process aid only one of the flavoring agents mentioned contains, isopropanol and ethanol are not used. Surprisingly, it has been shown that a combination of at least two of the specified flavoring substances are much larger Has more effect than with a single substance.

Most of the flavorings on the GRAS FEMA list are not water soluble, d. H. hydrophobic. They are mainly in fatty foods are used because of their lipophilic character usable directly without solvent. The amount However, lipophilic foods are relatively low. To in most of the time hydrophilic food or feed, cosmetics or pharmaceuticals to be able to develop their effect, they are preferred in connection with a water-soluble solubilizer. To claim this invention, health-friendly process aids for To make available, to meet, are exclusively for Food-approved solubilizing flavorings, e.g. B. alcohols used.  

The process aids are used undiluted and / or in water-soluble dilutions with water and / or food-grade solvents (e.g. alcohols) and / or in fat-soluble dilutions with vegetable (fat) oils.

In the process aids such. B. readily water-soluble alcohols, preferably in concentrations of 0.1 to 99 wt .-%, based on the Process aids, used in conjunction with other flavorings will. The processing aids can contain more than 50% bezyl alcohol contain. They preferably contain less than 50% by weight of ethanol, Isopropanol or benzyl alcohol or a mixture of these substances. It is particularly preferred if the proportion of the alcohols mentioned is less than 30 wt .-%, in particular less than 20 wt .-%. If process aids are used, the bezyl alcohol and contain at least one further flavoring agent, the proportion of Benzyl alcohol are also more than 50% by weight.

Surprisingly, the process aids, for example only 20% by weight ethanol or isopropanol in combination with aroma aldehydes and -phenols in concentrations in the alcohol range, a very strong fungicidal and bactericidal effects; even process aids that 1 % By weight of the water-soluble alcohols mentioned in connection with contain less than 3 ‰ aroma aldehyde and phenol, have a 70 to 100% microbicidal effect.

From the foregoing it follows that the invention Process aids surprising microbicidal effects on the environment of the production or the production process.  

It is preferred to use the process aids for the Production in food and feed, cosmetics, pharmaceuticals, Paints, paper and / or cellulose.

In particularly preferred embodiments, the processing aids are used to improve the shelf life and stabilize foods selected from the following group:
Bread, baked goods, baking agents, baking powder, pudding powder, beverages, dietetic foods, essences, delicatessen, fish and fish products, potatoes and products based on potatoes, spices, flour, margarine, fruits and vegetables and products based on fruits and vegetables, canned foods, starch products , Confectionery, soups, pasta, meat and meat products, milk, dairy and cheese products, poultry and poultry products, oils, fats and products containing oil or fat.

The process aid works in the environment of the susceptible to corruption Product, for example a food or feed, e.g. B. on Machine parts in contact with the one to be machined or processed Product stand, or in the air. Through direct contact with the Surface of the product susceptible to spoilage, they also work there, d. H. they develop their effect on the surface or when penetrating the product in this itself.

The particular advantage of the process aid described is therefore that it reliably decontaminates on the one hand, whereby its Efficacy against gram-positive and gram-negative bacteria, fungi  including yeasts and also viruses, while it has been proven on the other hand, no danger for the consumer of the food represents, since it is completely harmless for him and none has microbicidal, technological after-effects in food because The microbicidal effectiveness relates to the production environment that through the inventive measures of contaminating Free microorganisms.

The process aid which can be used according to the invention can be a Be a lubricant that simultaneously lubricates and decontaminates the lubricated parts and thus indirectly the durability stabilization of the products in contact with these parts.

According to the invention, the processing aid can furthermore be an emulsifying, Release agents or cleaning agents. Such agents are used for emulsification and / or cleaning and thus also the decontamination of surfaces, Objects, machines, facilities, devices, cutting surfaces or devices, transport devices and the like. It can also for decontaminating and cleaning food, Raw materials, cosmetics, pharmaceuticals, paints, paper, pulp, livestock, Poultry, fish and waste are used.

The process aid which can be used according to the invention can also be used be a spray. Such a spray enables one Fine distribution of the decontaminating agents on all Machine parts, transport devices, cutting devices, Worktops etc. and at the same time can lead to immediate after the cutting or separating process and / or packaging Portioning process of packaged food by enclosed food  Spray in a climate with decontaminating and / or durability-stabilizing properties are kept. Fogging or sprayable embodiments are also because of the comparatively less need very inexpensive.

Likewise, the spray in and / or on packaging such. B. Bags, boxes or the like are blown in or sprayed / nebulized in order to make the product packed in it more durable.

The spraying agents are also used in the production environment (environment, Cooling, ventilation, fresh air) at hygienic weak points (e.g. Cooling sections) can be atomized in order to increase the bacterial count reduce without harming the personnel working there.

The process aids can also be sprayed on Food surfaces or cut surfaces are used to cut the on eliminate food spoilage agents or to reduce.

Furthermore, these sprays can be used in transport facilities, storage and Cold rooms and the like are used.

In a further embodiment, the process aid is a Gas phase active agent, that of active decontamination and / or Deodorization in the gas phase in more or less closed Systems, such as packaging, waste systems, container systems, Transport or storage rooms and the like is used. From the effect of Gas phase agents benefit both the packaged, in the container  contained, transported or stored goods as well as the air and that respective environment.

The process aid has also proven to be a good heat Means of transmission proven. With heat transfer medium, cooling, Heating and heating means meant that in circulating circulation systems of liquid cooling, heating and heating systems as decontaminating Additives can be used. You will be watery or oily systems to prevent the growth of Microorganisms in the liquids added to z. B. with leaks cooling to prevent contamination.

In another embodiment, the process aid is a cutting or release agent for cutting knives and / or cutting devices of all Kind and for all perishable products to be cut to the Prevent contamination of the interfaces.

In the food industry often occur at the interfaces food contamination from gram-negative or gram positive pathogens, molds, yeasts and other possible ones Spoilage pathogens that affect the durability of the cut or separate products e.g. T. can significantly affect and cause both health and economic damage. The Contamination is caused by raw materials, product / raw material residues, Personnel due to machine parts or operational processes or entered through the air.

Traditionally, therefore, either the cut ones are still used today or separated or to be cut or separated  Food pasteurized or technically treated to make them decontaminate and make it more durable, or with Preservatives added. However, as mentioned above, is one thermal treatment not possible or permissible in every case and may lead to a reduction in the quality of the product.

A flanking measure to improve the durability of Food involves cleaning or even disinfecting the environment chemical disinfectants that are subject to the biocide regulation. These Substances are more or less toxic and should not be used in food be transmitted. However, chemical disinfection is one discontinuous measure that can only be determined pragmatically Production times are used on machine parts and in the environment can and after performing a rinse with water Removal of residual substances is required. Accordingly, the direct permanent elimination of spoilage agents is not guaranteed.

Machine hygiene has therefore been attempted in the prior art through better cleaning ability or through installations for Generation or maintenance of pure or low-germ or germ-free air to optimize. Experience has shown that this has not increased Shelf life of cut or separated foods or is no longer economically viable or is practically unsafe to implement.

An example from the sliced bread industry shows that by slicing or separating bread types such as whole dough, whole grain, white, mixed or Toasted bread and subsequent packaging the shelf life of the  Sliced bread is significantly reduced in contrast to whole bread. she lies depending on the type of bread between 2 and 5 days. By today mostly subsequent thermal treatment (pasteurization in Ovens or microwave ovens with a core temperature of 60 to 90 ° C) The shelf life of bread usually extends to 4 to about 20 Days when using normal breathable buttocks packaging of polyethylene bags. Other foils, e.g. B. made of polypropylene however, they can be much more expensive because of their lower Vapor permeability achieve a longer shelf life. packagings with polyester plastics and an entered nitrogenous Atmosphere lead to even longer durability. All of these measures however, they are either very expensive or only for expensive special products and markets can be used and lead z. T. considerable loss of quality the sliced bread, e.g. B. by condensation in the bread bag, too soft Bread consistency or drying out too early. These measures solve everyone not the actual causes of contamination by the cutting or separation process that both in the environment, as well as in the product or possible spoilage agents present on the machine the cutting device, e.g. B. the cutting blades, in the food registers or distributed in it.

As cutting or cutting aids are usually either mineral compositions that no longer exist in many countries are approved, or vegetable cutting oils are used, which are often already already contaminated, d. H. are bacterially contaminated. See e.g. B. G. Schuster: Investigations on mold contamination of sliced bread, baker & Confectioner 27 (11), pp. 345-347; G. Spicher: The sources of the direct Contamination of the bread with mold; The cutting oil as a factor mold contamination; Cereals, Flour and Bread 32 (4), pp. 91-94.  

For a cutting or separating agent that decontaminates with the Machine parts in contact with food during the Cutting process allowed and thereby an improved durability of the Cut material, there is therefore an urgent need, which by the cutting or release agent according to the invention is satisfied.

The cutting or separating agent can be used wherever industrial is cut or separated and the clippings through a corruption Bacteria or fungi or contamination by viruses. This applies e.g. B. for pulp and paper, but especially for food or feed.

In a preferred embodiment, this is the invention Process aids for cutting or separating bread, baked goods, Fish and fish products, potatoes and products Potato base, fruits and vegetables and products based on Fruit and vegetables, confectionery, starch products, pasta, meat and Suitable for meat products, cheese products, poultry and poultry products.

If the process aid is a cutting or Separating agent (e.g. for cutting bread), this can be done in the usual way Vegetable oil-fat wax base with the addition of microbicides Process aids based on flavorings are provided. The cutting or separating agent (e.g. for use in the Meat products industry) can preferably according to the invention consist exclusively of one or more flavorings.  

The vegetable oils, waxes and fats can also be natural emulsifiers, e.g. B. lecithins in a concentration of 1 to 25 wt .-%, are added, as it corresponds to the prior art. Exemplary emulsifiers are lecithins, citric acid monoglycerides, diacetyltartaric acid, N-acetylphosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidic acids, phosptatidylcholine. However, if the cutting or separating agent according to the invention is provided as an emulsion on an aqueous basis, vegetable oils, vegetable fats and vegetable waxes with unsaturated and saturated C ₁₆ -C ₁₈ fatty acids, which also have a viscosity of approx. 10 mPas (20 ° C) to approx Have used 500 mPas (20 ° C).

This, for example, from the above-mentioned fatty acids or oils and Cutting and release agents composed of emulsifiers can be used Mix with water in a ratio of 1: 1 to 1:40 as cutting or Separating emulsion (milk) can be used.

In practice, the cutting or separating agent is at least in Contact with the machine parts to be cut to decontaminate them. Experience shows that the funds are in Dosages of 1-20 g / kg of food are used, the Dosage of the cutting or separating device used and the Clippings is dependent.

The cutting and separating agents are mostly applied to the cutting or Separators applied, e.g. B. when cutting bread Circular disc cutting machines sprayed with which z. B. Sliced bread is then cut. According to the invention thereby parts of the cutting devices, for. B. circular knife, band slicer  (rotating band saws), electric or mechanical knives Knife devices, electric or mechanical saws or Sawing devices, electric or mechanical chainsaws or Devices wetted so that the cutting or separating agent on the corresponding machine part as well as on the by cutting or separating the resulting surface from decontamination or microbicidal can work.

The advantageous effect of the cutting and Release agent manifests itself in an extended shelf life of the clippings, e.g. B. of sliced bread. It is based not least on the fact that the cutting and Release agent penetrates the surface of the clippings and also the deeper layers of the cut food and decontaminated through the flavorings contained in the cutting oil.

The flavors described here also have a microbicidal effect the vapor phase, since most of the aromas evaporate easily. they therefore act in the so-called environment of the food, e.g. B. in the Packaging of the food if this after the cutting process e.g. B. is packed in a foil packaging.

This process of decontamination of the clippings after actual cutting process can be caused by a weak thermal Post-treatment of the food still significantly improved will.

In the following the invention will be described in more detail by means of examples described:

Bacteriological test methods for additives

• - Quantitative suspension test I (germ carrier test)
• - quantitative suspension test II (suspension test)
• - quantitative suspension test III (agar diffusion test).

Microorganisms: aerobic microorganisms (total bacterial count), Enterobacteriaceaen, enterococci, lactobacilli, yeast, mold. These methods can be used with different microorganisms different nutrient media effects of additives depending from the dosage and exposure time.

Quantitative suspension test: I - Germ carrier test

Suspension depending on the test germ:
Ringer's solution
Tryptone soy broth
Chromcult enterococcal broth
Seasoning broth
Germ carrier: 5 × 5 cm autoclaved cotton cloth or filter
Nutrient agar:
Total aerobes <plate count agar (casein peptone glucose yeast extract agar)
Chromocult <Enterococcus faecalis
Enterococcus faecium
Streptococcus bovis

OGYE selective medium (yeast extract glucose oxytetracycline) Microorganism molds)

Aspergillus niger
Saccharomyces

Deoxvcholate lactose agar Microorganisms

Lactose positive - Escherichia coli
Lactose weakly positive - Enterobacter (cloacae)
Lactose - weakly positive - Klebsiella (pneumoniae)
Lactose negative - Salmonella (typhimurium and enteritidis)
Lactose negative - Shigella (flexneri)
Lactose negative - Proteus (mirabilis)
Lactose negative - Pseudomonas
Lactose negative - Enterococcus (faecalis)
MRS AGAR (Lactobacillus)
Lactobacillus vulgaris

Baird Parker agar (with egg yolk tellurite emulsion) Microorganisms

Staphylococcus aureus
Staphylococcus epidermidis
Micrococcus (Enterococcus faecium)
Bacillus subtilis
Yeast: Endomyces tibuliger

Cereus selective agar acc. To Mossel (with egg yolk emulsion) Microorganisms

Bacillus cereus
Bacillus cereus
Bacillus subtilis
Escherichia coli
Pseudomonas aeruginosa
Proteus mirabilis
Staphylococcus aureus

Deoxycholate lactose agar Microorganisms

Lactose positive Escherichia coli
Lactose weakly positive - Enterobacter (cloacae)
Lactose-weak-positive - Klebsiella (pneumaniae)
Lactose negative - Salmonella (typhimurium and enteritidis)
Lactose negative - Shigella (flexneri)
Lactose negative - Proteus (mirabilis)
Lactose negative - Pseudomonas (Enterococcus faecal is)

TGE agar (casein peptone glucose meat extract agar) Microorganisms

Staphylococcus aureus
Streptococcus agalactiae
Enterococcus faecalis
Escherichia coli
Salmonella typhimurium
Pseudomonas aeruginosa
Bacillus cereus

Suspension test quantitative carrier test -

Others: special nutrient media and differentiations
For: Clostridia, Listeria and others

Contamination of the germ carrier

The germ carriers are contaminated after being placed in a sterile glass dish by pouring over the test germ suspension (≧ 10 ⁶ / per ml). After 1-10 min. long storage, the germ carriers are distributed in a glass dish lined with sterile filter paper and dried in an incubator at 36 ° C ± 1 ° C.

exam

The contaminated and dried germ carriers are sterile Glass bowls placed and soaked with (gr.% / Recipe); Stored for 1 h and for the intended agar / test germ and placed in the incubator incubated at the prescribed temperature.

According to the recommended (time / incubation), the germ carriers are diluted from 10 ¹ to 10 ⁸ at 9-fold dilution (depending on the test germ) and added to the agar provided in the plate casting process.

calculation

All of which have between 200 and 200 colonies. Determined using the weighted arithmetic mean:

C = number of colony-forming units per ml / g
σc = sum of the colonies of all Petri dishes used for the calculation
n ₁ = number of petri dishes of the lowest dilution level, which are used for the calculation (n ₁ = 2 for 2 petri dishes)
n ₂ = number of petri dishes of the next higher dilution level, which are used for the calculation
d = factor of the lowest evaluated dilution level, the dilution level related to n ₁

Quantitative suspension test II - suspension test

• a) Test germ suspension with the desired test germ, e.g. B. 10 ⁶ / ml inoculated for 1-60 minutes. Enter the desired recipe to be checked into the intended germ suspension tube (different percentage quantities). Wait for the action to take effect and pour or inoculate into the appropriate agar plates depending on the germ.
• b) Treat the test germ suspension with the desired formulation to be tested before inoculating the test germs (see a) (see a).
  Wait for the reaction times and then inoculate with the respective test germs and, depending on the test germ, inoculate or pour in the appropriate agar plates.

Quantitative suspension test III: AGAR DIFFUSION TEST

Pour nutrient agar plates, e.g. B. 10 ⁴ microorganisms / ml.

A sterile filter paper sheet (10 mm) is attached to the one to be tested Prescription soaked and placed on the nutrient agar plate.

After the incubation of (time / temperature depending on the germ) the formation of an inhibition zone as a positive reaction.  

Recipe examples

Claims (14)

1. Additive for improving the shelf life and / or stabilizing microbially perishable products, characterized in that it is a mixture that

• a) at least two GRAS aroma alcohols, excluding benzyl alcohol and
• b) contains at least one non-alcoholic, preferably hydrophilic, GRAS aroma substance, with the exception of polyphenol,

the mixing ratio of components a) to b) or c) to d) in each case between 1: 1 to 1: 10,000 and 10,000: 1 to 1: 1, preferably between 1: 1 to 1: 1000 and 1000: 1 to 1 : 1 lies. 2. Additive according to claim 1, characterized in that the components a) and b) in Mixture with at least one other monovalent or polyhydric alcohol with 2 to 10 carbon atoms, preferably 2 to 7 carbon atoms Atoms are present. 3. Additive according to one of claims 1 or 2, characterized in that the additive as component b) at least one organic acid and / or at least one of their physiological salts with 1 to 15 carbon atoms, preferably 2 contains up to 10 carbon atoms. 4. Additive according to one of claims 1 to 3,  characterized in that the additive as component b) Phenols, acetates, esters, terpenes, acetals, aldehydes and / or contains essential oils. 5. Additive according to one of claims 1 to 4, characterized in that the additive is a solubilizer, especially glycerin, propylene glycol, water, edible oils, fats contains. 6. Additive according to one of claims 1 to 5, characterized in that the ratio of components a) to b) is between 1: 1 to 1: 100 and 100: 1 to 1: 1. 7. Additive according to claim 2, characterized in that the mixing ratio of Components a) and b) to the further alcohols between each 1: 1 and 1: 10,000 or 10,000: 1 and 1: 1, preferably between 1: 1000 to 1: 1 or 1: 1 to 1: 1000. 8. Procedure for improving the durability and / or stabilization of microbial perishable products characterized in that a mixture according to one of the Claims 1 to 8 is added to the microbially perishable product. 9. The method according to claim 8, characterized in that the additive in amounts of 1 ppm to 10 wt .-% is added to the microbially perishable product. 10. The method according to any one of claims 8 or 9,  characterized in that the additive in amounts of 0.001 % By weight to 0.5% by weight added to the microbially perishable product becomes. 11. The method according to any one of claims 8 to 10, characterized in that the additive in amounts of 0.002 % By weight to 0.25% by weight of the microbially perishable product is added. 12. The method according to any one of claims 8 to 11, characterized in that before, after or during the process for the manufacture, processing or packaging of their products Surfaces and / or their surroundings, especially the Ambient air and / or the surfaces of the directly or indirectly devices coming into contact with the products or other Materials are loaded with one or more process aids are, which are preferably at least two microbicidal Flavorings included. 13. The method according to claim 12, characterized in that the processing aid in amounts of 0.01 to 5 g / kg, preferably 0.05 to 2g / kg of food, when used for the ambient air in amounts of 0.001 to 10 g / m ³ Air, and is used on the surfaces of devices in quantities of 0.000001g to 0.1 g / cm ² . 14. Use of the additive according to one of claims 1 to 8 for Improve shelf life and / or stabilize microbially  perishable products, especially food and Cosmetics.