DE19649952A1 - Process for the preservation of solid, liquid or pasty perishable products - Google Patents

Abstract

Method for preserving solid, liquid or paste-like perishable goods such as foodstuffs, animal feed and body-care and beauty products, wherein the product to be preserved is processed at high pressure. According to said method, a high degree of preservation is achieved while using a minimum amount of preservative or at least a tolerable preservative. This is done by mixing the product to be preserved with a microbiostatically active preservation agent and subsequently processing said product at high pressure.

Description

The invention relates to a method of preservation of solid, liquid or pasty perishable products such as food, feed and means for Body and beauty care, which is to be preserved Product is subjected to high pressure treatment.

The requirements for such a preservation process There are many kinds. Often it is not necessarily required that all existing microorganisms are removed be killed, what is essential is that what is present microorganisms do not spoil the product can. However, they must all form pathogens and toxins the microorganisms and enzymes that kill the bearings limit the ability of the product to be inactivated. But, at least for food, these sen sensory properties of the food if possible stay, as well as the nutritional value or valuable Ingredients such as vitamins and proteins.

The spoilage of the packaged products can cause the under take on various forms, aerobic micro organisms consume z. B. the inside of the packaging oxygen present and create concave dents in the Packaging.

Bulging packaging, so-called "bombs", are on the Activity of gas-forming spoilage organisms. Bows indicate that, among other things, Clostridia, lactic acid bac teria, Enterobacteriaceae, or denitrificants that have spoiled the packaged product.

Other spoilage organisms change the pH of the packaged product, e.g. B. Acid formation occurs as a result of fermentation:

• - These include the butyric acid-forming chlostridia as well as the lactic acid bacteria, lactic acid or Form acetic acid.
• - The Enterobacteriaceae produce formic acid, vinegar acid, among others, while yeast is the cause of vinegar acid, lactic acid and others could be.

But it can also alkalize the packaged Pro enter the duct by protein-degrading chlostridia, Pseudomonads and others release ammonia, for example.

Still other spoilage organisms cause color changes changes in packaged products, the so-called sulfate reduction decorators do this by creating sulfides. A The so-called pigment formers such. B. Pyocyanin-producing Pseudomonia aeruginose.

Packaged products can also have changes in odor travel. The sulphate reducers use hydrogen sulphide free, the same thing happens through the protein breakdowns that also produce odor-intensive amines.

The fermenting Ver acids and alcohols formed by organisms chen also an odor damage to the off packed product. The odor of rancidity due to lipolytes.

Some packaged products can go through the spoilage orga in terms of their viscosity the. For example, the so-called mucus builders increase the Viscosity while the polymer degrades and lipolytes them humiliate.

Such packaged products are unpleasant which spoilage organisms the phase separation of Emulsio nen have caused, e.g. B. this happens as a result of alcohols formed by fermenters or by being under different spoilage organisms break down the emulsifiers.

The spoilage of the packaged products is evident Lich, provided the damaging microorganisms are visible grow. For example, mold spots indicate fungus fall, the slime visible in packaged products is due to the activity of the mucus builders.

The aforementioned damage caused by spoilage has an adverse effect individual or multiple features of packaged Pro ducks

Other spoilage damage is due to one with the stipulation appropriate consumption of a packaged product Health hazard addressed.

In the case of cosmetic products, for. B. the danger of Contamination with gram-positive bacteria. An infection having Staphylococcus aureus makes itself through symptoms like Pus, sepsis, toxic shock syndrome, etc. noticeable. Streptococcus pyogenes produces similar symptoms. Wundin fects and urinary tract infections are attributed to the Contamination of the cosmetic product with Enterococcus spec. Tetanus is caused by Clostridium tetani called out. Among those transferable in cosmetic products gram-positive bacteria are also one of the causes of gangrene corresponding Clostridium perfringens.

But the gram-negative bacteria can also kill the kosme contaminate table agents. An infection by pseudomo nas aeruginosa is made up by symptoms such as pus, Sep sis, pyoderma, conjunctivitis, otitis, or respiratory tract fects recognizable. Conjunctivitis is also noted call by Klebsiella spec. Various by kosmeti Enterobacteriaceae transmissible agents belong to the gram-negative and cause infectious enteritis.

Cosmetic agents can also be the source of a ge be harmful to health. That's candida albicans causes thrush or conjunctivitis. The latter Symptom can also be an infection with Candida parapsi assign losis.

Eczema and dandruff are the result of exposure to Pityrosporuni oval. May cause mycoses of the skin when using a cosmetic product Spores of Trichophyton species or Microsporrum species penetrate the skin and become active there.

As well as the packaged product to its intended use Consumption is supplied, the originally present goes ne integrity of the preservation system lost. At For example, the packaging must be opened before use nen. As an inevitable consequence of opening, air enters the Package content added. Because of the access to air, the Oxidation of the contents of the packaging or its secondary ver germination will occur because germs will also germinate with the air Spores get into the contents of the package.

The usage time of a product with disintegrated Preservation system is therefore through the during the The deterioration mechanisms that begin to consume are limited. When using one packaged in a lidded jar ten skin cream can also reduce the secondary contamination by the Cream-removing finger from the very first one diving.

That is why with cosmetic products that last for a longer period of time Consumption times are provided such. B. skin cream or Oil-water emulsions (skin milk), the process for con to arrange the serving in such a way that it is originally there dene, the non-spoiling storage of the packaged product guaranteeing preservation system also still the Ver The contents of the package can be seen within the foresight prevents the use-up period.

In the food industry, product-specific con Serving systems common, in which essentially the Packaging and the addition of at least one food item preserving substance to protect against spoilage of the Food guaranteed.

Such preservation systems and the means of chemi The preservation of foodstuffs is described in the textbook [1]. It is shown that type and amount the food-preserving chemical to be added Substances are limited. This is i.a. in those with the Ver Toxic resp. allergenic side effects justified.

These additives are therefore often available from the consumer's point of view in the way of a positive purchase decision. It is i.a. an object of the present invention, here Art and Amount of food-preserving additives so shape cash to make that said, the purchase decision the consumer's formative reservations are less important will.

In the cosmetics industry are used to protect the products predominantly used chemical preservatives that can also be used in the food industry.

But since cosmetics are not intended for consumption because of the wide variety of cosmetic products available also a corresponding number of other chemical ones Preservatives have been provided to help ensure one Carry out preservation adapted to the respective product to be able to. A deodorant stick is preserved differently fourth as a toning facial toner.

The chemical preservatives preferably used in cosmetic products are classified chemically as follows:

• - Organic acids: e.g. B. Sorbic Acid, Pro pionic acid, dehydracetic acid re, undecylenic acid, ben zoic acid, formic acid, Salicylic acid
• - Aliphat.-halogenorg. Ver bindings (not formals hydroscopic): z. B. dibromodicyanobutane, Iodopropynyl butyl carbamate, Chlorhesidin, chloromethyl isothiazolone, chloroaceta mid
• - Aromat.-halogenorg. Ver bindings: z. B. 4-chloro-m-cresol, Bromochlorophene, dichloro benzyl alcohol
• - formaldehyde releasers: z. B. Dimethyldimethylol- Hydantoin (DMDM hydan toin), Bronopol® (1,3-nitropropanediol), Imidazolidinyl urea, Bronidox® (5-bromo-5-nitro- 1,3-dioxane), diazolidinyl urea
• - Parabens: e.g. B. methyl, ethyl, Propyl, butyl, isobutyl parabens
• - Inorganic compounds: e.g. B. sulfites, silver ions, boric acid
• - Quaternary ammonium ver bindings: z. B. benzalkonium chloride, Cetyl pyridine chloride
• - alcohols (not halogen org.): e.g. B. benzyl alcohol, Phe noxyethanol
• - phenols: e.g. B. o-phenylphenol
• - Mercury org. Ver bindings: z. B. thiomersal
• - Natural substances / natural extracts: z. B. Tea tree oil, Neem treet extract, essential Oils, usnic acid, Myavert C® (lipid peroxide se, thiocyanate, glucose oxidase)
• - Antibiotics: e.g. B. nisin, natamycin, Lysocyme.

When designing one for a special cosmetic Suitable preservation systems are available in Given the wide variety of chemical con serving materials take several viable routes.

For example, the following preservatives are added as alternatives to shampoos:

• - sorbic acid or its salts
• - parabens
• - Benzoic acid or its salts
• - dibromodicyanobutane
• - salicylic acid or its salts
• - DMDM hydantoin
• - Bronopol®
• - benzalkonium chloride
• - formic acid or its salts
• - phenoxyethanol
• - (Chlor) -Methylisothiazolinone.

Crucial to the choice of chemical to use The preservative is that on the one hand it is sufficient adequate toxic safety guaranteed and on the other hand but also good dermatological tolerance shows. The toxic high-quality Kon serving materials are often problematic behavior increase their dermatological tolerance by for example acute skin irritations, contact allergies, phototoxic or photoallergic skin reactions or Cause eye irritation.

It is therefore an object of the present invention to be here Type and amount of cosmetic-preserving additives to make it so that both the toxic and the dermatological safety of the cosmetic product balanced entry.

Unfortunately, in the industrialized countries in the last few years already in the infants more symptoms of Skin irritations, which are known as "Neuro dermitis ". The skin care of the under Atopic dermatitis sufferers preferably have with cosmetic preparations to happen when they are put together exposure to substances that have an irritating effect on the skin has been waived in advance. The protection of such pre prepared against the occurrence of secondary contamination is a Problem that coincides with the aforementioned tasks with of the present invention becomes solvable.

The use of chemical preservatives did that The aim of the growth of the spoilage organisms, d. H. the ver increasing their number to prevent. Will be at the An application of the preservative the spoilage organisms killed immediately afterwards, this is how the preserve works microbiocidal agent.

The preservative used only suppresses it the propagation of the spoilage organisms, so the Kon acts microbiostatic serving material. Nevertheless it will be like that treated product made sterile. However, the Sterility only after some exposure time, namely Lich then, if all copies of all in the product originally lich existing spoilage organisms their respective Le the end of the line and the product against secondary Contamination is protected by the packaging.

The addition of a preservative to a cosmetic Product can be dosed in such a way that it is microbiostatic works and also a good dermatological tolerance given is. Preservatives that have this property are classified as "mild". Mild preservation agents in this sense are inter alia. Sorbic acid, Ben zoic acid, phenoxyethanol. It is known that the sorbin acidic cosmetic products protect against microbial attack and is well tolerated.

She is:

• - in the concentration relevant for cosmetic products well tolerated by skin and mucous membranes,
• - Not irritating to the skin according to EC Directive 84/449 and OECD test guideline 404,
• - not phototoxic,
• - classified as "safe" by the CIR Expert Panel.

Sorbic acid is also by its long standing and world widely used as a food preservative rehearsing. In this context, their ADI value is 0-25 mg / kg Body weight and day (ADI = Acceptable Dialy Intake). Sorbic acid does not cause any environmental pro bleme as they are in terms of their water hazard class is located in level 0.

In interaction with cosmetic ingredients, Sor bic acid good compatibility with cosmetic raw materials and shows no antagonistic effect with common Conser additives on.

"Synergistic" effects with Dehydracetsäu are known re, benzoic acid, parabens, EDTA and glycols.

Sorbic acid is not inactivated by non-ionic acids cosmetic ingredients and emulsifiers.

The microbiostatic effect of sorbic acid is also sustainable in all probability given in the future, because so far there are no resistance developments against Sor bic acid became known.

Sorbic acid protects cosmetic products during storage and gives protection against secondary infections during the Ge need.

Sorbic acid remains active for a long time.

It is also an aim of the present invention that we spectrum of use as a "mild" cosmetic preservative sorbic acid from the well-known concentrations tations (500 ppm to 2000 ppm) to the low applications dung concentrations to expand.

For the food industry or the cosmetics industry are also economic and legal framework conditions of considerable importance. A preservation ver must be able to be implemented on a large scale and the comply with applicable legal guidelines. A Konser In addition, the process should be gentle on the product and the stabilization of the raw materials just as certain such as the microbiological protection of the product.

In the journal "Food Marketing and Technology", Octo ber 1996, pages 58 to 65, has already been described wor the fact that it could in principle be possible to named requirements with a preservation process to meet which of a combination of a high pressure treatment and the addition of suitable preservation materials. In this publication Tests of chemical preservatives which are independent of one to be preserved Product have been pressurized to solid notify whether the properties of the preservation negatively change the substance through the high pressure treatment. Further details about such a preservation In addition, this publication also provides information not to be found.

The object of the invention is to provide a generic Conser vation process for solid, liquid or pasty ver coarse products such as food, animal feed and To create means for body and beauty care, wel ches has a high preservative effect, but at the same time with as little or tolerable con serving ingredients.

This task is carried out with a method of the initially be signed type according to the invention solved in that the too preservative product with at least one microbiosta table-acting preservative added and on is then subjected to the high pressure treatment.

It has surprisingly been found to be possible is, with such a combined method the ge desired result to be achieved. This ver drive from a combinatorial effect of the mikrobio static preservatives with a microbiocidal High pressure treatment. Due to the high pressure treatment a large number of the microorganisms found in the product killed, the high pressure acts among other things. also on the cell membrane of the microorganisms and changes the permeabili ity of the membrane. This effect on the cell membrane of the Microorganisms are increased by the high pressure treatment beyond the effectiveness of the microbiostatic Kon serving materials, as they form the cell membrane of the microor organisms can then penetrate better. It is created like this with a surprising synergistic effect through which High pressure treatment will have the effect of the same time microbiostatic preservatives obviously increased, d. H. these are more effective than without high pressure plot. This has the consequence that compared to conventional Conservation method the proportion of chemical preservatives can be reduced and that at the same time also have a microbiostatic effect, d. H. relatively "mild" con Serving materials can be used, which the Ver tolerability of the actual product, what in particular in food and cosmetics is essential, not influence negatively. The effectiveness of the procedure also seems to be positively influenced by the fact that important enzymes in the Ver organisms are activated, causing disorders revealed during biosynthesis as a further cause can be considered for the sterilization effect.

In an advantageous embodiment of the invention is provided hen that the high pressure treatment at pressures of 1,000 up to 10,000 bar, preferably to conserve Fourth product of high pressure treatment over time room from one second to several hours will. There is an interaction between the height the applied pressure and the duration of the pressure plot. The longer the pressure treatment carried out becomes, the lower the high pressure can be, each Appropriate treatment of course depends on each product to be preserved.

Preferably the high pressure treatment can be at ambient temperature can be carried out, which turned out has that with the aforementioned pressure values by the Pressure treatment a temperature increase in the range of up to 20 ° C. A treatment at higher or Lower temperatures are of course not an option closed.

The high pressure treatment itself is basically one Batch process. This batch operation is so suitable probably for packaged as well as for unpacked products. Be but it is particularly advantageous to preserve that de product in a sales area before high pressure treatment ratio filled and in this container the high pressure treatment. The high pressure treatment of the Products in their final packaging then ensures that no contamination by wearing parts, lubricants or print media can take place. The treated pro Products then do not need any further processing and can be placed on the market immediately.

A device with which the high pressure treatment according to the invention development can be carried out is in DE 44 21 341 C1 be wrote.

Sorbic acid and its salts, benzoic acid and its salts, propionic acid and its salts, parabens, nisin, natamycin and / or SO ₂ -generating substances have proven particularly useful as microbiostatic preservatives for preserving food.

The aforementioned are for the preservation of animal feed microbiostatic preservatives suitable about it also hexamethylenetetramine or formic acid.

For the preservation of means for body and beauty organic acids, ali, are particularly suitable phatic halogen organic substances, aromatic halo organic substances, formaldehyde donors and / or Parabens.

Compared to other preservatives, sorbic acid has a preservative effect substances have a favorable partition coefficient between Oil and water. This remains with oil-in-water emulsions a relatively high proportion of sorbic acid / sorbate in the back alone microbiologically susceptible water phase.

Skin cream or skin milk, i.e. an oil-in-water emul sion that is only 0.03% to 0.07% (30 to 70 ppm) Sorbic acid is added and a high pressure treatment he drive, spoils within the anticipated ups and downs duration not.

This is particularly surprising since the limit concentration functions of sorbic acid, in which the incubation of Nutrient solutions are prevented for the vast majority number of different spoilage organisms above from 500 ppm to 2000 ppm is given; [1], pp. 164/165.

That is why there is a special design of the present the invention, the cosmetic oil-in-water emulsio at least one mild chemical preservative to be added and this preparation by means of high pressure treatment in the finished cosmetic product too convict.

In particular, it is planned to do this with oil-in-water based preparations, which in their pH- Value are adjusted to the pH value of human skin. Such preparations are according to the invention with 0.03% up to 0.07% sorbic acid added or by means of an acid equivalent potassium sorbate concentration.

The invention is illustrated below by way of embodiment play explained in more detail by way of example.

example 1

In a pilot plant according to DE 44 21 341 C1 was used as a case game for a body and beauty care product a face cream preserved in a jar packaging.

The face cream is an oil-in-water emulsion. The following approaches are provided for its production:

The initially unpreserved face cream is cold stirs can be produced by entering B in A and the this intermediate batch then added to batch C with stirring is set.

After that, the initially unpreserved Ge Potassium sorbate face cream as a biostatic preservative added in an amount of 0.3%. To The face cream prepared in this way was then placed in the deformable jar packaging in a pilot plant for the High pressure treatment entered which essentially from a printing cylinder with a diameter of 120 mm and a length of 400 mm and which the on enables a pressure of up to 6,000 bar.

At a temperature T of 25 ° C and a pressure of 4,000 bar, various samples were tested over 5, 10, Pressurized for 15, 20 or 25 or 30 minutes.

A correspondingly durable product resulted, which also in use, d. H. after opening the Ver packaging and the resulting contamination up to Remained stable for 36 months.

In order to demonstrate the toxic safety of the face cream preserved with the method according to the invention, the individual samples were primarily contaminated with high bacterial counts as follows prior to the high-pressure treatment, each sample being inoculated with only one species of the spoilage organisms:

- Pseudomonas aeruginosa cfu = 10 ^5.86 / ml - Staphylococcus aureus cfu = 10 ^6.86 / ml - Penicillium expansum cfu = 10 ^6.76 / ml - Candida albicans cfu = 10 ^7.21 / ml - Aspergillus niger cfu = 10 ^6.10 / ml - other germs cfu = 10 ^6.74 / ml

All germs that are initially contaminated in the preparation genes are contained by the high pressure treatment killed. On none of the culture media used and with no incubation temperature can be the originally germs present after the high pressure treatment point.

Example 2

The pilot plant was used as an example of a means for Body and beauty care a low-preservative Skin milk for sensitive, especially for neuro dermitis weakened skin in a deformable bottle preserved.

The skin milk is an oil-in-water emulsion. The following approaches are provided for its production:

The initially unpreserved skin milk is stirred cold can be produced by entering B in A and this Intermediate batch then added to batch C with stirring will.

After that, the initially unpreserved one became available Skin milk potassium sorbate as a biostatic preservative medium added in an amount of 0.03%. Afterward the skin milk prepared in this way was placed in the deformable Bottle in a pilot plant for high pressure treatment entered, which essentially consists of a Druckzylin the one with a diameter of 120 mm and a length of 400 mm and which requires the application of a pressure up to 6,000 bar.

At a temperature T of 25 ° C and a pressure of 4,000 bar, various samples were tested over 5, 10, Pressurized for 15, 20 or 25 or 30 minutes.

A correspondingly durable product resulted, which also in use, d. H. after opening the Ver packaging and the resulting contamination up to one Month remained stable.

In order to demonstrate the toxic safety of the skin milk preserved with the method according to the invention, individual samples of completely unpreserved skin milk were primarily contaminated with high bacterial counts as follows before the high-pressure treatment, each sample being inoculated with only one species of the spoilage organisms:

- Pseudomonas aeruginosa cfu = 10 ^6.29 / ml - Staphylococcus aureus cfu = 10 ^7.16 / ml - Penicillium expansum cfu = 10 ^7.00 / ml - Candida albicans cfu = 10 ^7.14 / ml - Aspergillus niger cfu = 10 ^6.25 / ml - other germs cfu = 10 ^6.75 / ml

All germs that are initially contaminated in the preparation genes are contained by the high pressure treatment killed. On none of the culture media used and with no incubation temperature can be the originally germs present after the high pressure treatment point.

Example 3

In the pilot plant was used as an example of a food tel a concentrate drink (Raspberry Flavor Drink), wel ches was filled into a flexible PE bottle, preserved fourth.

For this purpose, the samples were given 0.015% potassium sorbate as biostati Preservative added. Subsequently was the beverage sample in a pilot plant for high pressure treatment entered, which essentially consists of a Printing cylinder with a diameter of 120 mm and one Usable length of 400 mm and a movable yoke for opening and closing. This system enables pressures up to 6,000 bar with any pressure holding times.

In this case the samples were kept at a temperature of 19 ° C and a pressure of 2,000, 4,000 and 6,000 bar 5 and pressurized for 10 minutes. Here, too, surrendered an appropriately durable product.

Achieved shelf life: up to 12 months.

Of course, the invention is not limited to those illustrated Embodiments limited. It can also be a Konser vation material are used, which is not only microbi acts statically, but also additionally or alternatively microbiocidal.

List of publications

[1] Lück, E. and Jager, M. (1995): Chemische Lebens medium preservation, substances-effects-methods, Berlin: Springer Verlag, 3rd edition.

[2] PRESERVATECH, The International Conference and Exhibition featuring Preservatives and Preserva tion Techniques for Cosmetics, Toiletries and Pharmaceuticals. Conference Proceedings, Le Pa lais dew Congrés de Paris, FRANCE, 5-6 December 1995, publishing house for the chemical industry: H. Ziol kowski GmbH, Contribution by Dr. Martin Jager: "Sorbic Acid - The Gentle Alternative for Pre servation ".

[3] Niedner, R. (1992): The skin compatibility kos metically relevant preservatives. SÖFW- Journal 118, 541-543.

[4] Walker, R. (1990): Toxicology of sorbic acid and sorbates. Food Additives and Contaminants 7, 671-676.

[5] Yousef, R. El-Nakeeb, M. and Salama, S. (1973): Effect of some pharmaceutical materials on the bactericidal activity of preservatives. Canadian Journal of Pharmaceutical Science 8, (2) 54-56.

Claims (9)

1. A method for the preservation of solid, liquid or pasty perishable products such as food, feed and cosmetics, wherein the product to be preserved is subjected to a high-pressure treatment, characterized in that the product to be preserved with at least one microbiostatic active preservative is added and then subjected to high-pressure treatment. 2. The method according to claim 1, characterized, that the high pressure treatment at pressures from 1,000 to 10,000 bar. 3. The method according to claim 2, characterized, that the product to be preserved is the high pressure treatment over a period of one second to several hours which is subjected. 4. The method according to claim 2 or 3, characterized, that the high pressure treatment at ambient temperature is carried out. 5. The method according to claim 1 or one of the following, characterized, that the product to be preserved before the high pressure action filled into a sales container and in this Container is subjected to high pressure treatment. 6. The method according to claim 1 or one of the following, characterized in that for the preservation of food sorbic acid and its salts, benzoic acid and its salts, propionic acid and its salts, parabens, nisin, natamycin and / or SO ₂ generating substances as microbiostatic preservatives fabrics are used. 7. The method according to one or more of claims 1 to 5, characterized in that for the preservation of feed sorbic acid and its salts, benzoic acid and its salts, propionic acid and its salts, parabens, nisin, natamycin and / or SO ₂ generating substances and / or hexamethylenetetramine or formic acid are used as preservatives. 8. The method according to one or more of claims 1 to 5, characterized, that for the preservation of means for body and beauty health care organic acids, aliphatic halogen orga niche substances, aromatic halogen organic subs dance, formaldehyde and / or parabens as a preservative material can be used. 9. The method according to claim 1 or one of the following, characterized, that the product to be preserved additionally with little at least a microbiocidal preservative is moved.