IE54510B1

IE54510B1 - A preparation for antimicrobially treating feeds and foodstuffs

Info

Publication number: IE54510B1
Application number: IE2119/83A
Authority: IE
Original assignee: Riemer Freimut
Priority date: 1982-09-10
Filing date: 1983-09-09
Publication date: 1989-10-25
Also published as: IN160407B; NZ205540A; PL141856B1; KR840006223A; ES525504A0; CS248708B2; IT1170481B; PT77311A; FI76245C; WO1984000877A1; FI76245B; DK217384D0; DD218550A5; PT77311B; EP0119226B1; FI841866A; FI841866A0; ES8501212A1; PH23454A; AU1948883A

Abstract

In an empty antimicrobial treatment process, particularly for food products intended to be deep-frozen such as fish, meat, shrimps, poultry as well as fudder products, particularly dry fodder based on fish and whale waste, shrimp meal, milled animal carcasses, meat and dried blood fodder meals, a quaternary onium compound, particularly a quaternary ammonium compound, is mixed with at least another ingredient. In order to obtain a wider activity spectrum and an improved deposition effect, the other ingredient is at least an isothiazolinone compound. [DE3233607A1]

Description

FREIMUT KIKMEH ft PREPARATION FOR ANTIM1CR0BIALLY TREATING FEEDS AND FOODSTUFFS The invention concerns a preparation for antlmicrobially treating foodstuffs such as fish, meat, shrimps, fowl, and also feeds, especially dry feeds made from the wastes of whale and fish, shrimp meal, animal-body derived meal, meat-feed meal and blood-derived meal, especially foodstuffs or feeds intended to be deen frozen}in ammonium which preparation a quaternary ) compound is admixed with at least one further ingredient.

The German patent 4 510 -2other known chemical disinfectants and the physical germicidal methods, the preparation used above Is characterized by a relatively good depot effect and low toxicity, further by Its economy.

However the effective spectrum of that method against the various microorganisms has been found more restricted than desirable for universal applicability.

Again the depot effect does not fully satisfy. This is the case most of all for the antimicrobial treatment of the feeds not listed In the German patent 24 50 666 and also for foodstuffs, in particular those Intended to be kept deepfrozen. It is precisely in that area however, that because of the world-wide rising demand for deep-frozen foodstuffs and their shipping over very long distances, that the risk of salmonella Is very high. This infestation can take place during the processing stage, or by the temperature rising for a short time above 0°C during shipping. The development of pathogenic germs, especially salmonella, then becomes evident. Fatal cases of salmonellosis are ascertained daily worldwide.

Accordingly antimicrobial treatment of deep-freeze foodstuffs is indicated to preserve the goods free from pathogenic germs prior to the freezing process. Furthermore a certain depot effect is desirable so that no pathogenic germs, especially salmonella, can occur in the product or in the thawing liquid. Physical germicidal methods (heat sterilization, ultra-violet irradiation) cannot be applied at all, or only in a restricted scope. Heat sterilization cannot be used during the production cycle in deep-freeze manufacture The immense energy costs entailed by rapid cooling to the required temperatures together with danger of a meantime renewed infection of the goods can be seen at once.

A further drawback incurred by the means known from the German patent 24 5θ 666 Is that the solution, or the dispersion, must be heated to Improve the solubility and effectiveness in application. This fact too — besides the - 3 cost in equipment and energy — also restricts the scope of applicability.

It is therefore an object of the invention to create a preparation allowing antimicrobial treatment of a large number of feeds and foodstuffs, especially deep-freeze foodstuffs, said preparation furthermore being characterized by a very broad effective spectrum and improved depot effect.

This problem is solved by the invention in that the further ingredient which is to be mixed with the quaternary ammonium compound is at least one isothiazolinone compound. Such isothiazolinone compounds are described per se in, for instance, the U.S. Patent3,761,488, but not in combination with quaternary anmonium compounds in relation to the range of applications considered herein.

The invention thus comprises use of a quaternary anmonium compound with an isothiazolinone compound with a mixture ratio by weight of the two compounds in the range 1 : 1 to 20 : 1 as a preservative for food products intended especially for low-temperature cooling, and for fodder products, the isothiazolinone compound(s) having the following general formula: wherein both R and Rl signify hydrogen atoms, chlorine atoms, bromine atoms or methyl groups, and wherein Y signifies an alkyl group with three to eighteen carbon atoms, a cyclohexyl group, an aralkyl group with up to ten carbon atoms optionally substituted by a low-molecular alkyl group or a low-molecular - 4 alkoxy group, a 2- or 4-chlorobenzyl group, a 2,4- or 3,4-dichlorobenzyl group, a hydroxymethyl group, a phenyl residue optionally substituted by chlorine, low-molecular alkyl groups, a nitro group or carbethoxy group, or a carbamoxyalkyl group of the general formula: - C — hnr2 wherein X signifies an oxygen atom or a sulphur atom and R2 an alkyl group with one to eight carbon atoms, a carbethoxymethyl group, a chlorophenyl group, a 2,5- or 3,4-dichlorophenyl group, or a 4-nitrophenyl group.

The isothiazolinone compound(s) is(are) preferably an isothiazoline compound with the composition 5-chloro-2-methyl 4-isothiazoline-4-one and 2-methyl-4-isothiazoline-3-one in the ratio by weight 3 : 1, and has(have) the formula: - 5 The quaternary ammonium compound most suitably has the formula CH H3C - N -CH3 Cl wherein the substituent R is a Cq2-Cqg n-alkyl. The invention also encompasses a mixture as defined hereinabove for use as a preservative for food products intended especially for low-temperature cooling, or for fodder products.

The mixture of the invention is characterized by properties which could not be expected in the light of the known properties of the individual ingredients and accordingly must be based on synergy. Thus the antimicrobial effect and also the effective spectrum are substantially improved. Therefore the mixture may be used for the antimicrobial treatment of a large number of feeds and most of all for foodstuffs, being especially suited for deep-frozen foodstuffs. It was found that it provides an excellent depot effect over very long times. Its easy handling even under technically unfavorable conditions must be emphasized because it is effective and soluble at ordinary room temperatures, and even at a few degrees above 0°C. Heating, such as is required in the means of the German Patent 24 50 666, is not needed in this case. 5451(, - 6 None of the chemical disinfectants or the known physical germicidal methods available on the market can offer similar favorable properties.

Either they are inferior on toxicological or process-technological grounds, or as regards costs and effectiveness, especially the depot effect, when compared to the preparation of the invention.

These impressive advantages are unexpected because the quaternary ammonium compounds lack so broad a spectrum of effectiveness and their depot effect is comparatively brief. Furthermore they lose their germicidal action when in the presence of anion-active substances and accompanying substances containing proteins. The isothiazolinone compounds lack a mortifying effect with respect to such microorganisms as fungi, bacteria, yeasts and algae that however is essentially required in the treatment processes of washing, rinsing, dipping, spraying or steeping.

The isothiazolinone compounds of the general formula stated in Claim 1 were found especially suitable, especially favorable values being obtained using isothiazolinone compounds which are prepared as isothiazolinone compounds with the composition 5-chloro-2-methyl-4-1sothiazoline-3-one and 2-methyl-4-isothiazoline-3-one. The associated graphic representation of the formula is found in Claim 2. The molecular weights of these isothiazoline compounds are respectively about 148.5 and 114.

The applicable quaternary ammonium compounds are those indicated by the general formula provided in Claim 1, the quaternary ammonium compound with the formula stated in Claim 4, where the substituent R is an n-alkyl with the distribution of 40% of C12, 50% of CT4 and 10% of C16, having been found advantageous.

The weight ratio of the mixture of the quaternary ammonium compound to the isothiazolinone compound should be within the range of 1:1 to 10:1, preferably in the region of 9:1.

The preparation of the invention can be employed in a simple manner in antimicrobial treatment. When used for feeds, a weight ratio of one part of the preparation of the invention to 50 to 250 parts of the feed should be 545 10 - Ί observed. Where the preparation is used for foodstuffs, an aqueous solution with a concentration of 1:500 to 1:2,500 is recommended, for instance in washing, rinsing, spraying and steeping waters used in the last production step prior to the deep-freeze stage.

Manufacture of the preparation described herein takes place by mixing the isothiazolinecompound in question with the quaternary ammonium compound in question, the former being preferably mixed into the latter. The mixing preferably takes place at temperatures between 25 and 45°C, and in addition at atmospheric pressure. 545 10 The Invention Is Illustrated below.

Example 1 A mixture was prepared of 9 parts by weight of a quaternary ammonium salt with the substituents dimethyl, benzyl and n-alkyl, the latter being distributed In 40% of C12, 50% of Cl4 and 10% of C16, and 1 part by weight of an lsothiazollne compound of the composition 5-chloro-2-methyl4-lsothlazoline-3-one (3) + 2-methyl-4-lsothiazollne-3-one (1). This mixture was added in a ratio of 1:100 to a crude amount of fish meal or animal meal. The crude amounts were Inoculated with various salmonella strains (Salmonella Eimsbuettel, S. Livingstone, S. Montevideo), were wholly coated with Tetrathlonate enrichment medium,and Incubated at 4o°C. 24 h later, over-inoculation was performed on a selective medium (S.S. agar, Wilson&Blalr, McConckey) and salmonella growth was looked for. Several of the test samples were relnfested during the test duration to ascertain resistance to renewed salmonella Infestation.

During the first test interval of three months,no renewed salmonella infestation was determined with or without reinfection, whether in the fish or in the animal meal. The test samples were re-examined after 6, 8 and 12 months to determine whether the initially Inoculated salmonella strains can be isolated again after that storage time. In all samples the result was negative. Accordingly the mixture used in this example provides Immediate protection against salmonella infestation with a depot effect of at least 12 months in commercial storage. 4 510 Example 2 The same mixture as In example 1 was added in the ratio of 1:1000 to the washing, rinsing, spraying or steeping water used in treating foodstuffs for deep-freezing, each time at the particular last step before the deep-freeze stage. The ensuing quick-frozen products were stored according to manufacturers' recommendations, and, following thawing,were subjected to bacteriological examination for salmonella infestation. Neither salmonella nor other pathogenic germs were found in the product or in the thawwater after short or long deep-freeze storage times. An experiment in which a short thaw period at +5°C was followed by a new deep-freeze period again proved negative after the final product thaw.

Example 3 A conventional test was carried out to determine the bactericidal and fungicidal effects, the effectiveness of two test components being sought. The one test component was the mixture already known from examples 1 and 2, while the other, herein called the control component, was the illustratively cited mixture in the German patent 24 50 666.

In this mixture, one part by weight of a quaternary ammonium salt with the substituents dimethyl, ethyl, benzyl and n-alkyl, the latter In a distribution of 50Ϊ of C12, 30X of Cl4, 17X of Cl6 and 3ί of Cl8 was reacted with 2 parts by weight of an aqueous polyethylene glycol dispersion, resulting In a solid content of 20X and a molecular weight of about 600.

Both the test and the control components were always serially diluted in triptlcase soybean extract. Then they were subjected to a 1:100 inoculation with test bacteria, namely 24-hour old bacteria cultures, and to a suspension of mold traces, namely 7 to 14 days old mold cultures washed in 5451 - 10 7ml of deionized water. The bactericidal or fungicidal effectiveness was determined after 24 h of Incubation at 37°C for bacteria and after 48 h of Incubation at 28 to 30°C for the molds, this determination being visual. The resulting values are listed below in ppm of the active substances: were: Microorganism Test component Control component Aspergillus niger 500 Pseudomonas aeruginosa 25 Salmonella typhosa 9 Staphylococcus aureus 7 Escheria coll 10 1,000 The table shows that the effectiveness of the test component of the Invention compared to that of the control component known from the German patent 24 50 666, referred to the particular active substance, ls substantially Improved with respect to all the microorganisms cited herein The application of the preparation of the invention is not limited to the treatment of foodstuffs or feeds. The preparation is also suited for surface treatment, for example in slaughter-houses, cold-storage depots or hospitals, as well as /to disinfect walls, floors and devices installed or handled therein. Further, the preparation can successfully be used for the treatment of water, especially drinking-water and oilfield-water.

Claims

I. Use of a mixture of a quaternary ammonium compound with an isothiazolinone compound with a mixture ratio by weight of the two compounds in the range 1:1 to 20:1 as a preservative for food products intended especially for low-temperature cooling, and for fodder products, the isothiazolinone compound(s) having the following general formula: wherein both R and Rl signify hydrogen atoms, chlorine atoms, bromine atoms or methyl groups, and wherein Y signifies an alkyl group with three to eighteen carbon atoms, a cyclohexyl group, an aralkyl group with up to ten carbon atoms optionally substituted by a low-molecular alkyl group or a low-molecular alkoxy group, a 2- or 4-chlorobenzyl group, a 2,4- or 3,4-dichlorobenzyl group, a hydroxymethyl group, a phenyl residue optionally substituted by chlorine, low-molecular alkyl groups, a nitro group or carbethoxy group, or a carbamoxyalkyl group of the general formula: HNR 2 II X - 12 wherein X signifies an oxygen atom or a sulphur atom and R ? an alkyl group with one to eight carbon atoms, a carbethoxymethyl group, a chlorophenyl group, a 2,5- or 3,4-dichlorophenyl group, or a 4-nitrophenyl group.
2. Use according to Claim 1, characterised in that the isothiazolinone compound(s) is(are) an isothiazoline compound with the composition 5-chloro-2-methyl 4-isothiazoline-4-one and 2-methyl-4-1sothiazoline-3-one in the ratio by weight 3:1, and has(have) the formula: HC-C— 0 H—C Cl - C N—CH 3 H— C N - CH 3
3. , Use according to Claim 1, characterised in that the quaternary ammonium compound has the formula h 3 c CH N — CH 3 Cl - 13 wherein the substituent R is a C q2 -C 16 n-alk y 1 ·
4. Use according to Claim 3, characterised in that the n-alkyl has the distribution 40% C^, 50% and 10% C^ g .
5. Use according to Claim 1 or 2, characterised in that the mixture ratio by weight is approximately 9:1.
6. A preparation comprising a mixture as defined in any of Claims 1 to 5, for use as a preservative for food products intended especially for low-temperature cooling, or for fodder products.
7. Use of a preparation as defined in Claim 6 for fodder products in a wight ratio of one part of the preparation to 50 to 250 parts of the fodder product.
8. Use of a preparation as defined in Claim 6 for food products in an aqueous solution in a concentration of 1 : 500 to 1 : 2,500.
9. A method for manufacture of a preparation as claimed in Claim 6, substantially as described herein by way of example.
10. A preparation for the antimicrobial treatment of foodstuffs for humans or animals, substantially as described herein by way of example. Dated this 9th day of September, 1983. BY:- TOMKINS 4 CO., Applicant's Agents, (Signed)