NZ205540A

NZ205540A - Method of protecting a feedstuff against microbial spoilage

Info

Publication number: NZ205540A
Application number: NZ205540A
Authority: NZ
Inventors: Freimut Riemer
Original assignee: Freimut Riemer
Priority date: 1982-09-10
Filing date: 1983-09-09
Publication date: 1987-08-31
Also published as: PL141856B1; IE832119L; IT1170481B; FI76245B; FI841866A; PL243701A1; DK217384A; DE3233607A1; DK217384D0; DE3372695D1; EP0119226A1; FI76245C; ZA835703B; JPS59501534A; WO1984000877A1; TR22359A; GR78997B; DD218550A5; PT77311A; PT77311B

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £05540 Complete Specification Filed: Class: X&V51 S>k U Date. j NO*< giliaiilil'itl.l.aiaa. Publication Date: P.O. Journal NO DRAWINGS 205540 Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION "A PREPARATION FOR ANTIMICROBIALLY TREATING FEEDS AND FOODSTUFFS" I,WE FREIMUT RIEMER of German nationality of Hofgensweg 8, D-5135 Selfkant-Tuddern, Germany hereby declare the invention, for which I Are-pray that a patent may be granted to me/«67 and the method by which it is to be performed, to be particularly described in and by the following statement _1~ (followed by page \ *.) 205540 -IX- FREIMUT RIEMER A PREPARATION FOR AMTIMICROBIALLY TREATING FEEDS AND FOODSTUFFS. The invention concerns a preparation for anti-microbially treating deep-frozen 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, said means being admixed with a quaternary onium compound with at least one further ingredient. A method is kncwn in the art which describes the antimicrobial treatment of specific feeds wherein quaternary onium compounds together with polyalkylene glycols in an aqueous solution or dispersion are admixed to the feed and used on them at raised temperature. This method permits treating especially dry feed meals anti-microbially with satisfactory success. Compared to the 205540 -2- other known chemical disinfectants and the physical germicidal methods, the preparation used above is characterized by a relatively good long term action 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 length of effective antimocrobial action is not fully satisfactory , especially the antimicrobial treatment of foodstuffs, in particular those intended to be kept deep-frozen. 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 already 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 long term 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) can not 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 this known method is that the solution, or the dispersion, must be heated to improve the solubility and the effectiveness in application..This fact too — besides the -3- 205540 cost in equipment and energy - also restricts the scope of applicability. It is therefore an object of the invention to provide a preparation for antimicrobially treating a large number of feeds and foodstuffs, especially deep-frozen foodstuffs, said preparation furthermore being characterized by a broad effective antimicrobial spectrum and good long term effect. Such long term effect is herein referred as the depot effect. In accordance with the invention in addition to the quaternary onium compound, at least one isothiazolinone compound is also included. Such isothiazolinone compounds are described per se for instance the US Patent 37 61 488, but not in combination with quaternary onium compounds and not in relation to the range of applications considered herein. 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 a synergistic effect is obtained. Thus the antimicrobial effect and also the effective spectrum are substantially improved. Therefore the preparation can 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 unfavourable conditions must be emphasized because it is effective and soluble already at ordinary room temperatures, even at a few degress above 0°C. Heating, is not needed in the present invention. None of the chemical disinfectants or the known physical germicidal methods that the applicant is aware of on the market can offer similar favourable properties. Either they are inferior on toxicological or process-technological grounds, or on such grounds as cost|f.^aad:>v effectiveness, especially the depot effect, when "compare^ to the preparation of the invention. jL: f 23APR 1986d -4- 205540 These impressive advantages are unexpected because the quaternary onium compounds generally lack a broad spectrum of effectiveness and their depot effect is comparatively brief. Furthermore the onium compounds tend to lose their germicidal action when in the presence of anionic active substances and accompanying substances containing proteins. The isothiazolinone compounds are not generally microbicidal with respect to such microorganisms as fungi, bacteria, yeasts and algae. Such effect however is required in such treatment processes of washing, rinsing, dipping, spraying or steeping. The isothiazolinone compounds of the invention are preferably of the general formula I: X Z O r (i) ^.N-Y S"^ where X and Z are independently a hydrogen, chlorine or bromine atom or an alkyl group, and Y is an alkyl group of 1 to 18 carbon atoms, a cyclohexyl group, an aralkyl group with up to 10 carbon atoms optionally substituted by a lcwer (C^ to G^q) alkyl or alkoxy group, a 2- or 4-chlorobenzyl group, a 2,4- or 3,4-dichlorobenzyl group* a hydroxymethyl group, a phenyl group optionally substituted by a chlorine atom or a lower alkyl, nitro or carbethoxy group, or a group of formula » -c-nhr6 *5 where R5 is an oxygen or sulphur atom and is an alkyl group with 1 to 8 carbon atoms, a carbethoxymethyl group a chlorophenyl group, a 2,5- or 3,4-dichloro-phenyl group or a 4-nitrophenyl group. Especially preferred isothiazolinone compounds are 5-chloro-2-methyl-4-isothiazdline-3-one and 2-methy1-4-isothiazoline-3-one preferably present as a mixture o£ 3 parts of the former with 1 part of the J^tt^f.F^Jiese • f/M <'■ 01 " 2 3 APR 1986" -5- V c. Q J compounds have the formula: .0 cX The quaternary onium compounds can be a quaternary sulfonium compound or other quaternary sulfur containing compound but is preferably a quaternary ammonium compound substituted by suitable hydrocarbon containing groups. Numerous suitable bactericidal and fungicidal quaternary ammonium compounds are known, for example those described in U.S. Patent No. 2807614. More preferably the quaternary ammonium compound is one in which at least one of the nitrogen substituents is a higher (c^ t° C^g) molecular weight alkyl group. Even more preferably the quaternary ammonium compound is a compound of the formula II © X © (id in which at least one of the groups to R^ is an alkyl group of from 8 to 18 carbon atoms, and the other groups are lower molecular weight alkyl or aryl or aralkyl groups, and X © is a suitable anion such as a halide ion. Most preferably the quaternary'ammonium compound has the formula ^ ch,— n —ch-3 | J CI where the substituent R is a higher-molecular n-alkyl (C^q to C^g), most preferably where the substituent R is a n-alkyl _ E N /" mixed group with the distribution of 40% of C12 o0% o of C14 and 10% of C16. V % "16 JUN1987 \\ \ ©I h -6- 205540 The weight ratio of the mixture of quaternary onium compound to the isothiazolinone compound or compounds can vary and will generally be within the range of 1:1 to 20:1, preferably in the range 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 is generally adequate. Where the preparation is used for foodstuffs, an aqueous solution with a concentration of 1:500 to 1:2500 is recommended, for instance in washing, rinsing, spraying and steeping waters used in the last production step prior to the deep-freeze stage. The invention is illustrated by the following non-limiting examples: Example 1 * A mixture was prepared of 9 parts by weight of a quaternary ammonium with the substituents dimethyl, benzyl and n-alkyl, the latter being a combination of 40% of C12, 5035 of Cl4 and 10% of Cl6, and 1 part by weight of a mixture of two isothiazoline compounds 5-chloro-2-methyl- ^-isothiazoline-3-one and 2-methyl-4-isothiazoline-3-one 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) and where wholly coated with Tetrathionate enrichment medium and incubated at 40°C. 24 h later, over-inoculation was performed on a -7- 205540 selective medium (S.S. agar, Wilson&Blair, McConckey) and salmonella growth was looked for. Several of the test samples were reinfested 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 salmella infestation with a depot effect of at least 12 months in commercial storage. 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 last step before the deep-freeze stage. The resulting 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 thaw-water after short or long deep-frozen storage times. -An experiment in which a short thaw period at +5°C was followed by a new deep-firozen period again proved negative after the final product thaw. Example 3 A conventional test was carried out to determine the bactericidal and fungicidal effectiveness of two test </div>

Claims

<div class="application article clearfix printTableText" id="claims"> - 8 - 2055 4 0 components. One test component was the mixture described in Example 1, while the other, herein called the control component, was described in the German patent 24 50 666. In this control component, one part by weight of a quaternary ammonium salt with the substituents dimethyl, benzyl and n-alkyl; the latter being a combination of 50% of C12, 30% of C14, 17% of C16 and 3% of C18 was mixed with 2 parts by weight of an aqueous polyethylene glycol dispersion, (having a solid content of 20% and a molecular weight of about 600). Both the invention and the control components were always serially diluted in tripticase soybean extract. Then they were subjected to inoculation with test bacteria, namely 24-hour old bacteria cultures (in the proportion of 1 part of the test component to 100 parts of bacteria culture), and to a suspension of mold traces, namely 7 to 14 days old mold cultures washed in 7ml of deionized water. The bactericidal or fungicidal effectiveness was visually 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. The resulting values are listed below in ppm of the active substances: Microorganism Invention component Control component Aspergillus niger 500 1,000 Pseudomonas aeruginosa 25 70 Salmonella typhosa 9 20 Staphylococcus aureus 7 20 Escheria coli 10 25 The table shows the component of the invention compared to that of the control component known from the German patent 24 50 666.is substantially more effective with respect to all the microorganisms cited herein. 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 slaughterhouses, cold-storage depots or hospitals, such as to dis- / infect 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. - 9 - o n r: R /- r) 'u J J • ^ what i claim is:

1- A method of protecting a feedstuff against microbial spoilage -comprising, subjecting the feedstuff to the effect of an antimicrobial preparation comprising a quaVtern^y ammonium compound mixed with a synergistic amount of at least one isothiazolinone compound in the weight ratio of 1:1 to 20:1. ~ 2. A method as claimed in clam 1, characterized in that the or each isothiazolinone ccrnpcrund is of the following general formula I: (I) ^l-Y 'S where X and Z are independently a hydrogen, chlorine or bromine atom or an alkyl group, and Y is an alkyl group of 1 to 18 carbon atoms, a cyclohexyl group, an aralkyl group with up to 10 carbon atoms optionally substituted by a lower alkyl or alkoxy group, a

2- or 4-chlorobenzyl group, a 2,4- or 3,4-dichlorobenzyl group, a hydroxymethyl group, a phenyl group optionally substituted by a chlorine atom or a lower alkyl, nitro or carbethoxy group, or a group of formula -c-nhr6 II R5 where R5 is an oxygen or sulphur atom and Rg is an alkyl group with 1 to 8 carbon atoms, a carbethoxymethyl group, a chlorophenyl group, a 2,5- or 3,4-dichloro-phenyl group or a 4-nitrophenyl group. 3. A method as claimed in claim 1 or 2, characterized in that the isothiazolinone compound is a mixture of 5-chloro-2-methyl-4-isothiazoline-

3-one and 2-methyl-

4-isothiazoline-3-one in the proportions of 3 parts by weight of the former and 1 part by weight of the latter. ? C 5 50 - 10 - 4. A method as claimed in any one of claims 1 to 3 wherein at least one of the nitrogen substituents in the quaternary ammonium compound is a higher molecular hydrocarbon containing group.

5. A method as claimed in claim 4 wherein the quaternary ammonium compound has the formula N © X © in which at least one of the groups to R^ is an alkyl group of from 8 to 18 carbon atoms, and the other groups are lower molecular weight alkyl or aryl or aralkyl groups, and X® is a suitable anion. :/

6. A method as claimed in claim 5 in which the anion is a halide ion.

7. , A- method as claimed in any one of claims 1 to 6, characterized in that the quaternary ammonium compound has the formula: © CH. ■N CH: CI where the substituent R is a higher-molecular n-alkyl. - 11 - O n n: r, / o \ >„• v.' *"

8. A method as claimed in claim 7 in which a mixture of 3 quaternary ammonium compounds having the formula given in claim 7 is present such that 40% of the compounds have a C12~n~alkyl group as R, 50% of the compounds have a C14-n-alkyl group as R and 10% of the compounds have a C^g-n-alkyl group as R. freimut riemer By their Attorneys BALDWIN, SON & CAREY </div>