CA1069375A - Antimicrobial and antirancidity agent - Google Patents

Antimicrobial and antirancidity agent

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Publication number
CA1069375A
CA1069375A CA246,117A CA246117A CA1069375A CA 1069375 A CA1069375 A CA 1069375A CA 246117 A CA246117 A CA 246117A CA 1069375 A CA1069375 A CA 1069375A
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CA
Canada
Prior art keywords
aqueous material
tertiary butyl
butyl hydroquinone
weight
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA246,117A
Other languages
French (fr)
Inventor
David R. Erickson
Robert B. Tompkin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JBS USA LLC
Original Assignee
Swift and Co Inc
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Filing date
Publication date
Application filed by Swift and Co Inc filed Critical Swift and Co Inc
Application granted granted Critical
Publication of CA1069375A publication Critical patent/CA1069375A/en
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Abstract

ANTIMICROBIAL AND ANTIRANCIDITY AGENT
Abstract of the Disclosure:
An aqueous composition includes a normally biode-gradable component and contains teritary butyl hydroquinone to inhibit microbial growth. Oxidative rancidity is also controlled when the composition has a fat or oil content. A
method is described which adds teritary butyl hydroquinone to aqueous biodegradable materials in concentration that inhibit microbial growth.

Description

~069~75 Specification:
The present invention relates to an aqueous com-position containing tertiary butyl hydroquinone in bacterio-static concentrations and an improved method for inhibiting microbial growth in aqueous, normally biodegradable materials.
Terti-ary butyl hydroquinone (TBHQ) is known from the prior art to ha~e anti-rancidity properties in that, at rela-tively low concentrations, it inhibits oxidative rancidity of fats and/or oils-in various materials. Such materials include foods, soaps, food deri~atives, industrial oils, and the like.
It is believed that the rancidity is chemically induced when atmosp-heric oxygen reacts with fats or oils in such'items to accomplish an autoxidative'production of peroxides that break down into aldehydes and ketones which exhibit odors character-istic of rancidity. The prior art teaches that tertiary butyl hydroquinone, at relatively low concentrations, will prevent this autoxidation and the resulting oxidative rancidity of fats and oils. ' Many of these's~me'types of materials have'a water ' cont~nt as well as a fat-or oil content. Others, while they have'little'or no fat or oil, do contain water. These types of water-containing compositions or materials are exemplified by glues, gelatins, adhesives, starches, and the like. These types of materials can be considered as being normally sup-portive of microbial, mold or bacterial growt~. The'terms "aqueous material" or "aqueous, normally biodegradable mater-ial" are used interchangeably herein to refer to materials that include enough moisture so as to provide'a medium for the'growth of microorganisms, whether or not they also have' a fat and/or oil contentO
In many instances, it is desirable to control the growth'of microorganisms within these aqueous materials so as to retard undesirable decomposition and putrefaction.
Heretofore,it has not been recognized that tertiary butyl hydroquinone will, when added in relatively high concentra-tions, inhibit the growth of microorganisms within aqueous, normally biodegradable materials.
Accordingly, an object of the present invention is an improved aqueous material that is resistant to the growth of decomposing and putrefying microorganisms and a method for producing same.
Another object is an improved aquebus material con-taining fats-or oils and method for producing that material so that it resists both oxidative rancidity and the growth of microorganisms therein.
One other object o~ this invention is an improved aqueous material and method utilizing tertiary butyl hydro-quinone as an agent for inhibiting the'development of micro-organism growth.' The present invention is an improved aqueous material which includes tertiary butyl hydroquinone present in concentrations that inhibit microorganism growth and an improved method fsr inhibiting microorganism growth'within aqueous, normally biodegradab~e materials.
Other objects and advantages of the present in-vention will be apparent to those skilled in the art from the'detailed description of the invention which followsO
It has been determined that tertiary butyl hydro-quinone will inhibit the development of microorganisms within aqueous materials. Certain concentrations of tertiary butyl hydroquinone have been found to be bacteriostatic when in-cluded in a variety of aqueous materials which would other-wise support the growth of decomposing and putrefying micro-organisms.- These ~aterials can take the form of a variety ~Q69375 of products having a perceptible moisture content, such as foods, food derivatives, soaps, adhesives, industrial oils, and the like.
Tertiary butyl hydroquinone has been known to be useful to impede the development of oxidative rancidity within materials having a fat and/or oil contentO It has been dis-covered that TBHQ also has valuable additional qualities as an inhibitor to microbial growth'in aqueous materials applied at leveIs greater than those previously utilized to reduce oxidation. These levels -are'referred to herein as bacterio-static concentrations of TBHQ. Generally speaking, the bacteriostatic concentrations of TBHQ in aqueous materials which also contain fats or oils will not only, in accordance with'the present invention, inhibit microbial growth normally expected from the water content thereof but also will be of a concentration that is known to be more than adequate'to in-hibit oxidative rancidity within the fat or oil component.
The bacteriostatic concentrations of T3HQ contained in materials according to the present invention vary somewhat -' depending upon the make-up of the material itself and also upon the particular microorganism to be controlled. Such concentration variations will be evident from the'examples-herein. Basically, the degree to which TBHQ is effective as a bacteriostat is dependent upon the concentration of TBHQ, the conditions of manufacture ~e.g. degree of heat processing), the environmental storage conditions, and the type of micro-organisms present in each particular aqueous material which would normally grow to cause microbial deterioration.
The minimum leveI of these TBHQ bacteriostatic con-centrations can be defined in terms of when evidence of anti-microbial activity in the aqueous material begins to be real-ized. Often when this is the case when the concentration of io6s3q5 tertiary butyl hydroquinone approximates roughly 0.02 weight percent of the aqueous, normally biodegradable material. How-ever, it should be borne in mind that, in certain materials, bacteriostatic effects can first become evident at TBHQ con-centrations as low as 0.01 weight percent, based on thé weight of the materials, as indicated in the examples herein. Also, for example, bacteriostatic effects have been observed at levels as-low as 0.005 weight percent TB~Q within pasteurized fluid whole milk.
Similarly, the maximum upper level of the TBHQ con-centrations within the aqueous materials will be variable depending upon the aqueous, normally biodegradable material.
Usually, such'upper limit will be determined by economic considerations or considerations such as statutory maximum TBEQ levels and the like. A general statement in this regard can be'made only to the effect that levels of diminishing returns often occur at concentrations on the order of approxi-mateLy 0.1 weight percent TBHQ based on the weight of the aqueous material.
It is to be noted that the concentrations herein are determined differently from thbse'conventionally referred to as the concentration of added T~HQ, which conventional con-centration is based upon the amount of fat or oil present in the'system. In the present invention it is necessary to add the TBHQ on the'basis of the total weight of the aqueous material to be preserved.
The concentrations just discussed are, as previously mentioned, effective'to inhibit the growth of microorganisms within aqueous materialsO It is to be'understood that when the aquebus materials contain fat or oil, these same levels will, as known heretofore, be more than adequate to retard oxidative rancidity of such fat or oil that would otherwise 106i~375 be expected to become evident within such materials with the passage of time. Evidence of both microbial growth and the onset of oxidative rancidity will be significantly delayed due to the addition of these bacteriostatic concentrations of TBHQ.
The present method relates primarily to adding and mixing bacteriostatic amounts of tertiary butyl hydro-; quinone with aqueous, normally biodegradable materials so as to inhibit the growth and development of microorganisms. A
discussion of concentrations needed to achieve such newly discovered use of TBHQ as a bacteriostat are contained else-where in this description, from which it will be seen that the concentrations vary depending upon the make-up of the aqueous material being treated, preparation and storage con-ditions, and the like.
Depending upon the particular aqueous material being treated, tertiary butyl hydroquinone can be added directly thereto and mixed, or it may be added by using water or sc~e other substance as a carrier~ The TBHQ is normally mixed with the aqueous material in any conventional manner so as to achieve a reasonably unifonm distribution throughout the aqueous material.
The following examples are presented to illustrate the present invention. It will be understood that the specific embodiments and illustrations should not be taken in any manner as limiting the invention as defined in the appended claims.
E X A M P L E
An aqueous protein suspension of bone glue, having a 38 percent by weight solids content and which would normal-ly undergo rapid spoilage was treated by adding vàrious levels of tertiary butyl hydroquinone thereto. The levels in this and the other examples are designated as "% TBHQ (W/W)~l to indicate the weight percent of TBHQ that was added to the aqueous material, based on the weight of that naterial. Each sample was stored for 42 days and periodically observed for spoilage. Spoilage is determined for this composition by the presence of a strong ammonia-like odor. It is believed r that bacterial growth which causes spoilage causes the production of ammonia which then renders impossible conven-tional means for counting bacteria. The results are listed in the following table:
Z TBHQ (WIW) 6 DAYS 11 DAYS 17 DAYS 42 DAYS
0 (Control) Spoiled SpoilPd Spoiled Spoiled O. 001 " " " " ' '~
0.005 " " " " -0.01. " " " "
0.02 O.K. O.K. O.K. "
0-04 " " " O.K.
0.08 " " " "
OoOl From this data, it can be seen that bone glue, an aqueous pro-tein product containing a very low level of fat, had bacterial growth therein inhibited for at least 42 days with storage at room temperature when TBHQ at a concentration of 0.04 weight percent was added thereto. Significant inhibition of bacterial growth was also realized at a concentration of 0.02 weight per-cent.
E X A N P L E II
Various concentration of TBHQ were added to an aqueous ma~erial that was an aqueous protein suspension con-sisting of gelatin. Such a composition, without TBHQ, would normall~ undergo rapid spoilage. This gelatin had a 30 per-cent solids content based on weight. The samples were stored .. . .... . . . . . . ....

at room temperature for up to 42 days, with observations thereof having been made to detect the growth of mold on the surface thereof. These observations are as follows:
% TBHQ (W/W) 4 DAYS 6 DAYS 8 DAYS 11 DAYS 17 DAYS 42 DAYS
0 (Control) O.K. Moldy Moldy Moldy Moldy Moldy 0.001 " l~
0.005 ll ll ll 1l il ,.
0.01 " O.K.O.K. " " "
0.02 " " Moldy ~9 0.04 " " O.K. O.K.
0.08 ~' ll ll ll ll ll -0.1 " " " " O.K. "
These data indicate that the addition of TBHQ at levels from about 0.01 weight percent and higher based on the total weight of the aqueous material resulted in a delay in the spoilage of the gelatin suspension.
E X A M P L E III
~ . .
Tertiary butyl hydroquinone was added at various concentrations to aqueous adhesive suspensions containing starch and stored at room temperature for 42 days. The re-sults are as follows:
% TBH~ (W/W) 8 DAYS 11 DAYS17 DAYS 42 DAYS
0 (Control3 Moldy MoldyMoldy Moldy 0.005 " " " "
0,01 O.K. " " "
0.02 " " " "
0.04 17 O.K.
0.08 " " O.K. "
O. 1 " " " "
The length of time for mold to grow within the starch based adhesive, containing essentially no fat or oil, is seen to be proportional to the amount of TBHQ added to the system.

10~i937S

E X A M P L E IV
From the following data, it can be seen that the addition of TBHQ at a level as low as 0.005 percent (W/W) to pasteurized fluid whole milk prevents the growth of the normal spoilage bacteria associated with milk. Reported after four, seven, and seventeen days of storage at 36F. are the observed total plate counts per ml.
Z TBHQ (WtW) 0 DAYS 4 DAYS 7 DAYS 17 DAYS
0 (Control) 4 x 103 2.4 x 103 3.9 x 104 7.0 x 107 0.001 1.1 x 103 6.9 x 102 2.7 x 105 0.005 6.0 x 102 2.0 x 102 6.0 x 102 0.01 5.0 x 102 2.2 x 102 8.0 x 102 0.02 2.0 x 102 2 2 x 1o2 4 o x 1o2 0.04 2.0 x 102 2.9 x 103 6.0 x 102 0.08 2.0 x 102 2.7 x 102 8.0 x 102 0~1 2.0 x 102 2.3 x 102 2.3 x 103 E X A M P L E V
Experiments were conducted to evaluate the in-hibitory effect of TBHQ on the following microorganisms:
Pseudomonas aeruginosa Ps6, Esterichia coli Es9~ Straphylococcus aureus Stl2, fresh meat bacteria from fresh pork, and aerobic sporeformers fr~ soy flakes. For each microorganism, a standard plate count (SPC) agar was made with TBHQ, the TBHQ being added at various weight percents based upon the total weight of the respecti~e agars. Each was autoclaved for fifteen minutes at 121C. The pork and soy flake~ were diluted in phosphate buffer and spread onto the various agar media in Petri dishes. Each of the pure strains of Ps6, Es9 and Stl2 were grown for 24 hours at 37C in brain heart infusion (BHI) broth, and about 10 cells were spread onto prepoured plates containing the various agar media. Control plates without TBHQ in the agar medium were included for each bacteria as well as for the suspensions from soy flakes and fresh meat~ Results after four days of incubation, consisting of one day at 32C., followed by three days at room tempera-ture~ were as follows, reported as plate count for each of the agar media containing the various concentrat~ons of TBHQ, again reported as %(W/W3 of the aqueous material. In this example, the aqueous material is the agar.

Control 0.003 0.01 0.02 0.05 0.1 No % % % % %
TBHQ TB~Q TBHQ TBHO TBHO TBHQ
Pseudomonas 7.2 x Appr. Appr. Appr. Appr. 700*
aeruginosa 105 105 105 105 104 Escherichia 1.9 x Ap~r. Less* Less LessLess coli 105 10 than than than than Staphylococcus 2.5a x Less* Less Less Less Less aureus 10 than than than than than 10 10 10 10 10 : , Soy Flake 1.6 x 1.9 x Less* Less LessLess Bacteria 104 103 than than than than Fresh Meat 6.5 x 5.0 x 2.~ x 5.3 x 7.~ x 2.7 x*
; 20Bacteria lo6 1o6 10 105 10 1o2 Mold From Air Growth Growth Growth No* No No Growth Growth Growth The above results exhibit the effectiveness of TBHQ in inhibiting the growth of various types of bacteria and mold. An asterisk indicates when a level of effectiveness begins to become evident.
Obviously, many modifications and variations of the invention as hereinbefore set forth may be made without de-parting from the spirit and scope thereof, and only such limitations should be imposed as are indicated in the appended claims.

_g_

Claims (11)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. An aqueous composition having an improved microbial shelf life, consisting essentially of an aqueous material, with or without fat, said aqueous material containing water and a biodegradable material in which microbial growth normally occurs, and further including tertiary butyl hydroquinone, said tertiary butyl hydroquinone being present at bacteriostatic concentrations to inhibit the growth of microorganisms in said aqueous material, said bacteriostatic concentrations in the aqueous material being greater than concentrations known to inhibit oxidative rancidity and being at least about 0.005 weight percent based on the total weight of the aqueous material, said oxidative rancidity inhibiting concentrations being not more than 0.02 weight percent of the fat content of the aqueous material when the aqueous material contains fat.
2. The composition of claim 1, wherein said bacteriostatic concentration is at least about 0.01 weight percent tertiary butyl hydroquinone based on the weight of aqueous material.
3. The composition of claim 1, wherein said bacteriostatic concentration is at least about 0.02 weight percent tertiary butyl hydroquinone based on the weight of the aqueous material.
4. The composition of claim 1, wherein said aqueous material is pasteurized fluid whole milk, and said bacteriostatic concentration is at least about 0.005 weight percent tertiary butyl hydroquinone based upon the weight of the pasteurized fluid whole milk.
5. The composition of claim 1, wherein said bacteriostatic concentration is within the approximate range of from about 0.01 to about 0.1 weight percent tertiary butyl hydroquinone, based upon the weight of the aqueous material.
6. The composition of claim 1, wherein said aqueous material also contains fat or oil, and oxidative rancidity thereof is inhibited by said bacteriostatic concentra-tions of tertiary butyl hydroquinone.
7. A method for inhibiting the development of microorganisms in an aqueous material, said method comprising adding a microorganism growth inhibitor to an aqueous material, said aqueous material containing water and being a biodegradable material in which microbial growth normally occurs, said microorganism growth inhibitor consisting essentially of tertiary butyl hydroquinone at a bacteriostatic concentration that inhibits microbial growth in said aqueous material, said bacteriostatic concentration in the aqueous material being greater than the concentration known to inhibit oxidative rancidity and being based on the total weight of the aqueous material.
8. The method of claim 7, wherein said concentration is at least about 0.01 weight percent tertiary butyl hydro-quinone based upon the weight of the aqueous material.
9. The method of claim 7, wherein said concentra-tion is at least about 0.02 weight percent tertiary butyl hydroquinone based upon the weight of the aqueous material.
10. The method of claim 7, wherein said aqueous material is pasteurized fluid whole milk and said concentra-tion is at least about 0.005 weight percent tertiary butyl hydroquinone based upon the weight of aqueous material.
11. The method of claim 7, wherein said bacterio-static concentration of tertiary butyl hydroquinone likewise inhibits oxidative rancidity within a fat or oil present in said aqueous material.
CA246,117A 1975-06-16 1976-02-19 Antimicrobial and antirancidity agent Expired CA1069375A (en)

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