Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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SMB
Additive for the Improvement and/or Stabilization of the
Keeping Ouality of Microbiallar Perishable Products
The present invention relates to a method and an additive and its use for
the improvement and/or stabilization of the keeping quality of microbially
perishable products by the addition of additives.
Industrially processed food and feed products, cosmetics, pharmaceuticals
and other products susceptible to microbial perishing must be storable for
not too short a period of time in order to reach the consumer in an unper-
ished state after shipping and distribution on the usual pathways. In
addition, the consumer even expects the acquired product not to perish
immediately after having been bought, but to be storable for some days or
weeks, depending on the kind of product.
If not treated, most food and feed products would perish within a few days
since fungi and/or bacteria could thrive without any hindrance, at most
impeded by cooling, on an ideal, for them, substrate. Typical examples
include the perishing of bread from molds, e.g., Aspergillus niger, of meat
products (e.g., sausages) from enterobacteria or lactobacilli, the contami-
nation of poultry by Salmonellae, and many more. Since fungi including
yeasts or their spores, Gram-positive and Gram-negative bacteria are
present in every place except where a sterile environment has been created
by particular expensive measures, which cannot be applied industrially for
economic reasons, appropriate countermeasures must be taken.
Therefore, conventionally, food and feed products, cosmetics, pharmaceuti-
cals, paints, papers and pulps and other perishable products are rendered
storable using preservatives, which appear in the Codex Alimentarius list of
the Food and Agriculture Organisation (FAO/WHO Food Standard Pro-
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gramme) in Division 3, Food Additives, 3.73, Preservatives, as "synthetic
preservatives" and are mostly employed in the form of chemical monosub-
stances or their combinations.
From the prior art, a wide variety of additives for preserving perishable
products has been known. These include, for example, additives based on
flavoring agents, alcohols, organic acids, aldehydes, phenolics and essential
oils. Such compositions are described, for example, in the US Patent
Specification 4,446,161, US 49 27 651, WO 94/14 414, GB 172993 and
DE-OS 3138277, and in E. Luck (Chemische Lebensmittelkonservierung,
page 1977, 1986, Springer-Verlag).
The preservatives appearing in the mentioned list are bacteriostatically
and/or fungistatically active and substantially improve the keeping quality.
However, they are refused by many consumers since their effects on the
consumer's health are not known, and adverse effects, especially for a
repeated uptake over an extended period of time, cannot be excluded.
Another disadvantage is that all methods known to date are based on pH or
aW value changes.
One particular disadvantage of these preservatives is their being added to
the food product in high concentrations, as a rule. Thus, relatively large
amounts of these substances also arrive in the human body when the food
is ingested. This results in responses in the form of allergic diseases, which
today are often met at a high incidence.
An alternative to the preservation by the addition of synthetic preservatives
is the thermal inactivation of germs, e.g., by pasteurizing. Pasteurizing is a
thermal treatment at 70 to 85 °C with an exposure time of from 30 to
120
minutes.
Pasteurization substantially improves the keeping quality of thus treated
products, but is technically complicated and consumes very much energy.
In addition, the viability of spores is often not or only very incompletely
eliminated. Also, for thermally sensitive products, pasteurization cannot be
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used, or it leads to a significant loss in quality since the "degree of fresh-
ness" of the pasteurized product will be reduced, at least by the second
thermal treatment (at up to 85 °C), which is often necessary. In
addition, it
is often just the valuable components of food products, cosmetics or
pharmaceuticals, e.g., vitamins, amino acids and many pharmaceutically
active ingredients, which are thermolabile, so that a thermal treatment
under the usual pasteurization conditions is precluded.
Another possibility for improving the keeping quality is to place the product
susceptible to perishing in an air-tight package under nitrogen or C02, or to
supply it in vacuum packages, as is done, for example, with ground coffee.
However, these processes are expensive and tedious and thus, for many
food products, cannot be used.
Accordingly, it has been the object of the present invention to provide an
additive for the improvement of the keeping quality and/or stabilization of
microbially perishable products by the addition of additives, which additive
lacks the mentioned drawbacks of the prior art.
This object is achieved by the additive's being a mixture containing
a) polyphenol and
b) at least one GRAS flavor alcohol; or
c) benzyl alcohol and
d) at least one other GRAS flavor alcohol;
the mixing ratio of components a) to b) or c) to d) being from 1:1 to
1:10,000 or from 10,000:1 to 1:1, preferably from 1:1 to 1:1000 or from
1000:1 to 1:1. More preferably, the mixing ratio is from 1:1 to 1:100 or
from 100:1 to 1:1.
In the following, the substances which may be preferably used according to
the invention are further described in more detail:
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As the polyphenol (components a)), there may also be used their possible
derivatives, salts, acids, esters, oxidases, free and etherified, natural.
Examples of useful compounds include pyrocatechol, resorcinol, hydroqui-
none, phloroglucinol, pyrogallol, hexahydroxybenzene, usnic acid, acyl-
polyphenols, lignins, anthocyanidines, flavones, catechols, tannins, gallic
acid derivatives, carnosol, carnosolic acid, 2,5-dihydroxyphenylcarboxylic
and 2,5-dihydroxyphenylalkanecarboxylic, substitutions, derivatives, salts,
esters, amides, caffeic acid, esters, amides, gallotannin, tannic acids,
pyrogallol, gallotannic acids, flavonoids: flavone, flavonol, isoflavone,
gossypetin, myricetin, robinetin, apigenin, morin, taxifolin, eriodictyol,
naringin, rutin, hesperidin, troxerutin, chrysin, tangeritin, luteolin,
epigallo-
catechol gallate, quercetin, fisetin, kaempferol, galangin, rotenoids,
aurones, flavonols, flavonediols, extracts, e.g., from Camellia, Primula.
According to the invention, the mentioned polyphenols are used in combi-
nation with GRAS flavor alcohols. GRAS flavor alcohols have been recog-
nized by the FDA as commercially safe for use in foods (G.R.A.S. = gener-
ally recognized as safe in food). This distinguishes the alcohols according to
the invention, especially from those employed in US 4,446,161.
The mentioned GRAS flavor alcohols are those alcohols which are men-
tioned in the FEMA/FDA GRAS Flavour Substances Lists GRAS 3-15 No.
2001-3815 (as of 1997). This list contains natural and synthetic flavoring
agents approved by the American public health authority, FDA, for use in
foods (FDA Regulation 21 CFR 172.515 (Synthetic Flavoring Substances
and Adjuvants) and FDA Regulation 21 CFR 182.20 (Natural Flavoring
Substances and Adjuvants)).
According to the invention, component a) may be used with one or more
GRAS flavor alcohols (components b)). According to the invention, it is
preferred to use one or two GRAS flavor alcohols. It is particularly preferred
to use two GRAS flavor alcohols.
In detail, the following GRAS flavor alcohols may be employed, for example
(components a), c), d)): benzyl alcohol, acetoin (acetylmethylcarbinol),
ethyl alcohol (ethanol), propyl alcohol (1-propanol), iso-propyl alcohol (2-
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propanol, isopropanol), propylene glycol, glycerol, n-butyl alcohol (n-
propyl carbinol), iso-butyl alcohol (2-methyl-1-propanol), hexyl alcohol
(hexanol), L-menthol, octyl alcohol (n-octanol), cinnamyl alcohol (3-
phenyl-2-propene-1-ol), a-methylbenzyl alcohol (1-phenylethanol), heptyl
alcohol (heptanol), n-amyl alcohol (1-pentanol), iso-amyl alcohol (3-
methyl-1-butanol), anisic alcohol (4-methoxybenzyl alcohol, p-anisic
alcohol), citronellol, n-decyl alcohol (n-decanol), geraniol, ~-y-hexenol (3-
hexenol), lauryl alcohol (dodecanol), linalool, nerolidol, nonadieneol (2,6-
nonadiene-1-ol), nonyl alcohol (nonanol-1), rhodinol, terpineol, borneol,
clineol (eucalyptol), anisole, cuminyl alcohol (cuminol), 10-undecene-1-ol,
1-hexadecanol.
The GRAS flavor alcohols which are particularly preferred according to the
invention include benzyl alcohol. Thus, one particularly preferred combina-
tion contains polyphenol (component a)) and benzyl alcohol (component
b)). This mixture may optionally contain further GRAS flavor alcohols.
According to the invention, it is also possible to use GRAS flavor alcohols
(component d)) instead of the polyphenol, i.e., benzyl alcohol (component
c)) may be used in admixture with other GRAS flavor alcohols (component
d)).
The mixing ratio of polyphenol (component a)) or benzyl alcohol
(component c)) to the GRAS flavor alcohols (components b) and d)) is
preferably from 1:1 to 1:10,000 or from 10,000:1 to 1:1, more preferably
from 1:1 to 1:1000 or from 1000:1 to 1:1, even more preferably from 1:1
to 1:100 or from 100:1 to 1:1.
However, various alcohols can be additionally employed in components a),
b), c) and d). These are preferably monohydric or polyhydric alcohols
containing from 2 to 10 carbon atoms, preferably from 2 to 7 carbon
atoms.
Preferably, polyphenol and alcohols are used in such amounts that the
mixing ratio of alcohol to polyphenol is from 1:1 to 1:1000, or that of
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polyphenol to alcohols is from 1:1 to 1:1000, especially from 1:1 to 1:100
or from 100:1 to 1:1.
The components of the additive according to the invention mentioned in the
following are flavoring agents recognized in the FEMA/FDA GRAS Flavour
Substances List as GRAS (generally recognized as safe in food) 3-15 No.
2001-3815 (as of 1997).
Further, in the additive according to the invention, acids and/or their
physiologically acceptable salts can be employed. Preferably, organic acids
and/or their salts are used. These are preferably compounds containing
from 1 to 15 carbon atoms, preferably from 2 to 10 carbon atoms.
In detail, the following acids may be used, for example (component e)):
Acetic acid, aconitic acid, adipic acid, formic acid, malic acid (1-hydroxy-
succinic acid), capronic acid, hydrocinnamic acid (3-phenyl-1-propionic
acid), pelargonic acid (nonanoic acid), lactic acid (2-hydroxypropionic
acid), phenoxyacetic acid (glycolic acid phenyl ether), phenylacetic acid
(a-toluenic acid), valeric acid (pentanoic acid), iso-valeric acid (3-methyl-
butyric acid), cinnamic acid (3-phenylpropenoic acid), citric acid, mandelic
acid (hydroxyphenylacetic acid), tartaric acid (2,3-dihydroxybutanedioic
acid; 2,3-dihydroxysuccinic acid), fumaric acid. Lactic acid, for example, is
preferred.
Further, the following compounds may be used as component f) in the
additive according to the invention:
As phenols, there may be used, for example, thymol, methyleugenol,
acetyleugenol, safrol, eugenol, isoeugenol, anethole, phenol, methylchavi-
col (estragol; 3-4-methoxyphenyl-1-propene), carvacrol, a-bisabolol,
fornesol, anisole (methoxybenzene), propenylguaethol (5-propenyl-2-
ethoxyphenol).
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As acetates (component g)), there may be used, for example, iso-amyl
acetate (3-methyl-1-butyl acetate), benzyl acetate, benzylphenyl acetate,
n-butyl acetate, cinnamyl acetate (3-phenylpropenyl acetate), citronellyl
acetate, ethyl acetate (acetic ester), eugenol acetate (acetyleugenol),
geranyl acetate, hexyl acetate (hexanyl ethanoate), hydrocinnamyl
acetate (3-phenylpropyl acetate), linalyl acetate, octyl acetate, phenyl-
ethyl acetate, terpinyl acetate, triacetin (glyceryl triacetate), potassium
acetate, sodium acetate, sodium diacetate, calcium acetate.
As an ester (component h)), there may be used allicin, for example.
As terpenes (component i)), there may be used, for example, camphor,
limonene, ~3-caryophyllene.
The acetals (component j)) which can be used include, e.g., acetal,
acetaldehyde dibutyl acetal, acetaldehyde dipropyl acetal, acetaldehyde
phenethyl propyl acetal, cinnamic aldehyde ethylene glycol acetal, decanal
dimethyl acetal, heptanal dimethyl acetal, heptanal glyceryl acetal, benz-
aldehyde propylene glycol acetal.
Aldehydes (component k)) may also be used, e.g., acetaldehyde, anisic
aldehyde, benzaldehyde, iso-butyl aldehyde (methyl-1-propanal), citral,
citronellal, n-capraldehyde (n-decanal), ethylvanillin, furfurol, heliotropin
(piperonal), heptyl aldehyde (heptanal), hexyl aldehyde (hexanal), 2-
hexenal (~i-propylacrolein), hydrocinnamic aldehyde (3-phenyl-1-prop-
anal), lauryl aldehyde (dodecanal), nonyl aldehyde (n-nonanal), octyl
aldehyde (n-octanal), phenylacetaldehyde (1-oxo-2-phenylethane), pro-
pionaldehyde (propanal), vanillin, cinnamic aldehyde (3-phenylpropenal),
perillaldehyde, cuminaldehyde.
Preferably, according to the invention, solubilizers (component I)) are also
present as a component in the additive. Namely, the additives used
according to the invention are flavoring agents, in principle. Most of the
flavoring agents included in the GRAS FEMA list are not water-soluble,
i.e., they are hydrophobic. If employed in food products which predomi-
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_ g _
nantly contain lipids, they can be directly used without a solvent due to
their lipophilic character. However, the proportion of lipophilic foods is
relatively low. In order to be able to display their activity in the mostly
hydrophilic food or feed products, cosmetics or pharmaceuticals, they are
preferably used in connection with a water-soluble solubilizer, preferably
glycerol, propylene glycol, water, edible oils or fats.
According to the invention, there may also be used, for example, the
following essential oils and/or alcoholic or glycolic extracts or extracts
obtained by C02 high pressure methods (component m)) from the plants:
a) oils or extracts having a high content of alcohols:
melissa, coriander, cardamon, eucalyptus;
b) oils or extracts having a high content of aldehydes:
Eucalyptus citriodora, cinnamon, lemon, lemon grass, melissa,
citronella, lime, orange;
c) oils or extracts having a high content of phenols:
origanum, thyme, rosemary, orange, clove, fennel, camphor,
mandarin, anise, cascarilla, estragon and pimento;
d) oils or extracts having a high content of acetates:
lavender;
e) oils or extracts having a high content of esters:
mustard, onion, garlic;
f) oils or extracts having a high content of terpenes:
pepper, bitter orange, caraway, dill, lemon, peppermint, nutmeg
apple.
The mixing ratio of components a) or c) to b), d), e), f), g), h), j), k), I),
m) may respectively be from 1:1 to 1:10,000 or from 10,000:1 to 1:1,
preferably from 1:1 to 1:1000 or from 1000:1 to 1:1.
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The additives described are preferably used for the improvement and
stabilization of the keeping quality of the following groups of food products:
Breads, pastries, improvers, baking powders, blancmange powders,
beverages, dietetic food products, essences, delicatessen, fish and fish
products, potatoes and products based on potatoes, spices, flours and
meals, margarine, fruits and vegetables and products based on fruits and
vegetables, pickled preserves, starch products, sweets, soups, pasta food,
meat and meat products, milk, dairy and cheese products, poultry and
poultry products, oils, fats and products containing oils or fats.
The additives according to the invention are effective, in particular, against
molds, yeasts and bacteria (Gram-positive and Gram-negative). They are
excellently effective, in particular, against pathogens (Enterobacteriaceae,
e.g., E. coli, Salmonella, Enterococci, e.g., Staphylococci, Streptococci) and
also against perishing-causing agents, such as lactic-acid bacteria, e.g.,
Lactobacillus vulgaris, melds, e.g., Aspergillus niger, yeasts, e.g., Endomy-
ces tibuliger. Also, the additives according to the invention have a reductive
effect against viruses and microbial toxins, such as aflatoxins, enterotoxins.
The additives are preferably added to the microbially perishable product in
amounts of from 1 ppm to 10% by weight, preferably from 1 ppm to 1.0%
by weight. Particularly preferred amounts are from 0.001% by weight to
0.5% by weight. Especially preferred amounts are from 0.002% by weight
to 0.25% by weight.
According to the invention, it is surprising that the effect of the additives
according to the invention can be seen when concentrations as low as those
mentioned are used. This is all the more surprising since the food products
treated with the additives according to the invention have a significantly
higher keeping quality than the perishable products treated with conven-
tional preservatives.
It is also surprising that the advantages described are seen even for
microbial exposure times of less than 24 h, especially less than 60 minutes,
preferably from 1 to 60 minutes, most preferably from 5 to 15 minutes.
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Surprisingly, the additives according to the invention do not result in any
disadvantages in the taste, smell or color of the treated food product. One
particular advantage over the prior art is that no shifts of the pH or aW
value is observed, i.e., the activity of the additives employed is
surprisingly
independent of the pH and aw values. It is also surprising that the additives
can be used irrespective of humidity, fat, protein and carbohydrate con-
tents. Finally, the combinations according to the invention are insensitive to
temperature variations within a range of from -30 °C to 200 °C,
i.e., they
are both cold and heat resistant.
In addition to the additives described, the surfaces of the products and/or
their environment, especially the ambient air and/or the surfaces of the
equipment or other materials immediately or mediately contacting the
products, may be treated with one or more processing aids containing at
least two flavoring agents prior to, during or after completion of the process
for the manufacturing, processing or packaging of the products, i.e., in
addition to using the additives, an external treatment with processing aids
may also be performed according to the invention.
The flavoring agents contained in the processing aids are exclusively
natural or synthetic (but identical with naturally occurring) flavoring agents
which have been recognized as safe according to the FEMA (GRAS -
generally recognized as safe). The mentioned list is the FEMA/FDA GRAS
Flavour Substances Lists GRAS 3-15 No. 2001-3815 (as of 1997) which
includes natural and synthetic flavoring agents approved by the American
public health authority, FDA, for use in foods (FDA Regulation 21 CFR
172.515 (Synthetic Flavoring Substances and Adjuvants) and FDA Regula-
tion 21 CFR 182.20 (Natural Flavoring Substances and Adjuvants)). The
flavoring agents which meet these FDA standards may be used "quantum
satis", i.e., they may be contained in the food up to the maximum concen-
tration in which they do not cause any adverse effects on the smell or taste
of the food to which they are added. The flavoring agents listed according
to the FEMA are largely identical with the substances contained in the
corresponding European standard COE.
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In addition, the flavoring agents classified as "NATO" according to Article V
European Community Directive Flavourings (June 22, 1988) may also be
used according to the invention, provided they are considered safe accord-
ing to the above mentioned FEMA GRAS list. NAT4 substances are sub-
stances which are to be declared as "synthetic, but identical with naturally
occurring substances" under certain circumstances, e.g., if these sub-
stances are used in connection with and as a component of a natural or
synthetic (but identical with a naturally occurring) flavoring agent.
A particular advantage of the processing aids is the fact that they may be
added to foods without hesitation in a "quantum satis" concentration range
due to their components which are listed in the FEMA GRAS list and have
been recognized as safe by the US public health authority FDA, which is
perhaps the most critical public health authority of all.
Another particular advantage is that the processing aids do not affect the
smell and taste of the treated products.
The processing aids according to the invention are employed, for example,
in the form of lubricants, emulsifiers and cleaning agents, spraying media,
atomizing media, gas-phase active agents, heat transfer media, and cutting
media. The processing aids may also be employed as additives to the
agents mentioned.
It is essential that the processing aids are not added to or mixed with the
food products. Rather, only the surfaces or cuts of the food products are
treated with the processing aids. This may be done by directly treating the
surfaces or cuts of the food products with the processing aids. However, it
is also possible to add the processing aids to the surfaces of equipment,
production machines, packaging means, conveying means, packaging
materials and the ambient air.
It is surprising that the microbicidal activity of the processing aids can be
seen already when low concentrations are used. When applied to food
products, only from 0.01 to 5 g/kg, preferably from 0.05 to 2 g/kg, more
preferably from 0.05 to 1 g/kg of food is used. When used for the ambient
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air, for example, only from 0.001 to 10 g/m3 of air is used. For the surfaces
of equipment, even as little as from 0.000001 g to 0.1 g/cm2 surface area
is used.
If these concentrations are adhered to, the quantities detectable in the food
products are only around 0.001% by weight. In contrast, according to the
prior art, from 0.1 to 3% by weight of preservative will be present in the
food products as a rule. It is surprising that, in spite of these extremely
low
concentrations, an increase in storage life of up to 50% can be achieved
according to the invention as compared to conventionally preserved foods.
It is to be pointed out particularly and astonishing that as little as 0.001%
by weight of processing aids which are indirectly applied to food products is
sufficient to achieve a stabilization or improvement of the keeping quality
while the product quality is increased.
This effect is all the more surprising since the duration of the microbicidal
action of the flavoring agents used according to the invention is less than
24 hours, preferably less than 12 hours. It is particularly preferred to
select
such processing aids and concentrations that the duration of microbicidal
action is less than 1 hour, preferably less than 15 minutes.
In contrast, conventional preservatives are supposed to be active in the
food product as long as possible, i.e., for weeks and months. In spite of the
very short duration of action of the processing aids used according to the
invention (exposure time), the keeping quality or storage life is
significantly
increased as compared to food products treated with conventional pre-
servatives or preservation methods according to the prior art. Conse-
quently, according to the invention, when the above described additives
and the processing aid are combined, it is possible, surprisingly, to work
with significantly lower amounts than that required when the preservatives
which have been usual in the prior art are employed.
The processing aid which may be used according to the invention includes
flavoring agents selected from the group consisting of alcohols, aldehydes,
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phenols, acetates, acids, esters, terpenes, acetals and their physiologically
acceptable salts, essential oils and plant extracts.
Preferred embodiments of the processing aids according to the invention
include one or more flavoring agents selected from one or more of the
following groups:
I. Alcohols
Acetoin (acetylmethylcarbinol), ethyl alcohol (ethanol), propyl alcohol (1-
propanol), iso-propyl alcohol (2-propanol, isopropanol), propylene glycol,
glycerol, benzyl alcohol, n-butyl alcohol (n-propyl carbinol), iso-butyl
alcohol (2-methyl-1-propanol), hexyl alcohol (hexanol), L-menthol, octyl
alcohol (n-octanol), cinnamyl alcohol (3-phenyl-2-propene-1-ol), a-
methylbenzyl alcohol (1-phenylethanol), heptyl alcohol (heptanol), n-amyl
alcohol (1-pentanol), iso-amyl alcohol (3-methyl-1-butanol), anisic alcohol
(4-methoxybenzyl alcohol, p-anisic alcohol), citronellol, n-decyl alcohol
(n-decanol), geraniol, p-y-hexenol (3-hexenol), lauryl alcohol (dodecanol),
linalool, nerolidol, nonadieneol (2,6-nonadiene-1-ol), nonyl alcohol
(nonanol-1), rhodinol, terpineol, borneol, clineol (eucalyptol), anisole,
cuminyl alcohol (cuminol), 10-undecene-1-ol, 1-hexadecanol.
II. Aldehrdes
Acetaldehyde, anisic aldehyde, benzaldehyde, iso-butyl aldehyde (methyl-
1-propanal), citral, citronellal, n-capraldehyde (n-decanal), ethylvanillin,
furfurol, heliotropin (piperonal), heptyl aldehyde (heptanal), hexyl aldehy-
de (hexanal), 2-hexenal (~i-propylacrolein), hydrocinnamic aldehyde (3-
phenyl-1-propanal), lauryl aldehyde (dodecanal), nonyl aldehyde (n-non-
anal), octyl aldehyde (n-octanal), phenylacetaldehyde (1-oxo-2-phenyl-
ethane), propionaldehyde (propanal), vanillin, cinnamic aldehyde (3-
phenylpropenal), perillaldehyde, cuminaldehyde.
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III. Phenols
Thymol, methyleugenol, acetyleugenol, safrol, eugenol, isoeugenol,
anethole, phenol, methylchavicol (estragol; 3-4-methoxyphenyl-1-
propene), carvacrol, a-bisabolol, fornesol, anisole (methoxybenzene),
propenylguaethol (5-propenyl-2-ethoxyphenol).
IV. Acetates
Iso-amyl acetate (3-methyl-1-butyl acetate), benzyl acetate, benzyl-
phenyl acetate, n-butyl acetate, cinnamyl acetate (3-phenylpropenyl
acetate), citronellyl acetate, ethyl acetate (acetic ester), eugenol acetate
(acetyleugenol), geranyl acetate, hexyl acetate (hexanyl ethanoate),
hydrocinnamyl acetate (3-phenylpropyl acetate), linalyl acetate, octyl
acetate, phenylethyl acetate, terpinyl acetate, triacetin (glyceryl triaceta-
te), potassium acetate, sodium acetate, sodium diacetate, calcium
acetate.
V. Acids and/or their~harsiolo~ically acceptable salts
Acetic acid, aconitic acid, adipic acid, formic acid, malic acid (1-hydroxy-
succinic acid), capronic acid, hydrocinnamic acid (3-phenyl-1-propionic
acid), pelargonic acid (nonanoic acid), lactic acid (2-hydroxypropionic
acid), phenoxyacetic acid (glycolic acid phenyl ether), phenylacetic acid
(a-toluenic acid), valeric acid (pentanoic acid), iso-valeric acid (3-methyl-
butyric 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.
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VII. Terpenes
Camphor, limonene, ~-caryophyllene.
VIII. Acetals
Acetal, acetaldehyde dibutyl acetal, acetaldehyde dipropyl acetal, acetal-
dehyde phenethyl propyl acetal, cinnamic aldehyde ethylene glycol acetal,
decanal dimethyl acetal, heptanal dimethyl acetal, heptanal glyceryl
acetal, benzaldehyde propylene glycol acetal.
IX. Polyphenol
X. Essential oils and/or alcoholic or glycolic extracts or extracts obtained
b_y CO? high pressure methods from the~lants listed below:
a) oils or extracts having a high content of alcohols:
melissa, coriander, cardamon, eucalyptus;
b) oils or extracts having a high content of aldehydes:
Eucalyptus citriodora, cinnamon, lemon, lemon grass, melissa,
citronella, lime, orange;
c) oils or extracts having a high content of phenols:
origanum, thyme, rosemary, orange, clove, fennel, camphor,
mandarin, anise, cascarilla, estragon and pimento;
d) oils or extracts having a high content of acetates:
lavender;
e) oils or extracts having a high content of esters:
mustard, onion, garlic;
f) oils or extracts having a high content of terpenes:
pepper, bitter orange, caraway, dill, lemon, peppermint, nutmeg
apple.
CA 02294989 1999-12-20
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If the processing aid contains only one of the flavoring agents mentioned,
isopropanol and ethanol are not employed. Surprisingly, it has been shown
that a combination of at least two of the flavoring agents set forth above
has a significantly higher effect than one single substance.
Most of the flavoring agents included in the GRAS FEMA list are not water-
soluble, i.e., they are hydrophobic. If employed in food products which
predominantly contain lipids, they can be directly used without a solvent
due to their lipophilic character. However, the proportion of lipophilic
foods is relatively low. In order to be able to display their activity in the
mostly hydrophilic food or feed products, cosmetics or pharmaceuticals,
they are preferably used in connection with a water-soluble solubilizer. In
order to meet the requirement of this invention, to provide physiologically
safe processing aids, only those solubilizing flavoring agents are used
which are approved for use in food, e.g., alcohols.
The processing aids are used neat and/or in water-soluble dilutions with
water and/or solvents acceptable for foods (e.g., alcohols) and/or in lipid-
soluble dilutions with vegetable (fat) oils.
For example, in the processing aids, there may be used readily water-
soluble alcohols, preferably in concentrations of from 0.1 to 99% by weight,
based on the processing aid, in connection with other flavoring agents. The
processing aids may contain more than 50% of benzyl alcohol. Preferably,
they contain less than 50% by weight of ethanol, isopropanol or benzyl
alcohol, or of a mixture of these substances. It is particularly preferred for
the proportion of the mentioned alcohols to be less than 30% by weight,
especially less than 20% by weight. If processing aids are employed which
contain benzyl alcohol and at least one other flavoring agent, the proportion
of benzyl alcohol may also be more than 50% by weight.
Surprisingly, the processing aids which contain, for example, only 20% by
weight of ethanol or isopropanol in connection with flavoring aldehydes and
phenols in concentrations in the per mille range have very potent fungicidal
and bactericidal activities; even processing aids which contain 1% by
weight of the mentioned water-soluble alcohols in connection with less than
CA 02294989 1999-12-20
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3%0 of flavoring aldehyde and phenol have a 70 to 100% microbicidal
activity.
From the above, it can be seen that the processing aids according to the
invention have surprising microbicidal effects on the environment of the
production or the production process.
Preferred is the use of the processing aids for the production in food and
feed products, cosmetics, pharmaceuticals, paints, papers and/or pulps.
In particularly preferred embodiments, the processing aids are used for the
improvement and stabilization of the keeping quality of food products
selected from the following group:
Breads, pastries, improvers, baking powders, blancmange powders,
beverages, dietic food products, essences, delicatessen, fish and fish
products, potatoes and products based on potatoes, spices, flours and
meals, margarine, fruits and vegetables and products based on fruits and
vegetables, pickled preserves, starch products, sweets, soups, pasta food,
meat and meat products, milk, dairy and cheese products, poultry and
poultry products, oils, fats and products containing oils or fats.
The processing aid displays its activity in the environment of the perishable
product, for example, a food or feed product, e.g., on machine parts which
contact the product to be worked or processed, or in the air. Due to the
direct contact with the surface of the perishable product, they display their
activity there as well, i.e., they display their activity on the surface or,
when introduced in the product, within the product itself.
Therefore, a particular advantage of the processing aid described is that it
is a reliable decontaminant, on one hand, its effectivity against Gram-
positive and Gram-negative bacteria, fungi including yeasts and also
viruses having been proven, while on the other hand, it is no danger to the
consumer of the food since it is absolutely harmless towards him and has
no microbicidal technological after-effect in the food, because its microbi-
CA 02294989 1999-12-20
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cidal activity relates to the production environment which is freed from
contaminating microorganisms by the measures according to the invention.
The processing aid to be used according to the invention may be a lubricant
which at the same time serves for lubrication, decontamination of the
lubricated parts and thus indirectly for the keeping quality stabilization of
the products contacting these parts.
Further, according to the invention, the processing aid may be an emulsi-
fier, release or cleaning agent. Such agents serve for emulsifying and/or
cleaning and thus also for the decontamination of surfaces, objects, ma-
chines, devices, equipment, cutting surfaces or devices, conveying devices
and the like. In addition, it may be used for decontaminating and cleaning
foods, raw materials, cosmetics, pharmaceuticals, paints, papers, pulps,
livestock, poultry, fish and waste.
The processing aid to be used according to the invention may also be a
spraying medium. Such a spraying medium enables finely distributing the
decontaminating agents on all machine parts, conveying devices, cutting
devices, working surfaces etc., and it may at the same time have the result
that foods packaged immediately after the cutting process and/or packag-
ing-portioning process are stored in a climate having decontaminating
and/or keeping quality stabilizing properties due to entrapped spraying
agent. In addition, atomizable or sprayable embodiments are very inexpen-
sive due to the necessary amount's being comparably lower.
Similarly, the spraying agent may be blown or sprayed/atomized into
and/or onto packages, such as bags, cardboard boxes or the like in order to
thereby confer to the product packaged therein a longer storage life.
The spraying agents also serve for atomizing in the surroundings of the
production (environment, cooling system, air supply, fresh air) at hygieni-
cally weak points (e.g., cooling lines), thereby to reduce the number of
germs without causing damage to the people working there.
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The processing aids may also be employed for spraying onto food surfaces
or cuts in order to eliminate or reduce the perishing-causing agents present
on the foods.
Further, these spraying agents may be employed in conveying means,
storage and cooling rooms and the like.
In another embodiment, the processing aid is a gas-phase active agent
which serves for the active decontamination and/or deodorization in the gas
phase within more or less closed systems, such as packages, waste sys-
tems, container systems, shipping or storage rooms and the like. Both the
packaged product contained, shipped or stored in the container and the air
and the respective environment benefit from the activity of the gas-phase
agent.
In addition, the processing aid has proven to be a good heat transfer
medium. "Heat transfer medium" means cooling, heating and warming
media which can be used as decontaminating additives in circulating
systems of liquid cooling, heating and warming systems. They are added to
aqueous or oily systems for preventing the growth of microorganisms in the
liquids in order to prevent contamination, for example, when cooling
systems are leaking.
In another embodiment, the processing aid is a cutting medium for cutting
blades and/or cutting devices of all kinds and for all perishable products to
be cut in order to prevent contamination of the cutting surfaces.
In the food industry, contaminations by Gram-negative or Gram-Positive
pathogens, molds, yeasts and other possible perishing-causing agents are
often observed on the cutting surfaces of foods, which may reduce the
storage life of the cut products, and in part substantially so, and thus cause
damage in terms of both health and economy. The contaminations are
imported by raw materials, residues of products/raw materials, workers,
machine parts or operational processes or by the air.
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Therefore, conventionally, either the cut foods or foods to be cut are
pasteurized or technically treated to decontamine them and thus confer to
them a higher storage life, or else preservatives are added. However, as
mentioned above, a thermal treatment is not always possible or allowable
and may lead to a reduction of the product quality.
An accessory measure for improving the keeping quality of foods is the
cleaning or even disinfection of the environment using chemical disinfec-
tants, which treatment is subject to the biocide regulation. These sub-
stances are more or less toxic and must not be transferred into food
products. However, chemical disinfection is a discontinuous measure which
can be performed, in practice, only at certain production times for machine
parts and in the environment, after which rinsing with water for removing
any residual substances is required. Accordingly, a direct permanent
elimination of perishing-causing agents cannot be ensured.
Therefore, in the prior art, it has been tried to optimize the machine
hygiene through better cleanability or through installations for the produc-
tion or maintenance of pure or low-germ or germ-free air. However,
experience has shown that this did not cause an increased keeping quality
of cut food products, or it is no longer reasonable economically, or it cannot
be safely performed in practice.
An example from the sliced bread industry shows that the cutting or slicing
of breads such as whole-dough, whole-meal, white, wheat-and-rye bread
or bread for toasting followed by packaging substantially reduces the
storage life of the sliced bread as compared to unsliced bread. Depending
on the kind of bread, it is between 2 and 5 days. The subsequent thermal
treatment (pasteurizing in ovens or microwave ovens at a core temperature
of 60 to 90 °C), which is mostly performed today, normally extends the
storage life of bread up to from 4 to about 20 days if normal vapor-per-
meable polyethylene bag packages are used. Other plastic sheets, e.g., of
polypropylene, which are substantially more expensive, however, can
achieve a longer storage life due to their lower vapor permeability. Pack-
ages with polyester plastic materials and an introduced nitrogen-containing
CA 02294989 1999-12-20
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atmosphere result in an even longer storage life. However, all these
measures either are very expensive, or they can be applied only to expen-
sive special products and markets, and in part they lead to significant
quality losses of the sliced bread, e.g., through condensate formation in the
bread bag, too soft bread consistencies or premature drying. None of these
measures affect the actual causes of contamination by the cutting process,
which introduces or distributes the potential causative agents of perishing,
present in the environment as well as in the product or on the machine, in
the food product via the cutting device, e.g., the cutting blades.
As cutting aids, there are usually employed either mineral compositions,
which are no longer allowable in many countries, or vegetable cutting oils
which are often inherently contaminated, i.e., bacterially loaded. See, for
example, G. Schuster: Investigations on mould contamination of sliced
bread, Backer & Konditor 27(11), p. 345-347; G. Spicher: Die Quellen der
direkten Kontamination des Brotes mit Schimmelpilzen; Das Schneidol als
Faktor der Schimmelkontamination; Getreide, Mehl and Brot 32(4), p.91-
94.
Therefore, there is an urgent need for a cutting medium which allows for a
decontamination of the machine parts contacting the food product during
the cutting process and thereby causes an improved keeping quality of the
cut product; this need is satisfied by the cutting medium according to the
invention.
The cutting medium can be employed wherever industrial cutting is per-
formed and the cut product can be subject to perishing from bacteria or
fungi or to a contamination by viruses. This applies, for example, to pulps
and papers, but particularly to food or feed products.
In a preferred embodiment, the processing aid according to the invention is
useful for the cutting or slicing of bread, pastries, fish and fish products,
potatoes and products based on potatoes, fruits and vegetables and
products based on fruits and vegetables, sweets, starch products, pasta
food, meat and meat products, cheese products, poultry and poultry
products.
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If the processing aid is a cutting or slicing medium (e.g., for the slicing of
bread), it may be provided with a usual base of vegetable oil/fat/wax with
the addition of microbicidal processing aids based on flavoring agents.
According to the invention, the cutting medium (e.g., for use in the meat
products industry) may preferably consist exclusively of one or more
flavoring agents.
Natural emulsifiers, e.g., lecithins, may also be added to the vegetable oils,
waxes and fats in a concentration of from 1 to 25% by weight, in accor-
dance with the prior art. Exemplary emulsifiers are lecithins, citric acid
monoglycerides, diacetyltartaric acid, N-acetylphosphatidyl ethanolamine,
phosphatidyl inositol, phosphatidyl serine, phosphatide acids, phosphatidyl
choline. However, if the cutting medium according to the invention is
provided as an aqueous-based emulsion, there are used vegetable oils,
vegetable fats and vegetable waxes with unsaturated and saturated C16-Cls
fatty acids which also have a viscosity of about 10 mPa~s (20 °C) to
about
500 mPa~s (20 °C).
The cutting medium, which is composed, for instance, of the above men-
tioned fatty acids or oils and emulsifiers, can be employed as a cutting
emulsion (milk) after mixing with water in a ratio of from 1:1 to 1:40.
In practice, the cutting medium is applied to at least the machine parts
contacting the product to be cut for decontaminating them. According to
former experience, the media are suitably employed in dosages of 1-
20 g/kg of food, the dosage depending on the cutting device employed and
the kind of product to be cut.
The cutting media are mostly applied to the cutting devices, e.g., in bread
slicing, they are sprayed onto circular knife slicing machines by means of
which bread is subsequently sliced. According to the invention, parts of the
cutting devices, e.g., circular knives, band slicers (rotating band saws),
electrical or mechanical knives or cutting devices, electrical or mechanical
saws or sawing devices, electrical or mechanical chain saws or devices, are
wetted so that the cutting medium can display its decontaminating or
CA 02294989 1999-12-20
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microbicidal activity on the respective machine part and also on the surface
generated by the cutting or slicing.
The beneficial effect of the cutting media to be used according to the
invention is manifested by a prolonged storage life of the cut product, e.g.,
sliced bread. Not least, it is based on the fact that the cutting medium
penetrates the surface of the cut product and also decontaminates the bulk
of the cut food product, namely through the flavoring agents contained in
the cutting oil.
In addition, the flavoring agents herein described have microbicidal activity
in the vapor phase since most flavoring agents are easily volatilized.
Therefore, they are active in the so-called surroundings of the food product,
e.g., within the package of the food product when it has been packaged
after the cutting process, e.g., in a plastic sheet package.
This process of decontamination of the cut product after the actual cutting
process can be enhanced by a gentle thermal aftertreatment of the cut
product.
In the following, the invention will be further described by Examples:
Bacteriological assaar methods for additives
- quantitative suspension assay I (germ carrier test)
- quantitative suspension assay II (suspension test)
- quantitative suspension assay III (agar diffusion test)
Microorganisms: aerobic microorganisms (total germ count), Enterobacteri-
aceae, Enterococci, Lactobacilli, yeasts, molds. These methods are capable
of determining the effects of the additives as a function of dosage and
duration of action using different microorganisms on different nutrient
media.
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Quantitative suspension assay I - germ carrier test
Suspension, depending on the germ being tested:
Ringer solution
Tryptone soybean broth
Chromcult Enterococcus broth
wort broth
Germ carrier: 5 x 5 cm autoclaved cotton cloth or filter
Nutrient agar: total aerobics < plate count agar
(casein peptone glucose yeast extract agar)
Chromocult < Enterococcus faecalis
Enterococcus faecium
Streptococcus bovis
OGYE selective nutrient medium (yeast extract - glucose - oxytetracyclin)
Microorganisms - molds
Aspergillus niger
Saccharomyces
Deoxycholate lactose agar
Microorganisms
Lactose-positive - Escherichia coli
Lactose slightly positive - Enterobacter (cloacae)
Lactose slightly positive - Klebsiella (pneumoniae)
Lactose-negative - Salmonella (typhimurium and enteritidis)
Lactose-negative - Shigella (flexneri)
Lactose-negative - Proteus (mirabilis)
Lactose-negative - Pseudomonas
Lactose-negative - Enterococcus (faecalis)
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MRS-AGAR (Lactobacillus)
Lactobacillus vulgaris
Baird-Parker agar (with eggyolk-tellurite emulsion)
Microorganisms
Staphylococcus aureus
Staphylococcus epidermidis
Micrococcus (Enterococcus faecium)
Bacillus subtilis
Yeasts: Endomyces tibuliger
Cereus Mossel's selective agar (with eggyolk emulsion)
Microorganisms
Bacillus cereus
Bacillus subtilis
Escherichia coli
Pseudomonas aeruginosa
Proteus mirabilis
Staphylococcus aureus
Deoxycholate lactose agar
Microorganisms
Lactose-positive - Escherichia coli
Lactose slightly positive - Enterobacter (cloacae)
Lactose slightly positive - Klebsiella (pneumoniae)
Lactose-negative - Salmonella (typhimurium and enteritidis)
Lactose-negative - Shigella (flexneri)
Lactose-negative - Proteus (mirabilis)
Lactose-negative - Pseudomonas (Enterococcus faecalis)
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TGE agar (casein peptone-glucose-meat extract agar)
Microorganisms
Staphylococcus aureus
Streptococcus agalactiae
Enterococcus faecalis
Escherichia coli
Salmonella typhimurium
Pseudomonas aeruginosa
Bacillus cereus
Suspension assay - quantitative germ carrier test
Others: special nutrient media and differentiations
for: Clostridia, t_isteria and others
Contamination of the germ carriers
The contamination of the germ carriers is effected after placing in a sterile
glass dish by pouring the test germ suspension (>_ 106/ml) over them.
After 1-10 min of storing, the germ carriers are distributed in a glass dish
covered with sterile filter paper, and dried in an incubator at 36 °C ~
1 °C.
Test
The contaminated and dried germ carriers are placed in sterile glass dishes
and soaked with (gr. %/formulation) each; stored for 1 h and placed for
the respectively designated agar/test germ and incubated in the incubator
at the prescribed temperature.
After the recommended incubation time, the germ carriers are diluted in a
9-fold dilution (depending on the test germ) of 101 to 108, and introduced
in the respectively designated agar by a plate casting method.
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Calculation
All having from to 200 colonies as determined using the weighed arithmetic
mean:
C - Ec
nlxl+nzx0.1
xd
C - number of colony-forming units per ml/g
~ c = sum of the colonies from all Petri dishes used for the calculation
nl = number of Petri dishes of the lowest dilution stage used for the
calculation (nl = 2 for 2 Petri dishes)
nz = number of Petri dishes of the next higher dilution stage used for the
calculation
d = factor of the lowest evaluated dilution stage, the dilution stage re-
lated to nl.
Quantitative suspension assay II - suspension test
a) Inoculate test germ suspension with the desired test germ, e.g.,
106/ml, expose for 1-60 min. Place desired formulation to be tested
into desiganted germ suspension tubes (different percentages). Await
end of exposure times 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 (see a) prior to inoculating the test germs (see a). Await end
of exposure times and then inoculate with the respective test germs,
and inoculate or pour into the appropriate agar plates depending on
the test germ.
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Quantitative suspension assay III - agar diffusion test
Cast nutrient agar plates which contain, e.g., 104 microorganisms/ml.
A sterile filter paper slip (10 mm) is soaked with the formulation to be
tested and placed on the nutrient agar plate.
After the incubation of (time/temperature depending on the germ), the
formation of an inhibition halo is read as a positive response.
Formulation Examples
Bacteriological Effectivity
LacticBenzyl GlycerolPropylene Prior art - Formulation
~
acid alcohol I col exam les
10' 10 10b 10y 5 min exp. time total germ count
10' 10' 108 109 15 min exp. time
10' 10' 108 109 60 min ex . time
10/ml control
10' 10' 10~ 5 min exp. time Enterobacteria
106 10' 10' 108 15 min exp. time
106 10' 10' 108 60 min ex . time
10/m I control
10' 10 10~ 10~ 5 min exp. time Enterococci
10' 10' 108 108 15 min exp. time
10' 10' 108 108 60 min ex . time
10/ml control
10' 10' 10' 10s 5 min exp. time Lactobacilli
104 105 105 105 15 min exp. time
104 105 105 105 60 min ex . time
10'/m ( control
10' 10' 10' 10~ 5 min exp. time yeasts
105 104 105 105 15 min exp. time
105 104 105 105 60 min ex . time
10'/ml control
10' 10' 10' 10s 5 min exp. time molds
105 104 105 105 15 min exp. time
105 104 105 105 60 min ex . time
10'/ml control
CA 02294989 1999-12-20
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3 2 1b 1a Invention - Formulation
tannin tannin tannin tannin ExampIeS -
1 part 1 part 1 part 1a
benzyl benzyl benzyl 1 b
alcoholalcohol alcohol
100 3 parts 1 part
parts
10' 10' 10' 10b 5 min exp. time total germ count
103 102 102 106 15 min exp. time
103 102 103 106 60 min ex . time
10/ml control
10z 101 102 10 5 min exp. time Enterobacteria
102 101 101 106 15 min exp. time
102 101 101 106 60 min ex . time
10/ml control
103 104 103 10 5 min exp. time Enterococci
102 103 102 106 15 min exp. time
103 102 101 106 60 min ex . time
10a/ml control
lOz 101 102 105 5 min exp. time Lactobacilli
102 101 101 104 15 min exp. time
102 101 101 104 60 min ex , time
10'/ml control
10z 101 101 104 5 min exp. time yeasts
102 101 101 104 15 min exp. time
101 101 101 104 60 min ex . time
10'/ml control
101 101 101 104 5 min exp. time molds
102 101 101 104 15 min exp. time
101 101 101 104 60 min ex . time
10'/ml control
CA 02294989 1999-12-20
- 30 -
9 8 7 6 5 4 Invention Formula-
-
tannin tannin tannin tannin tannin tannin Example tion
a
1000 1000 100 parts3 parts 1 part 1 part
parts parts
benzyl benzyl benzyl benzyl benzyl benzyl
alcohol alcohol alcohol alcohol alcohol alcohol
1 part 1 part 1 part 1 part 10000 1000
parts parts
105 104 104 103 103 103 5 min exp.total
time
104 105 10 103 103 103 15 min germ
exp. time
10 104 103 103 104 60 min count
exp. time
1081m1 control
104 104 103 103 103 103 5 min exp.Entero-
time
104 103 103 l OZ 103 10z 15 min bacteria
exp. time
103 103 103 10z 103 10z 60 min
exp. time
1081m1 control
10 104 104 103 103 10 5 min exp.Entero-
time
104 104 105 104 103 103 15 min cocci
exp. time
104 104 105 104 l Oz 103 60 min
exp. time
1081m1 control
104 104 104 103 104 103 5 min exp.Lacto-
time
104 103 104 104 103 102 15 min bacilli
exp. time
104 103 104 103 102 102 60 min
exp. time
1051m1 control
103 103 103 104 103 t Oz 5 min exp.yeasts
time
103 102 103 104 10z 10' 15 min
exp. time
103 1 OZ 103 103 102 10' 60 min
exp. time
105Im1 control
103 104 103 103 102 10' 5 min exp.molds
time
104 104 103 103 1 Oz 10' 15 min
exp. time
104 104 103 103 10' 10' 60 min
exp. time
1051m1 control
CA 02294989 1999-12-20
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11 10 Invention - Formulation
benzyl alcohol benzyl alcohol Examples -
1 part 1 part 1b
propylene glycolpropylene glycol
a its 1 a rt
10' 10~ 5 min exp. time total germ count
104 103 15 min exp. time
104 104 60 min ex . time
10a/ml control
10' 10' 5 min exp. time Enterobacteria
104 103 15 min exp. time
103 102 60 min ex . time
10/ml control
104 104 5 min exp. time Enterococci
104 103 15 min exp. time
104 103 60 min ex . time
10/ml control
104 10 5 min exp. time Lactobacilli
103 103 15 min exp. time
103 103 60 min ex . time
10'/ml control
104 10 5 min exp. time yeasts
103 103 15 min exp. time
103 103 60 min ex . time
10'/ml control
10' 10' 5 min exp. time molds
103 103 15 min exp. time
103 103 60 min ex . time
10'/ml control
CA 02294989 1999-12-20
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14 13 12 Invention - Formulation
benzyl alcoholbenzyl benzyl Examples -
alc. alc.
1 part 1 part 1 part 1b
propylene propylene propylene
glycol glycol glycol
10000 arts 1000 arts 100 arts
10' 10y 104 5 min exp. timetotal germ count
105 104 104 15 min exp.
time
105 104 105 60 min ex .
time
10/ml control
_
10' 105 104 5 min exp. timeEnterobacteria
105 104 104 15 min exp.
time
104 104 104 60 min ex .
time
10/ml control
10' 10' 10s 5 min exp. timeEnterococci
105 105 105 15 min exp.
time
105 105 105 60 min ex .
time
106/ml control
104 10 104 5 min exp. timeLactobacilli
104 104 ~ 104 15 min exp.
time
104 104 103 60 min ex .
time
10'/ml control
104 10 104 5 min exp. timeyeasts
104 104 104 15 min exp.
time
104 104 104 60 min ex .
time
10'/ml control
104 104 104 5 min exp. timemolds
104 104 104 15 min exp.
time
104 103 103 60 min ex .
time
10'/ml control
CA 02294989 1999-12-20
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16 15 Invention - Formulation
benzyl alcohol benzyl alcohol Examples -
100 parts 10 parts ib
glycerol glycerol 1c
1 a rt 1 a rt
10' 104 5 min exp. time total germ count
105 104 15 min exp. time
105 104 60 min ex . time
10/ml control
10' 104 5 min exp. time Enterobacteria
104 104 15 min exp. time
104 104 60 min ex . time
10/ml control
10S 104 5 min exp. time Enterococci
105 104 15 min exp. time
104 104 60 min ex . time
10a/ml control
104 104 5 min exp. time Lactobacilli
104 104 15 min exp. time
104 103 60 min ex . time
10'/ml control
104 104 5 min exp. time yeasts
104 104 15 min exp. time
104 103 60 min ex . time
10'/m l control
104 104 5 min exp. time molds
104 103 15 min exp. time
104 103 60 min ex . time
10'/ml control
CA 02294989 1999-12-20
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17 18 Invention - Formulation
lactic acid anisole Examples
1 part 1 part
tannin tannin
1 part 1 part
benzyl alcohol benzyl alcohol
2 a its 88 a its
10' 10~ 5 min exp. time total germ count
101 103 15 min exp. time
101 103 60 min ex . time
10/ml control
10' 10s 5 min exp. time Enterobacteria
101 103 15 min exp. time
101 lOz 60 min ex . time
10/ml control
10' 103 5 min exp. time Enterococci
103 103 15 min exp. time
102 104 60 min ex . time
10/ml control
101 10 5 min exp. time Lactobacilli
101 102 15 min exp. time
101 102 60 min ex . time
10'/ml control
101 10 5 min exp. time yeasts
101 102 15 min exp. time
101 102 60 min ex , time
10'/ml control
101 10 5 min exp. time molds
101 101 15 min exp. time
101 101 60 min ex . time
10'/ml control
CA 02294989 1999-12-20
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20 19 Invention - Formulation
tannin tannin Examples
3 parts 3 parts ie
benzyl alcohol benzyl alcohol
1 part 1 part
glycerol Water
96 arts 96 arts
10' 10' 5 min exp. time total germ count
103 103 15 min exp. time
102 103 60 min ex . time
10/ml control
10' 10~ 5 min exp. time Enterobacteria
102 102 15 min exp. time
102 lOZ 60 min ex . time
10/ml control
10' 10' 5 min exp. time Enterococci
103 103 15 min exp. time
102 103 60 min ex . time
10/ml control
10' 10~ 5 min exp. time Lactobacilli
102 103 15 min exp. time
102 103 60 min ex . time
10'/ml control
104 104 5 min exp. time yeasts
103 104 15 min exp. time
103 103 60 min ex . time
10'/ml control
10' 10' S min exp. time molds
103 103 15 min exp. time
102 103 60 min ex . time
10'/ml control
