U.S. patent application number 09/861559 was filed with the patent office on 2001-10-18 for potentiation of biocide activity using a diethanolamide.
This patent application is currently assigned to Buckman Laboratories International, Inc.. Invention is credited to King, Vanja M., Whittemore, Marilyn S., Zhou, Xiangdong.
Application Number | 20010031775 09/861559 |
Document ID | / |
Family ID | 21859894 |
Filed Date | 2001-10-18 |
United States Patent
Application |
20010031775 |
Kind Code |
A1 |
King, Vanja M. ; et
al. |
October 18, 2001 |
Potentiation of biocide activity using a diethanolamide
Abstract
A method for increasing the effectiveness of a biocide is
described. In the method, at least one biocide and at least one
diethanolamide are applied to a substrate or aqueous system subject
to the growth of microorganisms. The diethanolamide is applied in
an amount effective to increase the biocidal activity of the
biocide. Biocidal compositions are described where the biocide and
the diethanolamide are present in a combined amount effective to
control the growth of at least one microorganism. Methods for
controlling the growth of microorganisms on various substrates and
in various aqueous systems are also described. The combination of
the biocide and the diethanolamide is particularly useful as a
biocide in the leather industry, the lumber industry, the
papermaking industry, the textile industry, the agricultural
industry, and the coating industry, as well as in industrial
process waters.
Inventors: |
King, Vanja M.; (Memphis,
TN) ; Whittemore, Marilyn S.; (Memphis, TN) ;
Zhou, Xiangdong; (Memphis, TN) |
Correspondence
Address: |
MORGAN, LEWIS & BOCKIUS
1800 M STREET NW
WASHINGTON
DC
20036-5869
US
|
Assignee: |
Buckman Laboratories International,
Inc.
|
Family ID: |
21859894 |
Appl. No.: |
09/861559 |
Filed: |
May 22, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09861559 |
May 22, 2001 |
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09031515 |
Feb 27, 1998 |
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6235299 |
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Current U.S.
Class: |
514/367 ;
514/512; 514/625; 514/627; 514/678 |
Current CPC
Class: |
C02F 2103/023 20130101;
A01N 37/20 20130101; C02F 1/50 20130101; A01N 37/20 20130101; A01N
61/00 20130101; A01N 43/78 20130101; A01N 47/14 20130101; A01N
43/653 20130101; A01N 35/04 20130101; A01N 37/20 20130101; A01N
2300/00 20130101 |
Class at
Publication: |
514/367 ;
514/512; 514/678; 514/625; 514/627 |
International
Class: |
A61K 031/428; A61K
031/265; A61K 031/164; A61K 031/12 |
Claims
The claimed invention is:
1. A method to increase the effectiveness of a biocide comprising
the step of applying at least one biocide and at least one
diethanolamide to a substrate or aqueous system subject to the
growth of microorganisms, wherein said diethanolamide is applied in
an amount effective to increase the biocidal activity of the
biocide.
2. A method according to claim 1, wherein said biocide is potassium
N-hydroxymethyl-N-methyl thiocarbamate,
2-thiocyanomethylthiobenzothiazol- e, propiconazole,
2-bromo-4'-hydroxyacetophenone, sodium 2-mercaptobenzothiazole or a
mixture thereof.
3. A method according to claim 1, wherein said diethanolamide is a
C.sub.12-C.sub.22 fatty acid diethanolamide.
4. A method according to claim 3, wherein said C.sub.12-C.sub.22
fatty acid comprises stearic acid, palmitic acid, oleic acid,
isooleic acid, linoleic acid, or a mixture thereof.
5. A method according to claim 3, wherein said C.sub.12-C.sub.22
fatty acid diethanolamide is an N,N-diethanol tall oil fatty amide;
diethanolamides of a mixture of fatty acids comprising iso-oleic
acid, oleic acid, palmitic acid and stearic acid; or a mixture
thereof.
6. A method according to claim 1, wherein the weight ratio of
biocide to diethanolamide ranges from about 99:1 to about 1:99.
7. A method according to claim 6, wherein said weight ratio ranges
from about 60:10 to about 10:60.
8. A method according to claim 7, wherein said weight ratio ranges
from about 50:50 to about 25:75.
9. A biocidal composition comprising: (a) at least one biocide and
(b) at least one diethanolamide, wherein (a) and (b) are present in
a combined amount effective to control the growth of at least one
microorganism.
10. A biocidal composition according to claim 9, wherein said
diethanolamide is a C.sub.12-C.sub.22 fatty acid
diethanolamide.
11. A biocidal composition according to claim 10, wherein said
biocide is potassium N-hydroxymethyl-N-methyl thiocarbamate,
2-thiocyanomethylthiobe- nzothiazole, propiconazole,
2-bromo-4'-hydroxyacetophenone, sodium 2-mercaptobenzothiazole or a
mixture thereof, and said C.sub.12-C.sub.22 fatty acid
diethanolamide is an N,N-diethanol tall oil fatty amide;
diethanolamides of a mixture of fatty acids comprising iso-oleic
acid, oleic acid, palmitic acid and stearic acid; or a mixture
thereof.
12. A biocidal composition according to claim 9, wherein said
microorganism is selected from algae, fungi, and bacteria.
13. A biocidal composition according to claim 9, wherein said
composition is in a liquid form selected from the group consisting
of an aqueous solution, dispersion, emulsion or suspension.
14. A biocidal composition according to claim 9, wherein the weight
ratio of (a) to (b) ranges from about 99:1 to about 1:99.
15. A biocidal composition according to claim 14, wherein said
weight ratio ranges from about 60:10 to about 10:60.
16. A biocidal composition according to claim 15, wherein said
weight ratio ranges from about 50:50 to about 25:75.
17. A method for controlling the growth of microorganisms on a
substrate comprising the step of contacting a substrate susceptible
to the growth of microorganisms with (a) at least one biocide; and
(b) at least one diethanolamide, and wherein (a) and (b) are
present in a combined amount effective to control the growth of at
least one microorganism on said substrate.
18. A method according to claim 17, wherein said biocide is
potassium-N-hydroxymethyl-N-methyl thiocarbamate,
2-thiocyano-methylthiob- enzothiazole, propiconazole,
2-bromo-4'-hydroxyacetophenone, sodium 2-mercaptobenzothiazole or a
mixture thereof.
19. A method according to claim 17, wherein said diethanolamide is
C.sub.12-C.sub.22 fatty acid diethanolamide.
20. A method according to claim 19, wherein said C.sub.12-C.sub.22
fatty acid diethanolamide is an N,N-diethanol tall oil fatty amide;
diethanolamides of a mixture of fatty acids comprising isooleic
acid, oleic acid, palmitic acid and stearic acid; or a mixture
thereof and said microorganism is selected from algae, fungi, and
bacteria.
21. A method of claim 17, wherein said substrate is a hide, a
textile substrate, lumber, a seed, or a plant.
22. A method according to claim 17, wherein said combined amount
ranges from about 0.0001% to about 4% (w/w).
23. A method according to claim 22, wherein said combined amount
ranges from about 0.0001% to about 0.2% (w/w).
24. A method for controlling the growth of microorganisms in an
aqueous system capable of supporting growth of a microorganism
comprising the step of treating said aqueous system with (a) at
least one biocide, and (b) at least one diethanolamide and wherein
(a) and (b) are present in a combined amount effective to control
the growth of at least one microorganism.
25. A method according to claim 24, wherein said biocide is
potassium N-hydroxymethyl-N-methyl thiocarbamate,
2-thiocyano-methylthiobenzothiazo- le, propiconazole,
2-bromo-4'-hydroxyacetophenone or a mixture thereof, and said
diethanolamide is a C.sub.12-C.sub.22 fatty acid
diethanolamide.
26. A method according to claim 25, wherein said C.sub.12-C.sub.22
fatty acid diethanolamide is an N, N-diethanol tall oil fatty
amide; diethanolamides of a mixture of fatty acids comprising
iso-oleic acid, oleic acid, palmitic acid and stearic acid; or a
mixture thereof.
27. A method according to claim 24, wherein said microorganism is
selected from algae, fungi, and bacteria.
28. A method according to claim 24, wherein said aqueous system is
a latex, a metal working fluid, an aqueous emulsion, an aqueous
detergent, cooling water, or an aqueous resin formulation.
29. A method according to claim 24, wherein said combined amount
ranges from about 0.5 to about 5000 parts per million of the
aqueous system.
30. A method according to claim 29, wherein said combined amount
ranges from about 5 to about 1000 parts per million of the aqueous
system.
31. A method according to claim 30, wherein said combined amount
ranges from about 10 to about 25 parts per million of the aqueous
system.
32. A method for controlling the growth of microorganisms on pulp
or paper in a papermaking process, comprising the step of
contacting the pulp or paper with (a) at least one biocide, and (b)
at least one diethanolamide, and wherein (a) and (b) are present in
a combined amount effective to control the growth of at least one
microorganism.
33. A method according to claim 32, wherein said pulp is contacted
by mixing said biocide and said diethanolamide into a pulp slurry
prior to reaching a formation wire in a papermaking process.
34. A method according to claim 32, wherein said biocide is
potassium N-hydroxymethyl-N-methyl thiocarbamate,
2-thiocyanomethylthiobenzothiazol- e, propiconazole, and
2-bromo-4'-hydroxyacetophenone or a mixture thereof, and said
diethanolamide is a C.sub.12-C.sub.22 fatty acid.
35. A method according to claim 34, wherein said C.sub.12-C.sub.22
fatty acid diethanolamide is an N,N-diethanol tall oil fatty amide;
diethanolamides of a mixture of fatty acids comprising iso-oleic
acid, oleic acid, palmitic acid and stearic acid; or a mixture
thereof.
36. A method according to claim 32, wherein said microorganism is
selected from algae, fungi, and bacteria.
Description
FIELD OF THE INVENTION
[0001] The invention relates to compositions and methods for
controlling the growth of microorganisms on a variety of substrates
and in aqueous systems. More particularly, the invention relates to
a combination of at least one biocide with at least one
diethanolamide where the diethanolamide potentiates the biocide's
biocidal effect.
BACKGROUND OF THE INVENTION
[0002] A large variety of commercial, industrial, agricultural, and
wood materials or products are subject to microbiological attack or
degradation which reduces or destroys their economic value.
Examples of such materials or products include surface coatings,
lumber, seeds, plants, leather and plastics. The various
temperatures at which such materials or products are manufactured,
stored, or used as well as their intrinsic characteristics make
them susceptible to growth, attack, and degradation by common
microorganisms such as algae, fungi, yeasts, and bacteria. These
microorganisms may be introduced during manufacturing or other
industrial process, by exposure to air, tanks, pipes, equipment,
and humans. They can also be introduced while using a material or
product, for example, by multiple openings and reclosures of
packages or from stirring or removing material with contaminated
objects.
[0003] Aqueous systems are also highly subject to microbiological
growth, attack, and degradation. These aqueous systems may be
fresh, brackish or saltwater systems. Exemplary aqueous systems
include, but are not limited to, latexes, surfactants, dispersants,
stabilizers, thickeners, adhesives, starches, waxes, proteins,
emulsifying agents, cellulose products, metal working fluids,
cooling water, waste water, process water, aqueous emulsions,
aqueous detergents, coating compositions, paint compositions, and
resins formulated in aqueous solutions, emulsions or suspensions.
These systems frequently contain relatively large amounts of water
and organic material causing them to be environments well-suited
for microbiological growth and thus attack and degradation.
[0004] Microbiological degradation of aqueous systems may manifest
itself as a variety of problems, such as loss of viscosity, gas
formation, objectionable odors, decreased pH, emulsion breaking,
color change, and gelling. Additionally, microbiological
deterioration of aqueous systems can cause fouling of the related
water-handling system, which may include cooling towers, pumps,
heat exchangers, and pipelines, heating systems, scrubbing systems,
and other similar systems.
[0005] Another objectionable phenomenon occurring in aqueous
systems, particularly in aqueous industrial process fluids, is
slime formation. Slime formation can occur in fresh, brackish or
salt water systems. Slime consists of matted deposits of
microorganisms, fibers and debris. It may be stringy, pasty,
rubbery, tapioca-like, or hard, and may have a characteristic
undesirable odor that is different from that of the aqueous system
in which it formed. The microorganisms involved in its formation
are primarily different species of spore-forming and
nonspore-forming bacteria, particularly capsulated forms of
bacteria which secrete gelatinous substances that envelop or encase
the cells. Slime microorganisms also include filamentous bacteria,
filamentous fungi of the mold type, yeast, and yeast-like
organisms. Slime reduces yields in production and causes plugging,
bulking, and other problems in industrial water systems.
[0006] Various chemicals known as biocides have been used to
prevent microbiological deterioration of industrial systems, raw
materials, and products. Examples of such biocides include:
[0007] TCMTB formulations, containing the fungicide
2-(thiocyanomethylthio)-benzothiazole (TCMTB), which are known in
the art and have often been used to control or prevent biological
fouling, including biofilm and slime formation, in aqueous systems.
TCMTB has been used for industrial microorganism control for over
20 years. TCMTB is known to be useful in controlling bacteria and
fungi in various aqueous systems and is commercially available from
Buckman Laboratories, Inc., Memphis, Tenn., under the tradenames
BUSAN.RTM. 30WB and BUSAN.RTM. 1030 as a 30% active ingredient. The
preparation and use of 2-(thiocyanomethyl-thio)-benzothiazole as a
microbicide and a preservative is described in U.S. Pat. Nos.
3,520,976, 4,293,559, 4,866,081, 4,595,691, 4,944,892, 4,839,373,
and 4,479,961 give examples of microbicidal properties of
2-(thiocyanomethylthio)benzothiazole. U.S. Pat. No. 5,413,795
describes compositions having TCMTB adsorbed onto a solid carrier.
The disclosures of all of these patents are incorporated herein by
reference.
[0008] Kathon: a two component microbiocide mixture of
5-chloro-2-methyl-4-isothiazolin-3-one (CMI) and
2-methyl-4-isothiazolin-- 3-one (MI). Kathon is a broad spectrum
microbiocide used in the pulp and paper industry. Kathon is also
recommended to control bacteria and fungi in water-based paper
coatings and coating components. Kathon is available from Rohm and
Haas, Philadelphia Pa. and as BUSAN.RTM. 1078 from Buckman
Laboratories, Memphis, Tenn. BUSAN.RTM. 1078 is contains 1.15% by
weight of CMI and 0.35% by weight of MI as active ingredients. CMI
and MI have the following chemical structures: 1
[0009] Bronopol: 2-bromo-2-nitropropane-1,3-diol. Bronopol is
available as MYACIDE.RTM. from Angus Chemical Company, Northbrook,
Ill. Bronopol is used in water treatment, oil production fluids,
waste injection wells, and with pulp and paper. The chemical
formula of bronopol is: 2
[0010] IPBC: Iodopropargyl butyl carbamate. IPBC can be obtained
from Troy Chemical, Newark, N.J. IPBC is an effective fungicide,
particularly in surface coating compositions, such as paint
formulations. IPBC is disclosed in U.S. Pat. Nos. 3,923,870 and
5,219,875. IPBC has the following chemical formula: 3
[0011] IPC: Iodopropargyl carbamate. IPC, an effective microbiocide
in aqueous systems and on numerous substrates, is disclosed in U.S.
Pat. Nos. 4,945,109 and 5,328,926. The chemical formula of IPC is:
4
[0012] DBNPA: 2,2-Dibromo-3-nitrilopropionamide. DBNPA is available
from Dow Chemical Company, Midland, Mich. and Buckman Laboratories,
Memphis, Tenn. as the product BUSAN.RTM. 94. DBNPA is a broad
spectrum bactericide having particular use to control slime in the
pulp and paper industry. BUSAN.RTM. 94 contains 20% by weight of
DBNPA as its active ingredient. DBNPA has the chemical structure:
5
[0013] Tribromophenol: 2,4,6-Tribromophenol. Tribromophenol is an
antifungal agent available from Great Lakes Chemical, West
Lafayette, Ind. under the trade name GREAT LAKES PH-73. The
chemical formula of tribromophenol is: 6
[0014] BIT: 1,2-benzisothiazoline-3-one.
1,2-Benzisothiazoline-3-one is a biocide useful for a variety of
aqueous systems, such as metalworking fluids, paint, adhesives,
starch-based-products, cellulose ether solutions, resin and rubber
emulsions. 1,2-benzisothiazoline-3-one is available from ICI
Specialty Chemicals, Melbourne, Australia as the product PROXEL
GXL-20, an aqueous solution of dipropylene glycol 20% by weight of
1,2-benzisothiazoline-3-one as the active ingredient.
1,2-Benzisothiazoline-3-one has the following chemical structure:
7
[0015] Propiconazole, also known as
(RS)-1-2-[(2,4-dichlorophenyl)-2-propy-
l-1,3-dioxalan-2ylmethyl]-1H-1,2,4-triazole, is one commercial
biocide which has been shown to have a reasonably good
toxicological profile and biocidal activity. Propiconazole is
commercially available from Buckman Laboratories, Inc., Memphis,
Tenn., for example, as a formulation containing about 24% actives
under the tradename BUSAN.RTM. 1292. Propiconazole has the
following chemical structure: 8
[0016] Other biocides include potassium N-hydroxymethyl-N-methyl
thiocarbamate, a 30% active ingredient in BUSAN.RTM. 52 product and
2-bromo-4'-hydroxyacetophenone, a 30% active ingredient in
BUSAN.RTM. 90. These products are available from Buckman
Laboratories, Memphis, Tenn.
[0017] Despite the existence of such biocides, industry is
constantly seeking more cost-effective technology which offers
equal or better protection at lower cost and lower concentration.
The concentration of conventional biocides and the corresponding
treatment costs for such use, can be relatively high. Important
factors in the search for cost-effective fungicides include the
duration of biocidal effect, reduced environmental impact, the ease
of use and the effectiveness of the biocide per unit weight.
SUMMARY OF THE INVENTION
[0018] In view of industry's search for more cost effective
biocides, the invention offers an improvement over current products
or practices.
[0019] The invention relates to a method to increase the
effectiveness of a biocide. This method applies at least one
biocide and at least one diethanolamide to a substrate or aqueous
system subject to the growth of microorganisms. The diethanolamide
is applied in an amount effective to increase the biocidal activity
of the biocide. The combination of the biocide with a
diethanolamide achieves superior biocidal activity at lower
concentrations and lower cost than the biocide alone against
microbiological attack or degradation such as discussed above.
[0020] One embodiment of the invention provides a biocidal
composition. The composition contains (a) at least one biocide and
(b) at least one fatty acid diethanolamide. In the composition, the
biocide (a) and the diethanolamide (b) are present in a combined
amount effective to control the growth of at least one
microorganism.
[0021] Another embodiment of the invention provides a method for
controlling the growth of a microorganism on a substrate. This
method contacts a substrate susceptible to the growth of
microorganisms with at least one biocide and a diethanolamide. The
biocide and diethanolamide are present in a combined amount
effective to control the growth of at least one microorganism on
the substrate.
[0022] The combination of biocide and diethanolamide according to
the invention may be used for controlling the growth of
microorganisms in aqueous systems. Thus, another embodiment of the
invention provides a method for controlling the growth of
microorganisms in an aqueous system capable of supporting growth of
a microorganism. This method treats the aqueous system with at
least one biocide and at least one diethanolamide above. The
biocide and the diethanolamide are present in a combined amount
effective to control the growth of at least one microorganism in
the aqueous system.
[0023] The biocide and diethanolamide combination of the invention
is useful in preventing the microbiological attack, degradation, or
deterioration of various types of raw materials and products such
as leather, textiles, pulp, paper and paperboard, coatings, lumber,
as well as agricultural products such as seeds and crops.
Advantageously, the combination may be used in various industrial
processes used to prepare or manufacture these products.
Accordingly, additional embodiments of the invention employ the
combination to control the growth of microorganisms on or in such
industrial products, raw materials or processes.
[0024] The foregoing and other features and advantages of the
invention will be made more apparent from the following detailed
description and preferred embodiments.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The invention relates to a method to increase the
effectiveness of a biocide. This method applies at least one
biocide and at least one diethanolamide to a substrate or aqueous
system subject to the growth of microorganisms. The diethanolamide
is applied in an amount effective to increase the biocidal activity
of the biocide.
[0026] According to the invention, the combination of a biocide and
a diethanolamide demonstrates an unexpected, enhanced biocidal
effect. That is, the combination of a biocide and a diethanolamide
achieves superior biocidal activity at lower biocide concentrations
as compared to the biocidal capability of the biocide alone,
although the amount of diethanolamide used has no biocidal effect
itself. Thus, the diethanolamide potentiates the biocidal activity
of the biocide. Such a superior effect presents a distinct economic
advantage and increases an individual biocide's effectiveness per
unit weight.
[0027] According to the invention, a diethanolamide may be used to
increase the effectiveness of any biocide or a mixture of biocides.
Preferred biocides include potassium N-hydroxymethyl-N-methyl
thiocarbamate, 2-thiocyanomethylthiobenzothiazole, propiconazole,
2-bromo-4'-hydroxyacetophenone, sodium 2-mercaptobenzothiazole and
mixtures thereof. The diethanolamide may be used with and in the
same manner as the particular biocide is used. Preferably, one or
more diethanolamides are incorporated into the formulation of the
biocide.
[0028] In one embodiment, the invention relates to a biocidal
composition comprising at least one biocide and at least one
diethanolamide. The biocide and the diethanolamide are present in a
combined amount effective to control the growth of at least one
microorganism. Mixtures of diethanolamides may also be used.
[0029] A general synthesis of diethanolamides mixes a 1:1 molar
ratio of diethanolamine with a fatty acid or mixture of fatty
acids. The mixture is then heated at a reflux under vacuum for
several hours and water is removed. If a mixture of acids is used,
an averaged molecular weight is calculated based on the ratio of
individual acids in the mixture. Completion of the reaction can be
monitored by IR analysis or free fatty acid content.
[0030] Fatty acids are carboxylic acids derived from or contained
in an animal or vegetable fat or oil. Fatty acids are composed of a
chain of alkyl groups containing from about 4 to about 22 carbon
atoms (usually even numbered) and have a terminal carboxylic acid
group. Fatty acids may be straight or branched, saturated or
unsaturated and even aromatic. Fatty acids which may be used in the
preparation of the diethanolamide include, but are not limited to,
butyric acid, lauric acid, decanoic acid, undecylenic acid,
palmitic acid, stearic acid, palmitoleic acid, oleic acid, isooleic
acid, linoleic acid, linolenic acid, and phenyl stearic acid. Fatty
acids employed in this invention preferably have long alkyl chains
in the C.sub.12-C.sub.22 range, with C.sub.16-C.sub.20 being
preferred. Unsaturated fatty acids such as oleic, isooleic,
linoleic, and linolenic are preferred.
[0031] Mixtures of fatty acids may also be used in the preparation
of mixtures of diethanolamide. For example, tall oil fatty acids,
palm oil fatty acids, and coconut oil fatty acids are mixtures of
fatty acids which may be used to prepare a mixture of
diethanolamides. Tall oil fatty acid (TOFA), which is predominantly
a mixture of oleic acid (.about.45 wt. %) and linoleic acid
(.about.36 wt. %) and other fatty acids, is available from Arizona
Chemical Company, Panama City, Fla. Another mixture of fatty acids
is sold under the trade name Century MO-5 by Union Camp Chemical
Company of Jacksonville, Fla. The Century MO-5 fatty acid mixture
contains about 46 wt. % isooleic acid, 37 wt. % oleic acid and 17
wt. % of saturated fatty acids such as palmitic acid and stearic
acid. Mixtures of fatty acids represent a preferred embodiment of
the invention.
[0032] Depending on the application, biocidal compositions
according to the invention may be prepared in various forms known
in the art. For example, the composition may be prepared in liquid
form as an aqueous solution, dispersion, emulsion, or suspension, a
dispersion or suspension in a non-solvent, or as a solution by
dissolving the biocide and the diethanolamide in a solvent or
combination of solvents. Suitable solvents include, but are not
limited to, methyl ethers of glycols, M-pyrol, or petroleum
distillates. The biocidal composition may be prepared as a
concentrate for dilution prior to its intended use. Common
additives such as surfactants, emulsifiers, dispersants, and the
like may be used as known in the art to increase the solubility of
the biocide or diethanolamide in a liquid composition or system,
such as an aqueous composition or system. In many cases, the
biocidal composition of the invention may be solubilized by simple
agitation.
[0033] Biocidal compositions of the invention may also be prepared
in solid form, for example as a powder or tablet, using means known
in the art. In a preferred method of preparation, a liquid product
containing the biocide is deposited on a carrier such as
diatomaceous earth or kaolin and mixed with a diethanolamide in the
form of a liquid or solution to form a powder or tablet.
[0034] The biocide and the diethanolamide may be combined in a
single composition. Alternatively, the biocide and the
diethanolamide may be employed as separate components such that the
combined amount for the intended use is effective to control the
growth of at least one microorganism.
[0035] As discussed above, the diethanolamide potentiates the
biocidal effect of the biocide. Thus, combining a diethanolamide
with a biocide provides superior biocidal activity to control the
growth of microorganisms as compared to the biocidal capability of
the biocide alone. Although the diethanolamide may exhibit biocidal
activity at concentrations above certain threshold levels, the
diethanolamide is not biocidally effective at the concentrations
used.
[0036] According to the invention, control of the growth of a
microorganism on a substrate or in an aqueous system means control
to, at, or below a desired level and for a desired period of time
for the particular substrate or system. This can vary from the
complete prevention or inhibition of microbiological growth to
control at a certain desired level and for a desired time. The
combination of biocide and diethanolamide described here can, in
many cases, reduce the total microbiological count to undetectable
limits and maintain the count at that level for a significant
period of time. Accordingly, the combination may be used to
preserve a substrate or system.
[0037] The effective amount or percentage of the combination of a
biocide and a diethanolamide necessary to achieve the desired
result will vary somewhat depending on the substrate or aqueous
system to be protected, the conditions for microbial growth, the
particular biocide, and the degree of protection desired. For a
particular application, the amount of choice may be determined by
routine testing of various amounts prior to treatment of the entire
affected substrate or system. In general, an effective amount used
on a substrate ranges from about 0.0001% to about 4% (w/w);
preferably about 0.0001% to about 0.2%. With aqueous systems, an
effective amount may range from about 0.5 to about 5000 parts per
million, more preferably from about 5 to about 1000 parts per
million of the aqueous system, and most preferably from, about 10
to about 25 parts per million. Similar amounts effectively control
slime formation. For slime control, effective amounts preferably
range from about 1 to about 200 parts per million, and more
preferably, from about 1 to about 25 parts per million of the
aqueous system, and in some cases as low as 0.5 ppm.
[0038] In a preferred embodiment, combinations of a biocide and a
diethanolamide are those combinations having a weight ratio of
biocide to diethanolamide from about 99:1 to about 1:99. More
preferably the weight ratio is from about 60:10 to about 10:60, and
most preferably, from about 50:50 to about 25:75. The weight ratio
may vary depending on the biocide, the intended use, the
microorganism encountered as well as the particular material,
product, or system to which the combination according to the
invention is applied.
[0039] The combination of a biocide and a diethanolamide may be
applied in a variety of industrial uses and processes for
microorganism control. The combination may be used in place of and
in the same manner as other biocides traditionally used in the
particular industry. As discussed above, such industries include,
but are not limited to the leather industry, the lumber industry,
the papermaking industry, the textile industry, the agricultural
industry, and the coating industry. The combination of a biocide
and a diethanolamide may also be used with aqueous systems such as
those previously discussed which are subject to microbiological
attack and degradation. The problems caused by microbiological
attack and deterioration in these various applications has been
described above. The use of the combination of a biocide and a
diethanolamide according to the invention to control the growth of
microorganisms in particular exemplary applications is described
below.
[0040] The invention also relates to a method for controlling the
growth of microorganisms on various substrates. The method
comprises the step of contacting a substrate susceptible to
microbiological growth or attack with a biocide and a
diethanolamide, as described above. The biocide and diethanolamide
are present in a combined amount effective to control the growth of
at least one microorganism on the substrate. Preferably, the method
may be used to eliminate or prevent substantially all
microbiological growth on the substrate. As discussed above, the
biocide and the diethanolamide may be applied together or as
separate compositions. Preferred applications of this general
method are discussed below.
[0041] In the leather industry, the combination of a biocide and a
diethanolamide may be used to control the growth of microorganisms
on a hide during a tanning process. To achieve this control, the
hide is contacted with a combined amount of a biocide and a
diethanolamide effective to control the growth of at least one
microorganism on the hide. The combination of the biocide and the
diethanolamide may be used in the tanning process in similar
amounts and manner similar to that used to apply other biocides
used in the tanning industry. The type of hide may be any type of
hide or skin that is tanned, for example cowhide, snake skin,
alligator skin, sheep skin, and the like. The amount used, to some
extent, will depend on the degree of microbiological resistance
required and may be readily determined by one skilled in the
art.
[0042] A typical tanning process comprises a number of stages,
including, but not limited to, a pickling stage, a chrome-tanning
stage, a vegetable-tanning stage, a post-tan washing stage, a
retanning stage, a dyeing stage, and a fatliquoring stage. The
combination of a biocide and a diethanolamide may be used during
all process stages in the tanning process in addition to those
stages where a known microbiological problem is occurring. In each
stage, the combination of a biocide and a diethanolamide may be a
component of the appropriate tanning liquor applied to the hide
undergoing tanning.
[0043] Incorporating the biocide and a diethanolamide in a tanning
liquor protects the hide from microbiological deterioration during
the tanning process. Preferably, the combination is uniformly
dispersed, e.g., under agitation, into an appropriate liquor to be
used in a tanning process. Typical tanning liquors include, for
example, a pickling liquor, a chrome-tanning liquor, a
vegetable-tanning liquor, a post-tan washing liquor, a retanning
liquor, a dye liquor, and a fatliquor. This method of application
ensures that the combination applied to the hides protects against
microbiological attack, deterioration, or other microbiological
degradation.
[0044] In a somewhat analogous nature, the combination of the
invention may also be employed to control the growth of
microorganisms on a textile substrate in a textile manufacturing
process. Contacting the textile substrate with a combination of a
biocide and a diethanolamide according to the invention effectively
controls the growth of a microorganism on the textile substrate. In
a textile process, the combination may be used in similar amounts
and a manner similar to other biocides commonly used in such
processes. As one of ordinary skill would appreciate, particular
amounts generally depend on the textile substrate and the degree of
microbiological resistance required.
[0045] The step of contacting the textile substrate with the
combination of a biocide and a diethanolamide may be accomplished
using means known in the textile art. To control microbiological
growth, a textile process generally dips the textile substrate into
a bath containing a biocide, alone or with other chemicals used to
treat the textile substrate. Alternatively, the textile substrate
may be sprayed with a formulation containing a biocide. In the bath
or the spray, the combination of biocide and diethanolamide
according to the invention are present in a combined amount
effective to control the growth of at least one microorganism on
the textile substrate. Preferably, the bath and the spray are
aqueous-based compositions.
[0046] To preserve the value of its raw materials and products, the
lumber industry also must control the growth of microorganisms in
order to prevent microbiological degradation of lumber. The
combination of a biocide and a diethanolamide according to the
invention is effective to control the growth of microorganisms on
lumber.
[0047] The combination of a biocide and a diethanolamide may be
used to protect the lumber in similar amounts and a similar manner
employed for other biocides used in the lumber industry. Contacting
lumber with an effective amount of the combination may be
accomplished, for example, by spraying the lumber with an aqueous
formulation containing the combination of a biocide and a
diethanolamide, by dipping the lumber into a dip bath containing
the combination, or other means known in the art. Dipping the
lumber in an aqueous bath is preferred.
[0048] The biocide and the diethanolamide are preferably uniformly
dispersed in a bath (for example, by agitation) prior to the
dipping of the lumber into the bath. In general, the lumber is
dipped into the bath, raised, allowed to drip dry, and then air
dried. The dip time will depend, as is known in the art, on a
variety of factors such as the biocide, the degree of
microbiological resistance desired, the moisture content of the
lumber, type and density of the wood, etc. Pressure may be applied
to promote penetration of the combination into the lumber being
treated. Applying a vacuum to the upper surface of the lumber may
also be used to degas the lumber and promote increased wetting of
the lumber by a bath containing the biocidal combination.
[0049] The combination of a biocide and a diethanolamide according
to the invention also has uses in the agricultural industry. To
control the growth of microorganisms on a seed or plant, the seed
or plant may be contacted with a biocide and a diethanolamide in a
combined amount effective to control the growth of at least one
microorganism on the seed or plant. This contacting step may be
accomplished using means and amounts known in the agricultural
industry for other biocides. For example, the seed or plant may be
sprayed with an aqueous formulation containing the combination of
biocide and diethanolamide, or dipped into a bath containing the
combination. After being sprayed or dipped, the seed or plant is
generally dried by means known in the art such as drip drying,
heated drying, or air drying. For plants or crops, the combination
may also be applied using a soil drench. Soil drenching is
particularly advantageous when the microorganisms of concern
inhabit the soil surrounding the plant.
[0050] Yet another aspect of the invention is a method for
controlling the growth of microorganisms in an aqueous system
capable of supporting such growth. The aqueous system is treated
with a biocide and a diethanolamide such that the biocide and
diethanolamide are present in a combined amount effective to
control the growth of at least one microorganism in the aqueous
system. This includes controlling, and preferably preventing, slime
formation in the aqueous system.
[0051] Examples of various aqueous systems include, but are not
limited to, latexes, surfactants, dispersants, stabilizers,
thickeners, adhesives, starches, waxes, proteins, emulsifying
agents, cellulose products, aqueous emulsions, aqueous detergents,
coating compositions, paint compositions, alum compositions, and
resins formulated in aqueous solutions, emulsions or suspensions.
The combination may also be employed in aqueous systems used in
industrial processes such as metal working fluids, cooling waters
(both intake cooling water and effluent cooling water), and waste
waters including waste waters or sanitation waters undergoing
treatment of the waste in the water, e.g., sewage treatment.
[0052] As with the other uses discussed above, the combination of a
biocide and a diethanolamide according to the invention may be used
in the same amounts and in the same manner as biocides
traditionally used in these various aqueous systems. The
combination not only protects the aqueous system prior to use or
when stored, but in many cases protects the aqueous system when in
use or in appropriate applications even after the aqueous system
has dried. When used in a paint formulation for example, the
combination not only protects the paint in the can, but also the
paint film after being applied to a substrate.
[0053] Another embodiment of the invention is a method for
controlling the growth of microorganisms on paper or in a
papermaking process, e.g., in a pulp or paper slurry and on a
finished paper product such as paper board. The paper, pulp, or
slurry is contacted with a biocide and a diethanolamide in a
combined amount effective to control the growth of at least one
microorganism on the paper, the pulp or in a slurry. The contacting
step is accomplished using means and amounts known in the
papermaking art.
[0054] According to this aspect of the invention, for example, a
forming web on a papermaking machine (or a wet-lap pulp) may be
contacted with the combination of a biocide and a diethanolamide by
spraying an aqueous dispersion containing the biocide and
diethanolamide onto the pulp after the pulp leaves the presses in a
papermaking process. Or, the biocide and the diethanolamide may be
incorporated into a bath used at the wet or size press and the web
contacted by nipping the web to incorporate the combination into
the web with any other agents applied at the press. Alternatively,
the pulp may be contacted by mixing the biocide and diethanolamide
into the pulp/white water mixture, preferably prior to the pulp
reaching the formation wire.
[0055] When treating paper (which includes paperboard and other
cellulosic products or substrates), the biocide and diethanolamide
may be added into pulp slurries in the headbox, in the substrate
forming solution, or in the white water system to treat the water
system itself or for incorporation into the body of the paper.
Alternatively, as with other known biocides, the combination of a
biocide and a diethanolamide according to the invention may be
mixed into a coating used to coat the finished paper.
[0056] The activity of the combinations described above has been
confirmed using standard laboratory techniques as discussed below.
In many cases, the diethanolamide potentiates the biocidal affect
of the particular biocide. The following examples are intended to
illustrate, not limit, the invention.
EXAMPLES
Preparation of N,N-Diethanol Tall Oil Fatty Acid Amide
[0057] 1.24 moles of tall oil fatty acid (350 grams, 282
grams/mole) were added with 1.24 mole diethanolamine (130 grams,
105.14 grams/mole) to a three neck round bottom flask equipped with
a stirrer. The mixture was heated at reflux under vacuum for
several hours. Aliquots were removed to detect formation of amide
peak by IR to monitor completion of the reaction.
Potentiating Effect of Diethanolamides
[0058] The following materials and procedure were used to determine
the potentiating effect of a diethanolamide with various
biocides.
[0059] Materials
[0060] 1. Microorganisms
[0061] (1) Pseudomonas aeruginosa ("Ps. aeruginosa") ATCC 15442 (a
bacterium)
[0062] (2) Aspergillus niger ("A. niger") ATCC 9642 (a fungus).
[0063] 2. Biocides
[0064] (1) potassium N-hydroxymethyl-N-methyl thiocarbamate, a 30%
active ingredient in BUSAN.RTM. 52 product;
[0065] (2) 2-thiocyanomethylthiobenzothiazole as BUSAN.RTM.
1030;
[0066] (3) 24% active propiconazole as BUSAN.RTM.) 1292; and
[0067] (4) 2-bromo-4'-hydroxyacetophenone as BUSAN.RTM. 90.
[0068] 3. Diethanolamides
[0069] (1) N,N-diethanol tall oil fatty amide; and
[0070] (2) diethanolamide of Century MO-5.
[0071] 4. Growth Media
[0072] (1) Antibacterial Test:
[0073] NaCl, 8.0 g; glucose, 1.0 g; tryptone, 1.0 g; DI water, 1.0
L.
[0074] (2) Antifungal Test:
1 KH.sub.2PO.sub.4, 0.7 g; MgSO.sub.47H.sub.2O, 0.7 g;
MnSO.sub.47H.sub.2O, 1.0 mg; NaCl, 5.0 mg; FeSO.sub.47H.sub.2O, 2.0
mg; ZnSO.sub.47H.sub.2O, 2.0 mg; NH.sub.4NO.sub.3, 1.0 g; Glucose,
10.0 g; DI Water, 1.0 L.
[0075] Procedure
[0076] 5 ml of growth medium were suspended in test tubes, and the
culture medium was autoclaved at 121.degree. C. for 20 min. Biocide
stock aqueous solutions were added in each tube to give the desired
biocide-diethanolamide concentrations in parts per million. No
biocide was added to the control tubes. All tubes were inoculated
by adding 0.1 ml of inoculum to give a bacterial concentration of
about 10.sup.6 cells/ml (10.sup.6 spores/ml for fungal test). After
each addition, the tubes were shaken vigorously to mix the contents
thoroughly. All inoculated tubes were placed at 37.degree. C. for
antibacterial test and at 28.degree. C. for antifungal test.
Bacterial growth was checked after 5-7 days and fungal growth was
checked after 10-14 days.
[0077] The MIC of each biocide and diethanolamide acting alone and
in combination was determined on a growth-no-growth basis. Tables
1-16 present both the lowest concentrations of each biocide and
diethanolamide separately for which there was no growth, and the
lowest concentration of biocide in combination with diethanolamide
for which there was no growth. A plus (+) sign represents the
presence of fugal or bacterial mat and a minus (-) sign represents
the absence of fungal or bacterial mat. The only tables which
demonstrate a neutral effect are Tables 2 and 4 where both
diethanolamide of Century MO-5 and N,N-diethanol tall oil fatty
amide had a neutral effect against Ps. aeruginosa. This is due to
the fact that propiconazole does not have any antibacterial
activity within the concentration range tested, i.e., up to 2000
ppm.
2TABLE 1 Combination of BUSAN .RTM. 1292 with diethanolamide of
Century MO-5 against A. niger BUSAN .RTM. Diethanol- BUSAN .RTM.
Diethanol- 1292 amide 1292 amide (ppm) (ppm) Growth (ppm) (ppm)
Growth 5 0 + 20 10 + 10 0 + 20 20 + 20 0 + 20 50 + 40 0 + 20 100 +
60 0 + 20 200 + 80 0 - 20 500 + 0 10 + 40 10 + 0 20 + 40 20 + 0 50
+ 40 50 + 0 100 + 40 100 + 0 200 + 40 200 - 0 500 + 40 500 - 5 10 +
60 10 - 5 20 + 60 20 - 5 50 - 60 50 - 5 100 - 60 100 - 5 200 + 60
200 - 5 500 + 60 500 - 10 10 + 80 10 - 10 20 + 80 20 - 10 50 + 80
50 - 10 100 + 80 100 - 10 200 + 80 200 - 10 500 - 80 500 -
[0078]
3TABLE 2 Combination of BUSAN .RTM. 1292 with diethanolamide of
Century MO-5 against Ps. aeruginosa BUSAN .RTM. Diethanol- BUSAN
.RTM. Diethanol- 1292 amide 1292 amide (ppm) (ppm) Growth (ppm)
(ppm) Growth 100 0 + 500 10 + 200 0 + 500 20 + 500 0 + 500 50 + 800
0 + 500 100 + 1000 0 + 500 200 + 2000 0 + 500 500 + 0 10 + 800 10 +
0 20 + 800 20 + 0 50 + 800 50 + 0 100 + 800 100 + 0 200 + 800 200 +
0 500 + 800 500 + 100 10 + 1000 10 + 100 20 + 1000 20 + 100 50 +
1000 50 + 100 100 + 1000 100 + 100 200 + 1000 200 + 100 500 + 1000
500 + 200 10 + 2000 10 + 200 20 + 2000 20 + 200 50 + 2000 50 + 200
100 + 2000 100 + 200 200 + 2000 200 + 200 500 + 2000 500 +
[0079]
4TABLE 3 Combination of BUSAN .RTM. 1292 with N,N-diethanol tall
oil fatty amide against A. niger BUSAN .RTM. Diethanol- BUSAN .RTM.
Diethanol- 1292 amide 1292 amide (ppm) (ppm) Growth (ppm) (ppm)
Growth 5 0 + 20 10 + 10 0 + 20 20 + 20 0 + 20 50 + 40 0 + 20 100 +
60 0 + 20 200 + 80 0 - 20 500 + 0 10 + 40 10 - 0 20 + 40 20 - 0 50
+ 40 50 + 0 100 + 40 100 + 0 200 + 40 200 + 0 500 + 40 500 - 5 10 +
60 10 - 5 20 + 60 20 - 5 50 + 60 50 - 5 100 + 60 100 - 5 200 + 60
200 - 5 500 + 60 500 - 10 10 + 80 10 - 10 20 + 80 20 - 10 50 + 80
50 - 10 100 + 80 100 - 10 200 + 80 200 - 10 500 + 80 500 -
[0080]
5TABLE 4 Combination of BUSAN .RTM. 1292 with N,N-diethanol tall
oil fatty amide against Ps. aeruginosa BUSAN .RTM. Diethanol- BUSAN
.RTM. Diethanol- 1292 amide 1292 amide (ppm) (ppm) Growth (ppm)
(ppm) Growth 100 0 + 500 10 + 200 0 + 500 20 + 500 0 + 500 50 + 800
0 + 500 100 + 1000 0 + 500 200 + 2000 0 + 500 500 + 0 10 + 800 10 +
0 20 + 800 20 + 0 50 + 800 50 + 0 100 + 800 100 + 0 200 + 800 200 +
0 500 + 800 500 + 100 10 + 1000 10 + 100 20 + 1000 20 + 100 50 +
1000 50 + 100 100 + 1000 100 + 100 200 + 1000 200 + 100 500 + 1000
500 - 200 10 + 2000 10 - 200 20 + 2000 20 - 200 50 + 2000 50 - 200
100 + 2000 100 + 200 200 + 2000 200 + 200 500 + 2000 500 +
[0081]
6TABLE 5 Combination of BUSAN .RTM. 1030 with diethanolamide of
Century MO-5 against A. niger BUSAN .RTM. Diethanol- BUSAN .RTM.
Diethanol- 1292 amide 1292 amide (ppm) (ppm) Growth (ppm) (ppm)
Growth 0.25 0 + 0.75 10 - 0.50 0 + 0.75 20 - 0.75 0 - 0.75 50 - 1 0
- 0.75 100 - 2 0 - 0.75 200 - 0.75 500 - 0 10 + 1 10 - 0 20 + 1 20
- 0 50 + 1 50 - 0 100 + 1 100 - 0 200 + 1 200 - 0 500 + 1 500 -
0.25 10 + 2 10 - 0.25 20 + 2 20 - 0.25 50 + 2 50 - 0.25 100 + 2 100
- 0.25 200 + 2 200 - 0.25 500 + 2 500 - 0.50 10 - 0.50 20 - 0.50 50
- 0.50 100 - 0.50 200 - 0.50 500 -
[0082]
7TABLE 6 Combination of BUSAN .RTM. 1030 with diethanolamide of
Century MO-5 against Ps. aeruginosa BUSAN .RTM. Diethanol- BUSAN
.RTM. Diethanol- 1292 amide 1292 amide (ppm) (ppm) Growth (ppm)
(ppm) Growth 10 0 + 40 10 + 20 0 + 40 20 - 40 0 + 40 50 - 80 0 - 40
100 - 160 0 - 40 200 + 40 500 + 0 10 + 80 10 - 0 20 + 80 20 - 0 50
+ 80 50 - 0 100 + 80 100 - 0 200 + 80 200 - 0 500 + 80 500 - 10 10
+ 160 10 - 10 20 + 160 20 - 10 50 + 160 50 - 10 100 + 160 100 - 10
200 + 160 200 - 10 500 + 160 500 - 20 10 + 20 20 + 20 50 - 20 100 -
20 200 - 20 500 +
[0083]
8TABLE 7 Combination of BUSAN .RTM. 1030 with N,N-diethanol tall
oil fatty amide against A. niger BUSAN .RTM. Diethanol- BUSAN .RTM.
Diethanol- 1292 amide 1292 amide (ppm) (ppm) Growth (ppm) (ppm)
Growth 0.20 0 + 0.5 1 + 0.50 0 + 0.5 5 + 1 0 - 0.5 10 - 2 0 - 0.5
25 - 4 0 - 0.5 50 - 0.5 100 + 0 1 + 1 1 - 0 5 + 1 5 - 0 10 + 1 10 -
0 25 + 1 25 - 0 50 + 1 50 - 0 100 + 1 100 - 0.2 1 + 2 1 - 0.2 5 + 2
5 - 0.2 10 + 2 10 - 0.2 25 + 2 25 - 0.2 50 + 2 50 - 0.2 100 + 2 100
-
[0084]
9TABLE 8 Combination of BUSAN .RTM. 1030 with N,N-diethanol tall
oil fatty amide against Ps. aruginosa BUSAN .RTM. Diethanol- BUSAN
.RTM. Diethanol- 1292 amide 1292 amide (ppm) (ppm) Growth (ppm)
(ppm) Growth 10 0 + 40 1 + 20 0 + 40 5 + 40 0 + 40 10 - 80 0 - 40
25 - 160 0 - 40 50 - 40 100 - 0 1 + 80 1 - 0 5 + 80 5 - 0 10 + 80
10 - 0 25 + 80 25 - 0 50 + 80 50 - 0 100 + 80 100 - 10 1 + 160 1 -
10 5 + 160 5 - 10 10 + 160 10 - 10 25 + 160 25 - 10 50 + 160 50 -
10 100 + 160 100 - 20 1 + 20 5 + 20 10 + 20 25 + 20 50 + 20 100
+
[0085]
10TABLE 9 Combination of BUSAN .RTM. 52 with diethanolamide of
Century MO-S against A. niger BUSAN .RTM. Diethanol- BUSAN .RTM.
Diethanol- 1292 amide 1292 amide (ppm) (ppm) Growth (ppm) (ppm)
Growth 5 0 + 20 10 + 10 0 + 20 20 + 20 0 + 20 50 - 50 0 - 20 100 -
100 0 - 20 200 - 200 0 - 20 500 - 0 10 + 50 10 - 0 20 + 50 20 - 0
50 + 50 50 - 0 100 + 50 100 - 0 200 + 50 200 - 0 500 + 50 500 - 5
10 + 100 10 - 5 20 + 100 20 - 5 50 + 100 50 - 5 100 + 100 100 - 5
200 + 100 200 - 5 500 + 100 500 - 10 10 + 200 10 - 10 20 + 200 20 -
10 50 + 200 50 - 10 100 + 200 100 - 10 200 + 200 200 - 10 500 + 200
500 -
[0086]
11TABLE 10 Combination of BUSAN .RTM. 52 with diethanolamide of
Century MO-5 against Ps. aeruginosa BUSAN .RTM. Diethanol- BUSAN
.RTM. Diethanol- 52 amide 52 amide (ppm) (ppm) Growth (ppm) (ppm)
Growth 10 0 + 50 10 + 20 0 + 50 20 + 50 0 + 50 50 - 100 0 + 50 100
- 200 0 - 50 200 + 400 0 - 50 500 + 0 10 + 100 10 + 0 20 + 100 20 -
0 50 + 100 50 - 0 100 + 100 100 - 0 200 + 100 200 - 0 500 + 100 500
+ 10 10 + 200 10 - 10 20 + 200 20 - 10 50 + 200 50 - 10 100 + 200
100 - 10 200 + 200 200 - 10 500 + 200 500 - 20 10 + 400 10 - 20 20
+ 400 20 - 20 50 + 400 50 - 20 100 + 400 100 - 20 200 + 400 200 -
20 500 + 400 500 -
[0087]
12TABLE 11 Combination of BUSAN .RTM. 52 with N,N-diethanol tall
oil fatty amide against A. niger BUSAN .RTM. Diethanol- BUSAN .RTM.
Diethanol- 52 amide 52 amide (ppm) (ppm) Growth (ppm) (ppm) Growth
5 0 + 20 10 - 10 0 + 20 20 - 20 0 + 20 50 - 50 0 - 20 100 - 100 0 -
20 200 - 200 0 - 20 500 + 0 10 + 50 10 - 0 20 + 50 20 - 0 50 + 50
50 - 0 100 + 50 100 - 0 200 + 50 200 - 0 500 + 50 500 - 5 10 + 100
10 - 5 20 + 100 20 - 5 50 + 100 50 - 5 100 + 100 100 - 5 200 + 100
200 - 5 500 + 100 500 - 10 10 + 200 10 - 10 20 + 200 20 - 10 50 +
200 50 - 10 100 + 200 100 - 10 200 + 200 200 - 10 500 + 200 500
-
[0088]
13TABLE 12 Combination of BUSAN .RTM. 52 with N,N-diethanol tall
oil fatty amide against Ps. aeruginosa BUSAN .RTM. Diethanol- BUSAN
.RTM. Diethanol- 52 amide 52 amide (ppm) (ppm) Growth (ppm) (ppm)
Growth 10 0 + 50 10 + 20 0 + 50 20 + 50 0 + 50 50 + 100 0 + 50 100
+ 200 0 - 50 200 + 400 0 - 50 500 + 0 10 + 100 10 - 0 20 + 100 20 -
0 50 + 100 50 - 0 100 + 100 100 - 0 200 + 100 200 - 0 500 + 100 500
- 10 10 + 200 10 - 10 20 + 200 20 - 10 50 + 200 50 - 10 100 + 200
100 - 10 200 + 200 200 - 10 500 + 200 500 - 20 10 + 400 10 - 20 20
+ 400 20 - 20 50 + 400 50 - 20 100 + 400 100 - 20 200 + 400 200 -
20 500 + 400 500 -
[0089]
14TABLE 13 Combination of BUSAN .RTM. 90 with diethanolamide of
Century MO-5 against A. niger BUSAN .RTM. Diethanol- BUSAN .RTM.
Diethanol- 90 amide 90 amide (ppm) (ppm) Growth (ppm) (ppm) Growth
2.5 0 + 10 10 + 5 0 + 10 20 + 10 0 + 10 50 - 20 0 - 10 100 - 40 0 -
10 200 - 80 0 - 10 500 + 0 10 + 20 10 - 0 20 + 20 20 - 0 50 + 20 50
- 0 100 + 20 100 - 0 200 + 20 200 - 0 500 + 20 500 - 2.5 10 + 40 10
- 2.5 20 + 40 20 - 2.5 50 + 40 50 - 2.5 100 + 40 100 - 2.5 200 + 40
200 - 2.5 500 + 40 500 - 5 10 + 80 10 - 5 20 - 80 20 - 5 50 - 80 50
- 5 100 + 80 100 - 5 200 + 80 200 - 5 500 + 80 500 -
[0090]
15TABLE 14 Combination of BUSAN .RTM. 90 with diethanolamide of
Century MO-5 against Ps. aeruginosa BUSAN .RTM. Diethanol- BUSAN
.RTM. Diethanol- 90 amide 90 amide (ppm) (ppm) Growth (ppm) (ppm)
Growth 5 0 + 20 10 + 10 0 + 20 20 + 20 0 + 20 50 + 40 0 + 20 100 +
80 0 - 20 200 + 160 0 - 20 500 + 0 10 + 40 10 + 0 20 + 40 20 + 0 50
+ 40 50 + 0 100 + 40 100 + 0 200 + 40 200 - 0 500 + 40 500 - 5 10 +
80 10 - 5 20 + 80 20 - 5 50 + 80 50 - 5 100 + 80 100 - 5 200 + 80
200 - 5 500 + 80 500 - 10 10 + 160 10 - 10 20 + 160 20 - 10 50 +
160 50 - 10 100 + 160 100 - 10 200 + 160 200 - 10 500 + 160 500
-
[0091]
16TABLE 15 Combination of BUSAN .RTM. 90 with N,N-diethanol tall
oil fatty amide against A. niger BUSAN .RTM. Diethanol- BUSAN .RTM.
Diethanol- 90 amide 52 amide (ppm) (ppm) Growth (ppm) (ppm) Growth
2.5 0 + 10 1 + 5 0 + 10 5 + 10 0 + 10 10 + 20 0 - 10 20 - 40 0 - 10
50 - 80 0 - 10 100 - 0 1 + 20 1 - 0 5 + 20 5 - 0 10 + 20 10 - 0 20
+ 20 20 - 0 50 + 20 50 - 0 100 + 20 100 - 2.5 1 + 40 1 - 2.5 5 + 40
5 - 2.5 10 + 40 10 - 2.5 20 + 40 20 - 2.5 50 + 40 50 - 2.5 100 + 40
100 - 5 1 + 80 1 - 5 5 + 80 5 - 5 10 + 80 10 - 5 20 + 80 20 - 5 50
+ 80 50 - 5 100 + 80 100 -
[0092]
17TABLE 16 Combination of BUSAN .RTM. 90 with N,N-diethanol tall
oil fatty amide against Ps. aeruginosa BUSAN .RTM. Diethanol- BUSAN
.RTM. Diethanol- 90 amide 90 amide (ppm) (ppm) Growth (ppm) (ppm)
Growth 5 0 + 20 1 + 10 0 + 20 5 + 20 0 + 20 10 + 40 0 + 20 25 + 80
0 - 20 50 + 160 0 - 20 100 + 0 1 + 40 1 + 0 5 + 40 5 + 0 10 + 40 10
- 0 25 + 40 25 - 0 50 + 40 50 - 0 100 + 40 100 - 5 1 + 80 1 - 5 5 +
80 5 - 5 10 + 80 10 - 5 25 + 80 25 - 5 50 + 80 50 - 5 100 + 80 100
- 10 1 + 160 1 - 10 5 + 160 5 - 10 10 + 160 10 - 10 25 + 160 25 -
10 50 + 160 50 - 10 100 + 160 100 -
* * * * *