U.S. patent application number 12/930458 was filed with the patent office on 2011-06-16 for biocide composition comprising pyrithione and pyrrole derivatives.
Invention is credited to Robert Martin, Craig Waldron, Gareth Williams, Tina Williams.
Application Number | 20110144232 12/930458 |
Document ID | / |
Family ID | 38471723 |
Filed Date | 2011-06-16 |
United States Patent
Application |
20110144232 |
Kind Code |
A1 |
Waldron; Craig ; et
al. |
June 16, 2011 |
Biocide composition comprising pyrithione and pyrrole
derivatives
Abstract
The present invention is directed to a biocidal composition
comprising a blend of one or more pyrithione compounds, and one or
more pyrrole compounds of Formula I wherein said biocidal
composition is copper free or low copper content.
Inventors: |
Waldron; Craig; (Marietta,
GA) ; Martin; Robert; (Monroe, CT) ; Williams;
Gareth; (Kirkbymoorside York, GB) ; Williams;
Tina; (Kirkbymoorside York, GB) |
Family ID: |
38471723 |
Appl. No.: |
12/930458 |
Filed: |
January 7, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11368244 |
Mar 3, 2006 |
7893047 |
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12930458 |
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Current U.S.
Class: |
523/122 ;
106/18.33; 514/188 |
Current CPC
Class: |
A01N 43/36 20130101;
Y10T 428/31855 20150401; Y10T 428/31678 20150401; A01N 43/36
20130101; C09D 5/14 20130101; A01N 43/36 20130101; C09D 5/1625
20130101; Y10T 428/31906 20150401; Y10T 428/31935 20150401; Y10T
428/31989 20150401; A01N 59/16 20130101; Y10T 428/31699 20150401;
A01N 43/40 20130101; A01N 2300/00 20130101; A01N 59/20
20130101 |
Class at
Publication: |
523/122 ;
514/188; 106/18.33 |
International
Class: |
C09D 5/16 20060101
C09D005/16; A01N 55/02 20060101 A01N055/02 |
Claims
1-31. (canceled)
32. A biocidal composition comprising: A.) a pyrithione compound
being copper pyrithione and B.) one or more pyrrole compounds of
Formula (I): ##STR00003## wherein X is halogen, CN, NO.sub.2 or
S(O).sub.nR.sub.1; Y is hydrogen, halogen or S(O).sub.nR.sub.1; Z
is halogen, C.sub.1-C4haloalkyl or S(O).sub.nR.sub.1; n is an
integer of 0, 1 or 2; R.sub.1 is C.sub.1-C.sub.4haloalkyl; L is
hydrogen or halogen; M and Q are each independently hydrogen,
halogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, CN,
NO.sub.2, R.sub.2CO or NR.sub.3R.sub.4, or when M and Q are on
adjacent positions and are taken together with the carbon atoms to
which they are attached MQ represents the structure --OCH.sub.2O--,
--OCF.sub.2O--, or --CH.dbd.CH--CH.dbd.CH--; R is hydrogen,
C.sub.1-C.sub.4alkoxyalkyl, C.sub.1-C.sub.4alkylthioalkyl or
R.sub.6CO; R.sub.2 is C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy or NR.sub.3R.sub.4;
R.sub.3 is hydrogen or C.sub.1-C.sub.4alkyl; R.sub.4 is hydrogen,
C.sub.1-C.sub.4alkyl or R.sub.5CO; R.sub.5 is hydrogen or
C.sub.1-C.sub.4alkyl; and R.sub.6 is C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.2-C.sub.6
alkenyloxy, C.sub.1-C.sub.4haloalkoxy, phenyl optionally
substituted with one to three C.sub.1-C.sub.4alkyl groups, benzyl,
phenoxy, benzyloxy, C.sub.1-C.sub.4alkylcarbonyloxy,
C.sub.3-C.sub.6cycloalkyl, naphthyl, pyridyl, thienyl or furanyl;
and wherein said biocidal composition is low copper content.
33. The biocidal composition of claim 32, wherein said pyrrole
compound of Formula (I) is selected from a group consisting of
2-trihalogenomethyl-3-halogeno-4-cyano pyrrole derivative
substituted in position 5 and optionally in position 1, the
halogens in positions 2 and 3 being independently selected from the
group consisting of fluorine, chlorine and bromine, the substituent
in position 5 being selected from the group consisting of phenyl,
mono- and dihalogenophenyl, mono- and di-C1-4 alkyl phenyl, and
monohalogeno mono-C1-4-alkyl phenyl, any halogen on the substituent
in position 5 being selected from the group consisting of chlorine
and bromine, the optional substituent in position 1 being selected
from C1-4 alkyl and C1-4 alkoxy C1-4 alkyl.
34. The biocidal composition of claim 32, wherein said pyrrole
compound is
2-trihalogenomethyl-3-halogeno-4-cyano-5-(p-chlorophenyl)pyrrole.
35. The biocidal composition of claim 32, wherein the pyrithione
compound and said compound of formula I are present in a weight
ratio of 9:1 to 1:9.
36. The biocidal composition of claim 32, wherein the pyrithione
compound and said pyrrole compound of Formula I are present in a
weight ratio of 3:2 to 2:3.
37. The biocidal composition of claim 32, wherein the pyrithione
compound and said pyrrole compound of Formula I are present in a
weight ratio of 3:1 to 1:3.
38. The biocidal composition of claim 32, further comprising at
least one acrylic polymer or co-polymer selected from the group
consisting of copper acrylate polymer or co-polymer, zinc acrylate
polymer or co-polymer, silyl acrylate polymer or co-polymer, and
combinations thereof.
39. A coating composition comprising an effective biocidal amount
of a biocidal composition comprising: A) a pyrithione compound
being copper pyrithione; and B) one or more pyrrole compounds of
Formula (I): ##STR00004## wherein X is halogen, CN, NO.sub.2 or
S(O).sub.nR.sub.1; Y is hydrogen, halogen or S(O).sub.nR.sub.1; Z
is halogen, C.sub.1-C4haloalkyl or S(O).sub.nR.sub.1; n is an
integer of 0, 1 or 2; R.sub.1 is C.sub.1-C.sub.4haloalkyl; L is
hydrogen or halogen; M and Q are each independently hydrogen,
halogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl,
C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, CN,
NO.sub.2, R.sub.2CO or NR.sub.3R.sub.4, or when M and Q are on
adjacent positions and are taken together with the carbon atoms to
which they are attached MQ represents the structure --OCH.sub.2O--,
--OCF.sub.2O--, or --CH.dbd.CH--CH.dbd.CH--; R is hydrogen,
C.sub.1-C.sub.4alkoxyalkyl, C.sub.1-C.sub.4alkylthioalkyl or
R.sub.6CO; R.sub.2 is C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy or NR.sub.3R.sub.4;
R.sub.3 is hydrogen or C.sub.1-C.sub.4alkyl; R.sub.4 is hydrogen,
C.sub.1-C.sub.4alkyl or R.sub.5CO; R.sub.5 is hydrogen or
C.sub.1-C.sub.4alkyl; and R.sub.6 is C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.2-C.sub.6
alkenyloxy, C.sub.1-C.sub.4haloalkoxy, phenyl optionally
substituted with one to three C.sub.1-C.sub.4alkyl groups, benzyl,
phenoxy, benzyloxy, C.sub.1-C.sub.4alkylcarbonyloxy,
C.sub.3-C.sub.6cycloalkyl, naphthyl, pyridyl, thienyl or furanyl;
and wherein said biocidal composition is low copper content.
40. The coating composition of claim 39, wherein said pyrrole
compound of Formula (I) is
2-trihalogenomethyl-3-halogeno-4-cyano-5-(p-chlorophenyl)pyrrole.
41. The coating composition of claim 39, wherein the effective
biocidal amount is between 1% and 15% by weight, based on the total
weight of said coating composition.
42. The coating composition of claim 39, wherein the effective
biocidal amount is between 2% and 10% by weight, based on the total
weight of said coating composition.
43. The coating composition of claim 42, wherein the effective
biocidal amount is between 3% and 8% by weight, based on the total
weight of said coating composition.
44. The coating composition of claim 42, wherein the pyrithione
compound and said compound of formula I are present in a weight
ratio of 9:1 to 1:9.
45. The coating composition of claim 42, wherein the pyrithione
compound and said pyrrole compound of Formula I are present in a
weight ratio of 3:2 to 2:3.
46. The coating composition of claim 42, wherein the pyrithione
compound and said pyrrole compound of Formula I are present in a
weight ratio of 3:1 to 1:3.
47. The coating composition of claim 42, wherein said coating
composition is paint.
48. The coating composition of claim 42, wherein said coating
composition is a varnish.
49. The coating composition of claim 42, wherein said coating
composition is a lacquer.
50. The coating composition of claim 42, wherein said coating
composition is a wood sealant.
51. The coating composition of claim 42, further comprising at
least one acrylic polymer or co-polymer selected from the group
consisting of copper acrylate polymer or co-polymer, zinc acrylate
polymer or co-polymer, silyl acrylate polymer or co-polymer, and
combinations thereof.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to a biocidal composition. More
particularly, this invention relates to a biocidal composition
comprising a blend of at least one selected pyrithione compounds
and at least one selected pyrrole derivatives that prevent, or
inhibit growth of microbes and the method of using such biocidal
composition.
[0003] 2. Brief Description of Art
[0004] Many compositions and formulations are known in the art for
the prevention, inhibition, and treatment of growth or infestation
of microbes. Likewise, there are many compositions and coatings
specifically formulated for the prevention, inhibition, and
treatment of growth or infestation of fouling organisms.
[0005] Fouling organisms present a large problem for substrates and
objects that are exposed to water. The term "fouling organism"
includes both hard and soft fouling organisms. Hard fouling
organisms include barnacles, mollusks, and the like, while soft
fouling organisms include algae, fungi, and the organisms listed in
U.S. Pat. No. 5,712,275, which is incorporated by reference herein.
Such organisms present a constant problem for objects and
substrates that are exposed to marine water, fresh water, brackish
water, sewage water, waste water, rain water, and the like.
[0006] Fouling organisms grow on, infest, or adhere to various
kinds of substrates and objects that are exposed to any type of
water. Growth or infestation of fouling organisms on surfaces is
visually unappealing. Additionally, growth may cause some problems
in using the substrates and objects that fouling organisms have
attached or infested. For example, one problem that occurs
frequently is the attachment of hard fouling organisms to a ship
hull. The organisms cause the surface of the ship to become rough,
thereby reducing the ship's speed.
[0007] Additionally, wood and wood products often experience growth
and infestation of microbes such as fouling organisms, termites and
the like. Growth and infestation of such microbes leads to warping,
cracking, and deterioration of the wood and wood products.
Consequently the wood and wood products lose value, visual appeal,
and usefulness.
[0008] To combat this problem, coatings comprising biocides were
developed. Examples of biocides found useful include tributylin
compounds, pyrithione compounds, oxathiazine compounds, pyrrole
compounds, triphenylboron compounds and terbutyn.
[0009] Pyrithione compounds and select pyrrole compounds are
separately known and used as biocidal or antifouling agents.
However, it is not known in the art, nor is it obvious to combine
the two compounds. Examples of prior art references teaching the
use of pyrithione compounds and selected pyrrole compounds include
the following:
[0010] U.S. Pat. No. 5,057,153 to Ruggiero relates to an improved
paint or paint base composition characterized by enhanced biocidal
efficacy. The paint contains a biocide comprising pyrithione salt
and a copper salt. Additionally, in U.S. Pat. No. 5,246,489 to
Farmer Jr. et al. a process for generating copper pyrithione
biocide in-situ in a paint formulation is disclosed. The paint and
paint bases of this patent comprise pyrithione compounds as the
only biocide present in the formulation.
[0011] U.S. Pat. No. 5,098,473 to Hani et al. relates to paints and
paint bases, and more specifically to a process for providing a
stable gel-free dispersion of zinc pyrithione plus cuprous oxide
biocide in paint (see also U.S. Pat. Nos. 5,098,473; 5,112,397;
5,137,569; 5,185,033; 5,232,493; 5,298,061; 5,342,437; PCT Patent
Application No. WO 95/10568 and EP 0610251).
[0012] U.S. Pat. No. 4,957,658 to French et al. related to paint
and paint bases and more specifically to a process and composition
for providing reduced discoloration of paints and paint bases
containing a pyrithione and ferric ion.
[0013] U.S. Pat. No. 4,399,130 to Davidson et al. describes a
method using an effective amount of at least one metallic salt of
pyridine-2-thione-N-oxide to treat or prevent swine exudate
epidermitis.
[0014] U.S. Pat. No. 4,496,559 to Henderson et al. describes
selected derivatives of 2-selenopyridine-N-oxide for use as
fungicides and bactericides.
[0015] U.S. Pat. No. 4,565,856 to Trotz et al. relates to
pyrithione-containing polymers. The polymers described in this
patent are used as biocides in paints and wood preservative
products.
[0016] U.S. Pat. No. 4,610,993 to Wedy et al. describes a method of
administering an effective mount of at least one selected
pyridine-N-oxide disulfide compound to treat or prevent bovine
mastitis.
[0017] European patent number EP 0746979 describes a method for
controlling or combating the attachment of a fouling organism to an
underwater surface by contacting the organism with an
antifouling-effective amount of a 2-arylpyrrole compound.
[0018] U.S. Pat. No. 6,069,189 to Kramer et al., describes
antifouling paints that contain selected pyrrole derivatives.
Specific pyrrole compounds incorporated into the antifouling paint
include 2-trihalogenomethyl-3-halogeno-4-cyano pyrrole and
derivatives thereof. Kramer et al. found these compounds to be
particularly effective against barnacle infestation. Additionally,
this Kramer et al. reference found that bright or light colored
anti-fouling paint could be created despite the addition of these
compounds.
[0019] PCT Patent Application No. WO 03/039256 describes an
antifouling composition that comprises an amount of at least 3.5
wt. % based on the total weight of the dry mass of the composition
of
4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile,
or a salt thereof together with another biocide. The other biocide
is selected from bethoxazin, tolylfluanide, dichlofuanide, or
DCOIT.
[0020] Despite the advances made in the art, what is still needed
is a coating that comprises an biocidal composition that would be
effective against a large spectrum of microbes, and also
demonstrates high durability and low toxicity. Ideally, the coating
and the composition would be easily and inexpensively produced.
This invention is believed to be an answer to the above discussed
problems.
BRIEF SUMMARY OF THE INVENTION
[0021] Therefore, one aspect of the present invention is directed
to a biocidal composition comprising one or more pyrithione
compounds, and one or more pyrrole compounds of Formula I:
##STR00001##
wherein X is halogen, CN, NO.sub.2 or S(O).sub.nR.sub.1; Y is
hydrogen, halogen or S(O).sub.nR.sub.1; Z is halogen,
C.sub.1-C.sub.4haloalkyl or S(O).sub.nR.sub.1; n is an integer of
0, 1 or 2; R.sub.1 is C.sub.1-C.sub.4haloalkyl; L is hydrogen or
halogen; M and Q are each independently hydrogen, halogen,
C.sub.1-C.sub.4allyl, C.sub.1-C.sub.4haloalkyl, C.sub.r
C.sub.4alkoxy, C.sub.1-C.sub.4alkylthio,
C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, CN,
NO.sub.2, R.sub.2CO or NR.sub.3R.sub.4, or when M and Q are on
adjacent positions and are taken together with the carbon atoms to
which they are attached MQ represents the structure --OCH.sub.2O--,
--OCF.sub.2O--, or --CH.dbd.CH--CH.dbd.CH--; R is hydrogen,
C.sub.1-C.sub.4alkoxyalkyl, C.sub.1-C.sub.4alkylthioalkyl or
R.sub.6CO; R.sub.2 is C.sub.1-C.sub.4haloalkyl,
C.sub.1-C.sub.4alkoxy or NR.sub.3R.sub.4; R.sub.3 is hydrogen or
C.sub.1-C.sub.4alkyl; R.sub.4 is hydrogen, C.sub.1-C.sub.4alkyl or
R.sub.5CO; R.sub.5 is hydrogen or C.sub.1-C.sub.4alkyl; and R.sub.6
is C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl,
C.sub.1-C.sub.4alkoxy, C.sub.2-C.sub.6 alkenyloxy,
C.sub.1-C.sub.4haloalkoxy, phenyl optionally substituted with one
to three C.sub.1-C.sub.4alkyl groups, benzyl, phenoxy, benzyloxy,
C.sub.1-C.sub.4alkylcarbonyloxy, C.sub.3-C.sub.6cycloalkyl,
naphthyl, pyridyl, thienyl or furanyl, wherein said biocidal
composition is copper free or low copper content.
[0022] As defined herein, the term halogen designates Cl, Br, I or
F, and the term haloalkyl designates any alkyl group
C.sub.nH.sub.2n+1 having from 1 halogen atom to 2n+1 halogen atoms
wherein the halogen atoms are the same or different.
[0023] Another aspect of the present invention is directed to a
coating composition comprising an effective biocidal amount of a
biocidal composition comprising one or more pyrithione compounds
and one or more pyrrole compounds of Formula (I) as described above
wherein said biocidal composition is copper free or low copper
content.
[0024] Still another aspect of the present invention is directed to
a method of coating a substrate comprising applying a coating
composition that contains a biocidal composition comprised of one
or more pyrithione compounds and one or more pyrrole compounds of
Formula (I) as described above, to the substrate and drying the
coating composition on the substrate.
[0025] Yet another aspect of the present invention is directed to a
coated substrate comprising the coating composition that contains a
biocidal composition of the present invention and a substrate,
wherein said substrate is selected from a group consisting of wood,
plastic, leather, vinyl and metal.
[0026] One expected advantage of the present invention includes
increased protection against a large spectrum of microbes. Another
expected advantage of the present invention includes preservation
of wood and wood-products. Additionally, it is expected that the
present invention will be long-lasting, have low toxicity, and be
easily and inexpensively produced.
DETAILED DESCRIPTION OF THE INVENTION
[0027] The term "an effective biocidal amount" as used in the
present specification and claims relates to the amount of the
biocidal composition that has a positive effect on reducing,
eliminating, or preventing attachment or growth of microbes on a
substrate.
[0028] The term "microbe" as used in the present specification and
claims includes algae, fungi, biofilm, insects, fouling organisms
(including both hard and soft fouling organisms), or any organism
that can attach to, grow on, or damage materials such as wood,
concrete, paper, plastic, and the like.
[0029] The term "copper free or low copper content" as used in the
present specification and claims means that the compositions do not
contain copper or contain copper at a total weight percent of less
than 3% by weight, based on the total weight of formulation.
[0030] The term "wood products" as used in the present
specification and claims includes materials that contain or are
derived from wood, including, but not limited to, particle board,
chipboard, plywood, wafer board, wood laminated material, pressed
wood, and the like.
[0031] As indicated above, one aspect of the present invention is a
biocidal composition comprising one or more pyrithione compounds
and one or more pyrrole compounds according to Formula (I) as
described above. Each of these components is discussed in more
detail below.
[0032] Pyrithiones in general are widely known and frequently used
in a variety of applications including paint and personal care
products. Pyrithiones are excellent biocides, and can be found in
antifouling marine paint. Additionally, metal salts of pyrithione
including tin, cadmium and zirconium, are suitable for use in
shampoo.
[0033] Preferably, the pyrithione in the biocidal composition are
compounds with the following basic structure:
##STR00002##
[0034] Pyrithione compounds suitable for use in the present
invention include zinc pyrithione, copper pyrithione, sodium
Omadine.RTM., pyridine-N-oxide disulfide, Omadine.RTM. disulfide,
2,2'-dithio-pyridine-1,1-dioxide, or pyridine-2-thione-N-oxide.
Such pyrithione compounds have excellent biocidal effects. Zinc and
copper pyrithione are most preferable because of the low soluable
in salt water therefore making it more durable than other
pyrithione salts.
[0035] The zinc and copper pyrithione compounds can be prepared by
methods described in U.S. Pat. No. 2,809,971 to Berstein et al.
Other patents disclosing similar compounds and processes for making
them include U.S. Pat. Nos. 2,786,847; 3,589,999; and
3,773,770.
[0036] Additionally, the biocidal composition of the present
invention comprises one or more pyrrole compounds of Formula (I) as
shown above. Preferably, the pyrrole compounds are
2-trihalogenomethyl-3-halogeno-4-cyano pyrrole derivatives
substituted in position 5 and optionally in position 1, the
halogens in positions 2 and 3 being independently selected from the
group consisting of fluorine, chlorine and bromine, the substituent
in position 5 being selected from the group consisting of C1-8
alkyl, C1-8 monohalogenoalkyl, C5-6 cycloalkyl, C5-6
monohalogenocycloalkyl, benzyl, phenyl, mono- and
di-halogenobenzyl, mono- and dihalogenophenyl, mono- and di-C1-4
alkyl benzyl, mono- and di-C1-4 alkyl phenyl, monohalogeno
mono-C1-4-alkyl benzyl and monohalogeno mono-C1-4-alkyl phenyl, any
halogen on the substituent in position 5 being selected from the
group consisting of chlorine and bromine, the optional substituent
in position 1 being selected from C1-4 alkyl and C1-4 alkoxy C1-4
alkyl. Among the 2-arylpyrrole compounds suitable for use in the
methods and composition of the invention are:
4,5-dichloro-2-(alpha, alpha,
alpha-trifluoro-p-tolyl)pyrrole-3-carbonitrile;
4-bromo-5-chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile;
4-bromo-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile;
3,4-dichloro-2-(3,4-dichlorophenyl)pyrrole-5-carbonitrile;
4-chloro-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile;
4,5-dibromo-2-(p-chlorophenyl)-3-(trifluoromethylsulfonyl)pyrrole;
4-bromo-2-(3,5-dichlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile;
2-(p-chlorophenyl)-5-(trifluoromethyl)-4-(trifluoromethylthio)pyrrole-3-c-
arbonitrile;
4-bromo-2-(2,3,4-trichlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitri-
le;
4-bromo-2-(2,3,5-trichlorophenyl)-5-(trifluoromethyl)-pyrrole-3-carbon-
itrile; 4-bromo-2-(p-chlorophenyl)-5-(alpha, alpha, beta,
beta-tetrafluoroethylthio)pyrrole-3-carbonitrile;
4-bromo-2-(m-fluorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile;
2-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4-(trifluoromethylthio)pyrrole-
-3-carbonitrile; and
4-bromo-2-(p-chlorophenyl)-5-[(beta-bromo-beta, alpha,
alpha-trifluoro)-ethylthio]pyrrole-3-carbonitrile. Most preferably,
Formula (I) is
4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile.
[0037] The compounds of Formula (I) as discussed above can be
prepared by methods described in U.S. Pat. Nos. 5,310,938 and
5,328,928.
[0038] To ensure biocidal effectiveness, the pyrithione compounds
and the compounds of Formula (I) are preferably present in the
biocidal composition in a weight ratio of 9:1 to 1:9. More
preferably, the pyrithione compounds and compounds of Formula (I)
are present in the biocidal composition in a weight ratio of 3:2 to
2:3. Most preferably, the pyrithione compounds and the compounds of
Formula (I) are present in the biocidal composition in a weight
ratio of 3:1 to 1:3.
[0039] Another aspect of the invention comprises a coating
composition that contains the above biocidal composition. The
biocidal composition is present in the coating composition in an
effective biocidal amount. The effective biocidal amount is between
1%-15% by weight, based on the total weight of the coating
composition. Preferably, the biocidal composition is present in an
amount between 1% and 15% by weight, based on the total weight of
the coating composition. More preferably, the biocidal composition
is present in an amount between 1% and 10% by weight, based on the
total weight of the coating composition. Most preferably, the
biocidal composition is present in an amount between 3% and 8% by
weight, based on the total weight of the coating composition.
[0040] In addition to the biocidal composition, the coating
composition may also include additives. Such additives may include,
but are not limited to, organic binding agents; processing
additives; fixatives such as polyvinyl alcohol; plasticizers; UV
stabilizers; dyes; color pigments; anti-settling agents;
antifoaming agents; additional insecticides such as chlorinated
hydrocarbons, organophosphates and, the like; additional fungicides
and bactericides such as alcohols, aldehydes, formaldehyde
releasing compounds, and the like; phenols; organic acids such as
propionic acid, benzoic acids and the like; inorganic acids such as
boric acid; amides; azoles; heterocyclic compounds; N-haloalkylthio
compounds; and the like. Polymers, such as acrylic polymers or
acrylic co-polymers, that are self-polishing for use in, for
example, marine antifouling coatings may also be employed.
Preferably, these polymers are free of tin. Examples of acrylic
polymers and copolymers that may be implemented in the composition
of the invention include copper acrylate polymer or co-polymer,
zinc acrylate polymer or co-polymer, silyl acrylate polymer or
co-polymer, and the like. Additional polymers known in the paint
and coating arts may also be employed in the composition of the
invention. The additives present in the coating composition will
depend on the preferences of the user or manufacturer as well as
the end use of the coating composition.
[0041] The coating composition is formed by combining the biocidal
composition and additives into a paint base material, such as a
marine paint base. Methods of forming such a coating composition
are well known in the art. Examples of such methods include, but
are not limited to combining the biocidal composition and the
additives in a blending mechanism. The blending mechanism would
evenly disperse the biocidal composition throughout the additives.
Additional methods of forming the coating composition can be used
as known to those skilled in the art. In addition, any base paint
material that is suitable for marine applications, including water
or solvent-based formulations, may be used in the coating
composition of the invention. Such marine paints are known in the
art, as shown, for example, in U.S. Pat. Nos. 6,710,117; 4,981,946;
4,426,464; 4,407,997; and 4,021,392.
[0042] The coating composition can take a variety of forms. Those
forms include, but are not limited to paint, (especially
anti-fouling paint), varnish, lacquer, a wash, a wood sealant, or
any form that may be used to coat the material.
[0043] Another aspect of the invention comprises a method
comprising applying the coating composition described above to
material being sought to protect. The coating composition may be
applied in a variety of manners that include, but are not limited
to brushing on, spraying on, sponging on, atomizing on, or dipping,
immersing, or soaking the material in. Preferably the coating
composition is applied in an even fashion to the material. Once the
coating composition is applied to the material, it should be
allowed to dry to ensure proper adhesion to the material. Drying
can be accomplished by exposure to the air, or by using a mechanism
that allows for faster drying such as heat lamps, or a hot air
generator.
[0044] Material that can be protected by the coating composition
includes wood, leather, vinyl, plastic, concrete, plaster, paper,
and any other material that may be exposed to microbes or to water
containing such microbes. Ideally, the material should be porous
enough to allow the coating composition to penetrate and adhere to
the material.
[0045] Another aspect of the invention comprises a coated
substrate. The coated substrate comprises a material as described
above that has been coated with the coating composition. Substrates
that would benefit the most from application of the coating
composition include traditional marine substrates such as ship
hulls, docks, piers, buoys, fishing gear, fishnets, lobster traps,
bridges, and pilings. However, substrates coated with the coating
composition may also include concrete, wallboard, decks, siding, or
any other substrate that is in constant or frequent contact with
water or microbes.
[0046] The substrate is expected to exhibit biocidal properties
when it is coated with the coating composition. The biocidal
properties will prevent, inhibit, or treat attachment or growth of
microbes on or in the substrate. Prevention or treatment of such
growth will allow the substrate to be microbe free. In addition to
the substrate being visually appealing, being microbe free will
allow it to be used in the manner it was intended to be used.
[0047] Additionally, it is expected that wood or wood products that
are coated with the coating composition will exhibit resistance to
microbes. Application of the coating composition to wood and wood
products is expected to prevent microbes such as fungi, algae,
termites, and the like from destroying the visual appeal and use of
the wood and wood products. Commercial and residential products and
structures that would benefit from such application include
staircases, floors, cabinets, decks, piers, shingles, pilings,
fences, furniture, mailboxes, and the like.
Examples
[0048] The following Examples further illustrate the present
invention. All parts and percentages are by weight unless
explicitly stated otherwise. All temperatures are degrees Celsius
unless explicitly stated otherwise.
Paint Efficacy Testing
[0049] A series of nine paint formulations containing
4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile
(referred to in below table as Pyrrole) and zinc pyrithione (ZPT)
were tested by Duke University off the Beaufort, N.C. coast in 2004
for their antifouling effectiveness against barnacles and other
fouling organisms. The formulations were created in the laboratory
by the addition of various amounts of biocides to a resin
base-formulation (vinyl resin/wood rosin with Zn oxide filler).
Formulations include
4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile
alone and in combination with ZPT. A solvent based zinc oxide
coating was used as a control. Unprimed fiberglass rods (8 mm
diameter.times.11 cm length) were dip-coated with each formulation
(5 rods/formulation) and suspended from a test rack in the ocean
(one-meter below the surface). Rods were evaluated each month for
number of barnacles and bryozoans. The most promising results came
from the formulations in which
4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile
was blended with ZPT (See Table 1 below).
[0050] Bryozoans are highly complex colonial animals constructed of
individual "zooids", all connected by living tissue. The zooids are
protected within a cup- or box-shaped exoskeleton of calcified
chitinous tissue. The degree of calcification governs how rigid or
flexible is the overall structure. Bryozoans are eaten by a variety
of grazing animals, such as sea urchins and various molluscs.
[0051] The study confirms that
4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile
is an effective antifouling agent for hard fouling organisms such
as barnacles, that it is compatible with ZPT, and that it performs
better with ZPT as a co-biocide than it does alone.
TABLE-US-00001 TABLE 1 2 months Average 3 months Average 4 months
Average 5 months Average DATES Jul. 16, 2004 Aug. 13, 2004 Sep. 15,
2004 Oct. 13, 2004 ROD # of # of # of # of CODE # Bryozoans
BARNACLES BARNACLES Bryozoans BARNACLES Bryozoans BARNACLES CONTROL
- 1 7.8 18.2 0 14 4 14.5 M M No Biocide 8% Pyrrole 2 0.4 1 0 4 2.2
8.6 M 1 Biocide 6% Pyrrole 3 0.4 1.4 0 7 0.6 5.6 0.2 0.8 Biocide 4%
Pyrrole 4 0 0.8 0 5.6 0.4 4 0.4 1.6 Biocide 5% Pyrrole 5 0 0.4 0 1
0 3.4 0 0.8 4% ZPT 5% Pyrrole 6 0 0.6 0 1.8 0 1.4 0 0.4 2% ZPT 2%
Pyrrole 7 0 1 0 16 0 3.2 0.2 1.2 2% Pyrrole 8 0 0.2 0 12.2 0.4 4.4
0 2 4% ZPT 2% Pyrrole 9 0 0.8 0 9.4 0 3.8 0 1.2 2% ZPT Notes: "M"
refers to a mature fouling community. The growth cycle of certain
marine organisms can cause a difference in the average number per
month reading in the above table.
[0052] While the invention has been described above with reference
to specific embodiments thereof, it is apparent that many changes,
modifications, and variations can be made without departing from
the inventive concept disclosed herein. Accordingly, it is intended
to embrace all such changes, modifications and variations that fall
within the spirit and broad scope of the appended claims. All
patent applications, patents and other publications cited herein
are incorporated by reference in their entireties.
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