Biocidal compositions comprising mixtures of haloproynyl compounds and sulfur containing triazines

This invention is directed to a broad spectrum fungicide/algaecide composition which comprises a mixture of (a) at least one halopropynyl compound and (b) at least one sulfur-containing s-triazine, said mixture provided in an amount to prevent and/or protect a substrate from attack by one or more fungal and/or algael organisms. The composition can be used broadly in industrial systems and more particularly with substrates such as paints, coatings, stucco, concrete, stone, cementaceous surfaces, wood, caulking, sealants, textiles, and the like.

FIELD OF THE INVENTION 
This invention is directed to a biocidal composition and particularly a 
synergistic mixture or combination of a halopropynyl compound and a 
sulfur-containing s-triazine. 
BACKGROUND OF THE INVENTION 
Both exterior and interior surfaces and substrates of all types, when 
exposed to common environmental conditions, e.g. moisture, are prone to 
attack, discoloration and various kinds of destruction by fungal and 
algael organisms. As a result, there is a great need and requirement for 
an effective and economical means to protect for extended periods of time 
both exterior and interior surfaces and various type substrates from the 
deterioration and destruction caused by such microorganisms. 
Materials which need protection with a suitable antimicrobial composition 
controlling both fungal and algael microorganisms and their adverse 
effects include paints, coatings, stucco, concrete, stone, cementaceous 
surfaces, wood, caulking, sealants, and textiles as well as materials and 
other substances which may be attacked by fungi and/or algae. 
Commercial products designed for the simultaneous control of fungi and 
algae on such substrates are available, but such products suffer from a 
number of disadvantages and especially their inability to maintain 
sufficient activity after leaching by water. 
In addition, such products currently available in the marketplace are 
generally supplied as normally water-insoluble powders, as pastes, or as 
flowable dispersions which are difficult to incorporate in a manner to 
insure maximum effectiveness. On the other hand, an effective composition 
in the form of a solution would be highly desirable having advantages for 
ease of handling and incorporation in end use products and to insure 
proper distribution of the biocide on or in the surfaces and substrates to 
be protected, thus maximizing microbiological performance. 
Thus, a broad spectrum biocide composition highly effective against both 
fungi and algae, and which is essentially unaffected by leaching with 
water, in an environmentally, toxicologically suitable liquid media has 
many advantages and is desirable for a wide number of uses in industry. 
With respect to compositions and/or mixtures, methods of manufacture and/or 
uses and applications of combinations of fungicides and algaecides, the 
prior art and references describing these combinations is limited. 
There are a number of organic compounds and especially certain carbamates, 
such as the halopropynyl carbamates which are known primarily for their 
fungicidal activity. 3-iodo-2 propynyl butyl carbamate, hereinafter 
referred to as IPBC, is the best known and the most widely used of the 
known haloalkynyl carbamate fungicides. In addition to its fungicidal 
activity, IPBC also has been associated with algaecidal activity. In this 
regard, Great Britain Patent 2,138,292 and U.S. Pat. Nos. 4,915,909 and 
5,082,722 contain such disclosures. IPBC is a highly active broad spectrum 
fungicide. Nevertheless, its spectrum of action is sometimes incomplete 
against the broad range of naturally occurring fungal species. For this 
reason, U.S. Pat. No. 5,389,300 describes using a phenol derivative, such 
as o-phenylphenol, with an iodopropargyl compound, such as IPBC, for 
protecting freshly sawn timber from such pests. 
Certain s-triazines are known for their algaecidai activity. They have been 
found to be especially effective for use in agricultural applications. One 
such example of this algaecide is N.sup.2 tertbutyl-N.sup.4 
-ethyl-6-methylthio-1,3,5-triazine-2,4 diyldiamine and a second such 
example is 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine. 
U.S. Pat. No. 4,710,220 for example, describes formulations containing a 
polyethoxylated compound and certain s-triazines, with N.sup.2 
-tert-butyl-N.sup.4 -ethyl-6-methylthio-1,3,5-triazine-2,4-diyldiamine, 
hereafter referred to as Terbutryn, as one example. Even so, Terbutryn is 
probably more widely known as a herbicide, and in particular, is widely 
disclosed for use as a herbicide in combination with a variety of other 
compounds. For example, in U.S. Pat. No. 3,957,481 it is used in 
combination with metobromuron for controlling weeds when cultivating 
leguminosae and solana; in U.S. Pat. No. 4,640,705 and Great Britain 
Patent 2,126,092 it is used in combination with trifluralin and 
ethylfluralin respectively, for preemergent control of weeds, particularly 
blackgrass, in cereal crops and in French Patent 2,438,970 it is used with 
neburon and nitrofen to control weeds in winter wheat. Nowhere, however, 
has it been suggested to combine Terbutryn with a halopropynyl compound 
and particularly a haloalkynyl carbamate fungicide for any purpose. 
In this regard, while U.S. Pat. No. 4,721,523 describes a herbicidal 
combination of certain widely-known carbamate derivatives with a 
photosynthesis-inhibiting compound, including as one of nine possible 
compound classes certain triazine derivatives (identifying Terbutryn as 
one of a dozen examples), the disclosed carbamates do not include the 
haloalkynyl carbamates. 
In a similar fashion, while U.S. Pat. No. 5,374,631 describes using a 
mixture of an iodopropargyl compound, including IPBC, with an s-triazine 
to control fungal and bacterial growth in metalworking fluids, the only 
triazine identified is hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine. 
Thus, the prior art has completely failed to appreciate any benefit from 
combining a halopropynyl compound and particularly a haloalkynyl carbamate 
with a sulfur-containing s-triazine. 
BRIEF DESCRIPTION OF THE INVENTION 
The present invention is based on the surprising synergistic effect that a 
combination of a halopropynyl compound, and particularly a halopropynyl 
carbamate fungicide, and a sulfur-containing s-triazine algaecide has on 
the increased efficacy of the resulting combined product, especially 
against fungi. 
In accordance with a preferred embodiment of the invention, it has now been 
discovered that synergistic combinations containing in particular both the 
fungicide, 3-iodo-2-propynyl butyl carbamate (IPBC) and the herbicide, 
N.sup.2 -tertbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5-triazine-2,4 
diyldiamine(Terbutryn) gives a surprising and unexpected biocidal effect 
against mold and blue-stain fungi. This increased biocidal effect has 
especially been shown to occur when the product is used against the fungi 
Aureobasidium pullulans and Alternaria alternata. This discovery is of 
outstanding commercial importance because the increased effect has 
especially been demonstrated after the test samples have been exposed to 
leaching with water. Particularly surprising is the good effect against 
Alternaria alternata, which often is found to be very difficult to control 
on exposed surfaces such as paints, coatings, stucco, concrete stone, 
cementaceous surfaces, wood, caulking, sealants, textiles, and the like. 
Relative proportions of the two components in compositions according to the 
present invention may be varied widely since the combination also provides 
excellent algaecidal properties. Depending on the degree of environmental 
pressure on the exposed area, it can be an advantage to select and adjust 
the proportions of the two components relevant to and depending upon which 
organism is more problematic to control and for which maximum protection 
is desired. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention is directed to a synergistic combination of a 
halopropynyl compound, particularly a halopropynyl carbamate such as IPBC, 
and a sulfur-containing s-triazine, particularly Terbutryn. 
A halopropynyl compound for use in the present invention can be identified 
by the following structure: 
EQU YC.tbd.C--CH.sub.2 X 
wherein Y is a halogen, preferably iodine and X can be (1) oxygen which is 
part of an organic functional group; (2) nitrogen which is an organic 
functional group; (3) sulfur which is part of an organic functional group; 
or (4) carbon which is part of an organic functional group. 
The functional group of which oxygen is a part is preferably an ether, 
ester, or carbamate group. The functional group of which nitrogen is a 
part is preferably an amine, amide, or carbamate group. The functional 
group of which sulfur is a part is preferably a thiol, thiane, sulfone, or 
sulfoxide group. The organic functional group of which carbon is a part is 
preferably an ester, carbamate or alkyl group. 
Examples of compounds which may be used as the halopropynyl compound 
fungicide of this invention are especially the fungicidally active 
iodopropargyl (iodopropynyl) derivatives. In this regard, please see U.S. 
Pat. Nos. 3,923,870, 4,259,350, 4,592,773, 4,616,004, 4,719,227, and 
4,945,109, the disclosures of which are herein incorporated by reference. 
These iodopropynyl derivatives include compounds derived from propargyl or 
iodopropargyl alcohols such as the esters, ethers, acetals, carbamates and 
carbonates and the iodopropargyl derivatives of pyrimidines, tiazolinones, 
tetrazoles, triazinones, sulfamides, benzothiazoles, ammonium salts, 
carboxamides, hydroxamates, and ureas. Preferred among these compounds is 
the halopropynyl carbamate, 3-iodo-2-propynyl butyl carbamate. This 
compound is included within the broadly useful class of compounds having 
the generic formulas: 
##STR1## 
Wherein R is selected from the group consisting of hydrogen, substituted 
and unsubstituted alkyl, aryl, alkylaryl, and aralkyl groups having from 1 
to 20 carbon atoms or from cycloalkyl and cycloalkenyl groups of 3 to 10 
carbon atoms, and m and n are independently integers from 1 to 3, i.e., 
not necessarily the same. 
Suitable R substituents include alkyls such as methyl, ethyl, propyl, 
n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, 
octadecyl, cycloalkyls such as cyclohexyl, aryls, alkaryls and aralkyls 
such as phenyl, benzyl, tolyl, cumyl, halogenated alkyls and aryls, such 
as chlorobutryl and chlorophenyl, and alkoxy aryls such as ethoxyphenyl 
and the like. 
Especially preferred are such iodopropargyl carbamates as 3-iodo-2-propynyl 
propyl carbamate, 3-iodo-2-propynyl butyl carbamate, 3-iodo-2-propynyl 
hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-iodo-2-propynyl 
phenyl carbamate, and mixtures thereof. 
Examples of compounds which may be used as the sulfur-containing s-triazine 
component of this invention include the known, algaecidally active 
s-triazine compounds. Those included, without limitation thereto, are 
N.sup.2 -tert-butyl-N.sup.4 
-ethyl-7-methylthio-1,3,5-triazine-2,4-diyldiamine and 
2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine. These 
compounds are represented by the genetic formula: 
##STR2## 
in which R.sup.1, and R.sup.2 independently of one another are each a 
C.sub.2 to C.sub.6 alkyl group or a C.sub.3 to C.sub.6 cycloalkyl. 
As C.sub.2 -C.sub.6 -alkyl, R.sup.1 and R.sup.2 are for example: ethyl, 
propyl, isopropyl, butyl, secbutyl, pentyl, isopentyl, hexyl, 
1,2-dimethylpropyl, 1,2-dimethylbutyl or 2,3-dimethylbutyl. Particularly 
preferred are branched-chain C.sub.3 -C.sub.6 -alkyl groups, for example 
isopropyl, 1,2-dimethylpropyl or tert-butyl. 
As C.sub.3 -C.sub.6 -cycloalkyl, R.sup.1 and R.sup.2 are for example: 
cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, cyclopropyl being 
preferred. 
Preferred sulfur-containing s-triazines of the formula are those wherein 
R.sup.1 is a branched-chain C.sub.3 -C.sub.6 -alkyl, for example 
isopropyl, 1,2-dimethylpropyl or tert-butyl; or wherein R.sup.1 is 
cyclopropyl. 
Likewise preferred are compounds of the formula wherein R.sup.1 is ethyl or 
cyclopropyl, and wherein R.sup.2 is tert-butyl, 1,2-dimethylpropyl or 
isopropyl. 
Relative proportions of the halopropynyl compound and the sulfur-containing 
s-triazine in the composition can vary widely and an optimum proportion 
likely will be affected by the intended application and the particular 
compounds selected. In any event, it is expected that compositions 
containing a little as 1 part of the halopropynyl compound to 9 parts of 
the s-triazine and conversely as little as 1 part of the s-triazine to 9 
parts of the halopropynyl compound will be useful. Typically, useful 
compositions will contain from 2:1 to 1:2 parts of the halopropynyl 
compound to the s-triazine and more usually from 2:1 to 1:1 relative parts 
by weight. 
In accordance with the invention, the combined fungicidal and algaecidal 
constituents can be included in a final formulation for use in such end 
use applications as paints, coatings, stucco, concrete, stone, 
cementaceous surfaces, wood, caulking, sealants, textiles, and the like, 
in a broad range from about 0.004% to 2.0% active concentration. Such 
compositions can be prepared from highly concentrated compositions of the 
active ingredients by appropriate dilution. The optimum useful range is 
about 0.1% to 0.3% of combined products in the final formulations for such 
end use systems. With the use of such modified formulations in end use 
systems, it is possible to protect surfaces as well as other substrates 
for extended periods of time against growth from both algae and fungi. 
Compositions of the present invention will generally be formulated by 
mixing the two active ingredients in a selected proportion with a liquid 
vehicle for dissolving or suspending the active components. The vehicle 
may contain a diluent, an emulsifier and a wetting-agent. Expected uses of 
the biocidal compositions include protection of wood, paint, coatings, 
adhesives, paper, textiles, plastics, cardboard, lubricants, caulkings, 
and the like. An extensive list of potential industries and applications 
for the present invention can be found in U.S. Pat. No. 5,209,930 which is 
herein incorporated by reference. The synergistic combinations of the 
halopropynyl compound fungicide, particularly a halo-propynyl carbamate, 
and the sulfur-containing s-triazine are preferably formulated as liquid 
mixtures, but may be provided as wettable powders, dispersions, or in any 
other suitable product type which is desirable and most useful, provided 
that the synergistic fungicidal and algaecidal activity are not affected. 
In this regard, the composition of the present invention can be provided 
as a ready-for-use product in the form of aqueous solutions and 
dispersions, oil solutions and dispersions, emulsions, aerosol 
preparations and the like or as a concentrate. 
Useful solvents for the halopropynyl compound, particularly the preferred 
iodopropynyl butyl carbamate, and sulfur-containing s-triazine, especially 
Terbutryn, combination are several glycol ethers and esters like propylene 
glycol n-butyl ether, propylene glycol tert-butyl ether, 
2(2-methoxymethylethoxy)-tripropylene glycol methyl ether, propylene 
glycol methyl ether, dipropyleneglycol methyl ether, tripropylenelene 
glycol methyl ether, propylene glycol n-butyl ether and the esters of the 
previously mentioned compounds. Other useful solvents are n-methyl 
pyrrolidone, n-pentyl propionate and dibasic esters of several 
dicarboxylic acids and mixes thereof. 
The preferred solvents for these products are propylene glycol n-butyl 
ether, 1-methoxy-2-propanol, and the dibasic isobutyl ester blend of 
succinic, glutaric and adipic acids. 
When preparing formulations of the present invention for specific 
applications, the composition also will likely be provided with other 
adjuvants conventionally employed in compositions intended for such 
applications such as organic binding agents, additional fungicides, 
auxiliary solvents, processing additives, fixatives. plasticizers, 
UV-stabilizers or stability enhancers, water soluble or water insoluble 
dyes, color pigments, siccatives, corrosion inhibitors, antisettlement 
agents, anti-skinning agents and the like. Additional fungicities used in 
the composition are preferably soluble in the liquid vehicle. 
According to the present invention, substrates are protected from 
infestation by fungal and algael organisms simply by treating said 
substrate with a composition of the present invention. Such treating may 
involve mixing the composition with the substrate, coating or otherwise 
contacting the substrate with the composition and the like. 
A surprising aspect of the invention was found to be that the mixtures of a 
halopropynyl compound, and particularly a iodopropynyl carbamate and a 
sulfur-containing s-triazine are especially efficacious in controlling the 
mold and blue stain fungi Aureobasidium pullulans and Alternaria 
alternata. These two organisms are both generally present in air, soil and 
water, and appear on most surfaces when moisture is present. Accordingly, 
these two fungi are a major commercial problem on surfaces coated with 
paints and other wood protection products and on other treated surfaces 
since in a short time, they can create a very heavy, dark staining which 
not only discolors the surface but attacks the coating and destroys it as 
well. Thus, such pests have a very destructive overall effect and a method 
for their control has long been sought. 
The fungi used in the tests, presented hereinafter, were selected because 
they are among the most problematic staining organisms which occur on 
exposed surfaces. While synergistic effects have been demonstrated against 
the specific organisms shown below in Tables 1 and 2, many other fungi can 
be controlled by these novel biocidal compositions. 
The novel compositions of the invention contain, at least, one herbicide 
from the sulfur-containing s-triazine group which is not presently known 
to have any fungicidal effect. However, they are highly efficacious 
against algae growing on the same areas as the mold fungi. The 
halopropynyl compound, and particularly the iodopropynyl carbamate is a 
fungicide used for protection against staining organisms and wood 
destroying fungi. With the Combination of these two biocides: a herbicide 
and fungicide it would be expected to obtain a product active against 
algae and fungi simultaneously. Surprisingly, it was found that the 
activity against the fungi Aureobasidium pullulans and Alternaria 
alternata was stronger than would be expected from any known dam. The data 
obtained from a solution in which the two compounds have been combined 
clearly shows that a synergistic and unexpected effect between the two 
compounds occurs.

The following examples are presented to illustrate and explain the 
invention. Unless otherwise indicated, all references to parts and 
percentages are based on weight. 
EXAMPLES 
Example 1 
The compositions of the invention were found to be effective against both 
algae and fungi. Specifically, algae and fungi which may be inhibited 
include without limitation, Stichococcus basillaris, Chlorella vulgaris, 
Chlorella vulgaris var. viridis, Trentepohlia aurea, Aspergillus niger, 
Aureobasidium pullulans, Alternaria alternata. The preferred combination 
of compounds, including an iodopropynyl carbamate and a sulfur-containing 
s-triazine were tested in various ratios from 2:1 to 1:6. 
The biological tests were carried out separately for algae and for fungi. 
Detailed descriptions of the tests are outlined below. 
In the algae test, an algae inoculum was prepared by washing a one-week old 
plate of each species into 100 ml isotonic water. The active formulations 
were applied on filter paper at the rate of 225 g/m.sup.2. After a drying 
time of one week, the filter paper was divided into two parts, one part 
was immersed into tap water at room temperature, leached for 24 hours and 
then dried. The other part was allowed to remain unleached. 1.26 cm.sup.2 
discs were cut from the leached and unleached filter paper and placed on 
the agar plates. A suspension of 0.5 ml algae was spread over the plate 
and the test paper with an appropriate spatula. 
The plates were incubated at 15.degree. C. and evaluated after 2 weeks. 
When the combination samples were tested against fungi, each sample was 
coated upon filter paper in duplicate, and then air dried for 1 week. One 
of the filter papers was exposed (leached) for 24 hours in room 
temperature tap water and air dried for 24 hours. Each sample was then cut 
into 1 inch squares of which 2 were placed in petri dishes containing 
solidified Malt Agar and seeded with Aspergillus niger, conidia and hypha 
fragments; 2 were placed in petri dishes containing solidified Malt Agar 
and seeded with Aureobasidium pullulans, conidia and hypha fragments, and 
2 were placed in petri dishes containing solidified Malt Agar and seeded 
with Alternadia alternata, conidia and hypha fragments. The petri dishes 
were incubated for a period of 3 weeks at 28 degrees C. 
Tables 1 and 2 show the results of the comparative tests which were carried 
out as described above. The formulations tested were comprised of 0.1% of 
3-iodo-2-propynyl-butylcarbamate (IPBC), 0.1% and 0.2% of N.sup.2 
tertbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5-triazine-2,4 diyldiamine 
(Terbutryn) and mixtures of 0.1% IPBC and 0.1% Terbutryn. Test results 
actually show that unexpected synergistic results in inhibition and growth 
reduction were obtained with the tested mixtures as compared with effects 
to be expected or predicted from the individual ingredients when tested 
against fungi, i.e., Aspergillus niger, Aureobasidium pullulans and 
Alternaria alternata. 
TABLE 1 
__________________________________________________________________________ 
COMATIVE TEST RESULTS AGAINST ALGAE AND FUNGI 
OF IPBC, TERBUTRYN, AND THE COMBINATION OF 
IPBC AND TERBUTRYN 
ALGAE* A. NIGER A. PULLULANS 
A. ALTERNATA 
% Unleached 
Leached 
Unleached 
Leached 
Unleached 
Leached 
Unleached 
Leached 
__________________________________________________________________________ 
IPBC 0.1 
4 4 Z10 Z8 Z5 0 Z2 0 
TERBUTRYN 
0.2 
Z25 Z23 5 5 5 5 5 5 
IPBC + 
TERBUTRYN 
0.2 
Z25 Z23 Z12 Z8 Z7 Z4 Z4 Z2 
RATIO 1:1 
__________________________________________________________________________ 
Legend: 
Z = Zone of Inhibition (in mm) 
0 = No growth 
1 = Trace Growth 
2 = Light Growth 
3 = Moderate Growth 
4 = Heavy Growth 
5 = Very Heavy Growth 
*Test Algae Mixture: Stichococcus basillaris, Chlorella Vulgaris, 
Chlorella Vulgaris var. viridis and Trentepohlia aurea 
TABLE 2 
__________________________________________________________________________ 
COMATIVE TEST RESULTS AGAINST ALGAE AND FUNGI 
OF IPBC, TERBUTRYN, AND THE COMBINATION OF 
IPBC AND TERBUTRYN 
ALGAE* A. NIGER A. PULLULANS 
A. ALTERNATA 
% Unleached 
Leached 
Unleached 
Leached 
Unleached 
Leached 
Unleached 
Leached 
__________________________________________________________________________ 
IPBC 0.1 
4 4 Z10 Z8 Z5 0 Z2 0 
TERBUTRYN 
0.1 
Z25 Z20 1 5 5 1 5 5 
IPBC + 
TERBUTRYN 
0.2 
Z25 Z23 Z12 Z8 Z7 Z4 Z4 Z2 
RATIO 1:1 
__________________________________________________________________________ 
Legend: 
Z = Zone of Inhibition (in mm) 
0 = No growth 
1 = Trace Growth 
2 = Light Growth 
3 = Moderate Growth 
4 = Heavy Growth 
5 = Very Heavy Growth 
*Test Algae Mixture: Stichococcus basillaris, Chlorella Vulgaris, 
Chlorella Vulgaris var. viridis and Trentepohlia aurea 
Example 2 
Liquid Formulations--Synergistic Combinations 
TABLE 3 
______________________________________ 
Ingredient % W/W 
______________________________________ 
A. 1:1 combination 
3-iodo-2-propynyl butyl carbamate 
20 
N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5- 
20 
triazine-2,4-diyldiamine 
DBE dibasic ester 3 
propylene glycol n-butyl ether 
57 
B. 1:1 combination 
3-iodo-2-propynyl butyl carbamate 
20 
N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5- 
20 
triazine-2,4-diyldiamine 
Propylene glycol n-butyl ether 
60 
C. 2:1 combination 
3-iodo-2-propynyl butyl carbamate 
26.6 
N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5- 
13.4 
triazine-2,4-diyldiamine 
Propylene glycol n-butyl ether 
60 
D. 1:2 combination 
3-iodo-2-propynyl butyl carbamate 
13.4 
N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5- 
26.6 
triazine-2,4-diyldiamine 
Propylene glycol n-butyl ether 
60 
______________________________________ 
A suitable reaction vessel equipped with an appropriate mixing unit is 
charged with the indicated mounts of solvents in Examples 2A through 2D of 
Table 3. The mixing unit is started and the indicated amounts of the 
carbamate and triazine compounds were added. Mixing was continued until 
the biocides were completely dissolved. The mixture was then filtered 
(with filter-aid) before transfer to appropriate containers. 
A number of liquid formulations were prepared as described above and were 
then incorporated into paints by mixing. The precise composition of 
biocides are set forth in detail in Table 3. They were tested according to 
the method as described in Example 1. The test results showed synergistic 
activity against algae and fungi when the combinations of two ingredients 
of carbamate and triazine were used at 0.1 total active level. Shown in 
Table 3 are examples of the preferred solvents used in the preparation of 
liquid formulations. 
TABLE 4 
______________________________________ 
WETTABLE POWDER 
Parts/Wt 
______________________________________ 
Example 3A - Ingredient 
3-iodo-2-propynyl butyl carbamate (IPBC) 
520 
Silicon dioxide (silica) 50 
Aluminum-Silicate (Clay) 363 
Sulphonated Napthalene Condensate (Dispersant) 
60 
Alkylated Napthalene Sulphonate (Dispersant) 
7 
TOTAL 1000 
Example 3B - Ingredients 
N.sup.2 -terbutyl-N.sup.4 -ethyl-6-methylthio-1,3,5-triazine- 
520 
2,4-diyldiamine (Terbutryn) 
Silicon dioxide (silica) 50 
Aluminum-Silicate (clay) 363 
Sulphonated Napthalene Condensate (Dispersant) 
60 
Alkylated Napthalene Sulphonate (Dispersant) 
7 
TOTAL 1000 
______________________________________ 
A mixture was prepared as reported as Example 3A and Example 3B in ratio 
1:1, using a shaker such as that used for similar paint products to 
produce a final product with 50% (w/w) activity. 
The biocide formulation was incorporated into a styrene-acrylic paint 
formulation and tested according to the method described in Example 1 with 
similar synergistic results obtained. 
TABLE 5 
______________________________________ 
DISPERSION 
Ingredient A Part/Wt. 
Ingredient B Part/Wt. 
______________________________________ 
Propylene glycol 
7 Propylene glycol 
7 
3-iodo-2-propynyl butyl 
42 N.sup.2 -terbutyl-N.sup.4 -ethyl-6- 
42 
carbamate (IPBC) methylthio-1,3,5-triazine-2, 
4-diyldiamine (Terbutryn) 
Aerosil 1 Aerosil 1 
(Hydrophobic Silica) (Hydrophobic Silica) 
Mix 
Dispersant 2.0 2.0 
(Nonylethoxylate) 
Wetting Agent 
1.0 Wetting Agent 1.0 
(Ethoxylated Sulphate) 
(Ethoxylated Sulphate) 
Wetting Agent 
1.0 Wetting Agent 1.0 
(Ethoxylated Sulphate) 
(Ethoxylated Sulphate) 
Water 34.40 Water 34.40 
Thickener 1.0 Thickener 1.0 
100 100 
______________________________________ 
Ingredients A and B as shown in Table 5 were made using a dispersing mill 
(with cooling mantle) and using 1 mm glass beads to a fineness grind 5 
microns or less. Some of the water may be omitted in order to obtain a 
thicker grinding paste as desired. 
A mixture of A and B was made by combining the ingredients in a ratio of 
1:1 to produce a synergistic combination product of the algaecide and the 
fungicide. 
This product was then mixed into a styrene-acrylic paint using a laboratory 
mixer for a 5 minute mixing period. It was tested as described in Example 
1 with similar results. 
While certain specific embodiments of the invention have been described 
with particularity herein, it will be recognized that various 
modifications thereof will occur to those skilled in the art and it is to 
be understood that such modifications and variations are to be included 
within the preview of this application and the spirit and scope of the 
appended claims.