Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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The present invention relates to industrial aqueous
fungicidal compositions which protect industrial products and
raw materials from microorganisms, especially fungi.
Heretofore, the economic growth caused by the growth
of microorganisms, such as bac-teria and :Eungi, in industrial
produc-ts and raw materials has been serious. For example, fun~i,
such as Asperigllus and Cladosporium grow on walls and ceilings,
coated with an aqueous emulsion paint or a water paint causing
serious disadvantages in hygiene and appearance. Fungi such
as Chaetomium, Rhizopus and Aspergillus grow on products such
as soap cartons, causing serious damage including deterioration
of paper strength and hygiene. Various chemicals have been
proposed to prevent such damage. However they are not
satisfactory.
In attemp-ts to find chemicals effective for
protecting such industrial products and raw materials against
such serious damage caused by microor~anisms N-arylmaleimides
known as agricultural germicides have been studied. As a result,
N-(3,5-dichlorophenyl)maleimide known to have germicidal
activity aga~nst bacteria such as Staphylococcus aurcus and
Eschericha coli (Japanese Examined Patent Publication No.
38819/1974), has been found to have inferior fungicidal activity
to find fungicidal compounds for industrial purposes.
The present invention provides an industrial aqueous
fun~icidal composition, especially an aqueous slurry or pasty
fungicidal composition, such as an aqueous emulsion paint, a
water paint, an aqueous adhesive, a printing paste and a pulp
slurry.
According to the present invention -there i5 provided
an aqueous slurry or pasty fungicidal composition including
N-(2,4,6-trichlorophenyl)maleimide as an active ingredient.
It has been found that N-(2,4,6-trichlorophenyl)
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maleimide having a meltiny point of 130DC as colorless powdery
~ crystals obtained by a dehydrocyclization of 2,4,6-trichloro-
i aniline and maleic anhydride has an especially good fungicidal
activity agatnst noxious funyi and is very effective for
prol-ecting various industrial products and raw materials
from damage due to microorganisms, especially fungi. The
present invention provides industrial fungicidal compositions
containing N-(2,4,6-trichlorophenyl)maleimide as an active
ingredient. -
N-(2,4,6-trichlorophenyl)maleimide used in the present
i invention can be produced by adding a solution of 2,4,6-trichloro-
~ aniline in a solvent, such as toluene dropwise into a solution
, :
of maleic anhydride in a solvent, such as toluene, with stirring
at about 65C for 2 hours and adding sulfuric acid and refluxing
the mixture with stirring for 4 hours to effect reaction and
distilling off the solvent after the reaction, pouring the
reaction mixture into water and then filtering the precipitated
crystals having a melting point of 130 to 132C.
The compound of the present invention can be used
by itself and also can be used in a suitable form such as wettable
powder, dust, tablet or suspension obtained by admixing with a
diluent, or bulking filler or an additive, such as a dispersing
; agent, penetrant and a wetting agent. Most conventional
industrial fungicides are not easily soluble in organic solvents
whereby their field of the application is quite limited.
However, the compound of the present invention is readily soluble
in most solvents, such as benzene, toluene, xylene, solvent naphtha,
chloroform, methyl isobutyl ketone, and dimethylformamide
whereby an emulsion type composition can be prepared and the
field of application are not so limited. The compound of the
present invention can be combined with conventional industrial
- funyicide such as phenol type fungicides e.g. 2,4,6-trichloro-
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phenol; chlorine type fungicides e.y. tetrachloroi oph-thalnitrile,
and organ~tin compound fungicides e.g. tributyl-tin-oxide and
such a synergistic effect may be achieved without reducing the
effect of the compounds.
The N-arylmaleimides are known agricultural germicides.
The agrlcultural germicides controlling plant virus growing on
plants are quite different from the industrial fungicides for
inhibiting fungi grown on industrial products and raw materials
in view of locations of applications, types of microorganisms
to be controlled and physical properties of the compositions.
Although N-(3,5-dichlorophenyl)maleimide has high
activity against viruses, the N-(2,4,6-trichlorophenyl)maleimide
of the present invention has greatly superior activity against
fungi. An excellent fungicidal effect when used as an industrial
fungicide is found. N-(2,4,6-trichlorophenyl)maleimide is
especially superior to other maleimide derivatives in the form
of an aqueous suspension or pasty composition, such as an aqueous
emulsion paint, a water paint, an aqueous adhesive, especially
adhesives for bonding paper, etc., a printing paste and a pulp
slurry. N-(2,4,6-trichlorophenyl)maleimide is preferably
incorporated in the composition in the form solubilized with a
surfactant, especially in the form of an emulsifiable concentrate
or a wettable powder.
The content of N-(2,4,6-trichlorophenyl)maleimide
in the composition is not critical and is sufficient to impart
the fungicidal activity and can be considered from the minimal
growth inhibition, and is preferably more than 100 ppm, especially
more than 200 pp~.
The present invention will be further illustrated
by the following Examples and References:
_ AMPLE 1
(Tests for minimal growth inhibition concentration)
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Each wettable powder was prepared by mixing and pulver-
izing 50 wt. parts of each active ingredient, 2 wt. parts of
a surfactant (Neopelex: a trademark of Kao-Atlas Co.), 2 wt.
parts of an extract (Sunex P: a trademark of Sanyo Pulp Co.),
and 46 wt. parts of diatomaceous earth. Each minimal growth
inhibition concentration against various fungi was measured
by the agar dilution method by using the prepared wettable
powders. The results are shown in Table 1.
TABLE 1
~ . .
¦Mlnimal growth inhibition concentration (ppm)
Active ingredient I_ _
A.n P.c T.v R.n C.h C.g
, _ _. _
N--(2,4,6-trichloro-
phenyl)maleimide 25 12.5 25 100 50 100
References:
(a) 2-(4-thiazoyl)
benzimidazole 50 50 100 500 100 200
(b) tributyl-tin-
oxide 25 12.5 50 250 100 100
(c) N-(3,5-dichloro-
phenyl)maleimide 100 100 500 500 250 250
A.n: Aspergillus niger
P.c: Penicillium citrinum
T.v: Trichoderma viride
R.n: Rhizopus nigricans
C.h: Cladosporium herbarum
C.g: Chaetomium globosum
(a) and (b):Commercially available fungicides
(c): compound disclosed in Japanese Examined
Patent Publication 38819/1974
EXAMPLE 2
(Fungicidal Test of Water Paint)
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A water paint was prepared by mixing 27 wt.o of acrylic
emulsion having 50% of a resin content, 8 wt.% of titanium oxide,
23 wt.% of kaoline, 18 wt.% of heavy calcium carbonate, 20 wt.%
of 2% a~ueous solution of carboxymethyl cellulose and 4 wt.% of
water Each wet-table powder prepared in Example 1 was incorporated
in the water pain-t at a concentration of 2000 ppm or 500 ppm of the
active ingredient. The water paints incorporating the wettable
powder were tested by the wet fungi resistant test method of
Japanese Industrial Standard Z-2911. The results are shown in
Table 2.
TABLE 2
__ _ _ _
Concent- Culturing time
ration
Active ingredient(ppm) 3 day 7 day ¦ 14 day
N-(2,4,6-trichloro-
phenyl) 2000 3 3 3
maleimide 500 3 3 2
. _
2~(4-thiazoyl)- 2000 3 3 ¦ 3
benzimldazol 500 3 1
tributyl-tin-
oxide 3
N-(3,5-dichloro-
phenyl) 2000 3 2 1
maleimide 500 3 0 0
. _
Non-treatment ~ __~
Rating: 3: no growth of fungi
2: growth of fungi in area of less than
1/3 on test piece
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, ~
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1: growth of fungi in area of about 1/3 on
test piece
0: growth of fungi in area of more than 1/3
on test piece
EXA~PLE 3
-
(Fungicidal test of printing paste)
.
In a 500 ml beaker was placed 300 g of a printing
paste as a solution of 1 wt.% wheat starch and 1 wt.~ of
tragacanth gum. Each wettable powder prepared in Example 1
was incorporated in the prin-ting paste at a concentration of
1000 ppm or 2000 ppm of the active ingredient. The beaker was
sealed with aluminum foil and kept in a constant temperature
oven at 30DC. The growth of fungi on the surfaces of the
printing pastes were observed. The results are shown in Table 3.
TABLE 3
. . _
Concent~ Culturing time
ration _ I ~ -
Active ingredient (ppm) 4 day 7 day 10 day
N-(2,4,6-trichloro- _
phenyl) 2000 _ _
maleimide 1000 _ _ _ -
_
2-(4-thiazoyl)-
benzimidazol 2000 _
1000 ~ ++ '":
tribu~yl-tin-oxide ~ _ . ~
Non-treatment ~ ++ ++
_ting:
-: no growth of fungi
+: growth of fungi in area of less than 1/3 on
surface in beaker
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+ : growth of fungi in area of about 1/3 on surface
in beaker
-~: growth of fungi in area of more than 1/3 on
surface in beaker.
EXAMPLE 4
(Fungicidal test of wall paper)
Casein glue as an adhesive was prepared by boiling an
aqueous solution of casein.
Each wettable concentrate of Example 1 was incorporated
into the adhesive at a concentration of 2000 ppm of the active
ingredient. The treated casein glue was used for bonding wall
paper on a concrete having a thickness of 5 cm x 5 cm to ob-tain
a test piece. The test piece was placed at a center of the plate
culture medium made of 1000 ml of water, 40 g of glucose, 10 g
of peptone and 25 g of arger in a Petri dish and a suspension
of mixed spores of Aspergillus niger, Trichoderma viride,
Pencillium citrinum and Rhizopus nigricans was uniformly sprayed
in the Petri dish. The Petri dish was covered with a cover and
kept in a constant temperature oven at 2~C for 15 days to
culture it for 15 days. The results are shown in Table 4.
TABLE 4
_ Culturing time
Acti~e lngredient ~ day ¦ 10 day ~ 15 day
N-(2,4,~-trichloro- _ _ _
phenyl) maleimide
.
2-(4-thiazoyl)-ben- _ _ _
zimidazol
_ _
tributyl-t~in-oxide _ +
Non-treatment L +-~+
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Rating:
- : no growth of fungi
+ : growth of fungi in area of less than 1/3 on
surface in beaker
+ : growth of fungi in area of about 1/3 on surface
in beaker
~-+: growth of fungi in area of more than 1/3 on
surface in beaker
Test 1. Funglcidal test of we-t pulp
Each emulsifiable concentrate was prepared by mixing
20 wt. parts of each active ingredient, 10 wt. parts of a
surfactant (~orpol 800 A: a trademark of Toho Kagaku K.~.),
5 wt. parts of a surfactant (Emulgen 800: a trademark of Kao-
Atlas Co.), and 65 wt. parts of xylene. The emulsifiable
concentrate was diluted with wa-ter to prepare each emulsion at
a concentration of 200 ppm or 50 ppm of the active ingredient.
The emulsion was sprayed by a sprayer at a rate of 30 ml. per
1 kg of a we-t straw pulp! The treated pulp was held in a plastic
film bag and kept in a constant temperature oven at 30C to
observe the growth of fungi on the surface of wet pulp. The
results are shown in Table 5.
The commercially available 2-(4-thiazoyl)benzimidazole
was difficulty soluble to organic solvents whereby it could ;-
not be emulsified to use it in the test.
TAsLE 5
Concent- Culturing time
ration
Active ingredient (ppm) 5 day 10 day 20 day
_ : .
N-(2,4,6-trichloro- 1 200 _ _ _
phenyl) maleimide ¦ 50 _ _
tributyl-tin-oxide 200 _ _ +++
~ _ _
non-treatment _ ~ _ ++ +~+
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Test 2. Funyicidal test of wood:
Each emulsifiable concentrate of Test 1 was diluted
with water to prepare each emulsion at a concentration of 200
ppm or 50 ppm of the active ingredient. Each pine wood chip
(size of 5 cm x 5 cm x 30 cm) having a water content of 70 to
75% was dipped in the emulsion for 3 minutes. The treated pine
wood was maintained in a chamber at 30C and a humidity of 80%.
The growth oE fungi on the wood chip was observed. The results
are shown in Table 6.
The commercially available 2-(4-thiazoyl) benzimidazole
was difficultly soluble in organic so]vents and it could not be
emulsified for use in the Test.
TABLE 6
_ _ _ _ Concent- Culturing time
Active ingredient r(ppm)n 10 day .D d~ 30 day
1~-(2,4,6-trichloro- 200 _ _ _
phenyl)maleimide 50 _ _ _
__ ....
20 ~ L-t.in-oxi ~ ~ _
non-treatment L + ++ +++
::
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