Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
The present invention relates to the method for controlling the
growth of bacteria, fungi and algae which propagate on industrial raw mater
ials and products and in water in circular water systems,
The bacteria and fungi on industrial raw materials and products
degrade the quality of industrial raw materials and products and cause vari~
ous other barrier. The damage is very serious. The bacteria, fungi and
algae in water in circular water systems produce mats of slime which restrict
the flow of water and reduce the efficiency of heat exchangea The algae
which propagate on the bottom of ships cause the slowdown of speed. The
troubles caused by bacteria~ fungi and algae are considerable problems.
Many compounds having bactericidal~ fungicidal and algicidal
activity are used in order to prevent the damage caused by the bacteria, or
fungi to industrial raw materials and products and the barrier caused by
slime in circular water systems. These compounds are, for example~ organic
mercury compounds, organic tin compoundsy phenols substituted halogen atoms,
organic sulfur compounds~ formalin~ cresol and quarternary ammonium salts.
;.:
These compounds however~ have va~ious defects, for example, strong toxicity
agai~st human and live-stock, pollution of environment, irritative or
offensive odor, a bad influence upon industrial raw materials and products ~;
20 and a weak bactericidal and fungicidal activity. ~-
It is,therefore, the object of the present invention to provide
methods for controlling the growth of bacteria~ fungi and algae which propa-
gate on industrial raw materials and products and in water in circular water
- srstems without the defects mentioned above and to provide bactericidal
,
fungicidal algicidal compositions used for the methods~
The method Or the present invention comprises app]ying to industrial
raw materials~ industrial products and water in circular water systems an
effectiYe amount of one or more compound~ of N~ dichlorovinyl) salicyla-
mide or a metallic salt thereof.
The bactericidal~ f~mgicidal and algicidal composition of the pre-
"
f,
~3~7S~L ~
sent invention comprise 99.5-5% by weight of a suitable adjuvarlt and 0.5-95%
by weight of one or more of N-(~-dichlorovinyl) salicylamide or metallic
salts thereof.
The industrial raw materials and produc~s are organic matter~ for
example~ cellulosic materials such as wood, wood0n articles, paper, cotton,
fibres, textiles and bamboo, petroleum products such as plastics, plastic
articles, oils and paints, leathers and past, inorganic matter such as
metal articles, and the products consisting of organic and inorganic matters
such as ships and sheds for animals.
i ,
The circular water system means a system in which water is used ~ ~ ;
many times by recycle. The circular water systems are, for example, the
water systems in cooling towers for airconditioning, swimming pools, cooling
equipments for reactors and paper manufacturing industry.
Suitable adjuvants of bactericidal~ fungicidal and algicidal com-
' position of the present invention are, for example, carriers, extenders,
;~ emulsifying agents, wetting agents, fixing agents and surface active agents,
The term "carrier" is used herein to mean a diluent or a vehicle by which the
active compound is brought into contact with bacteria, fungi and algaeO
Solid carrier materials and liquid carrier materials are usually
used as carriers in the present invention. Solid carrier materials are, for
; example, clay, kaolin, talc, diatomaceous earth, silica and calcium carbonate~
- liquid carrier materials are, for example, benzene, alcohol, acetone, xylene~
methylnaphthalene~ cyclohexanone, dimethylformamide, diethylsulfoxide, animal
and vegetable oils, fatty acids and esters thereof and various surface active
agents.
! In the method of the present invention~ N~ dichlorovinyl)
~alicylamide and metallic salts thereof (hereinafter referred to as the
....
active compounds) are applied to the industrial raw materials, industrial
products and water in circular water systems in various forms and methods.
For instance, the active compounds, themselves, may be directly applied to
~38~4
said materials, products and water. However, in general, one or more active
compounds are mixed with suitable adjuvants and formed into the bactericidal,
fungicidal and algicidal compositions such as emulsifiabl~ concentrate, wet-
table powder, dus~, granule and pellet.
The bactericidal, fungicidal and algicidal composition of the
present invention comprises about 0.5 to 95, preferably 2 to 70, weight per-
cent of the activ~ compound and about 99.5 to 5, preferably 98 to 30 weight
percent of one or more suitable adjuvants.
In order to prevent the growth of bacteria, fungi on the surface
of wood, wood articles, fibers, textiles, paper, leathers and the inside of
cotes etc., usually, the surfaces are treated with 0.1-10 g/m2 of the active
compound in the form of a composition by means of spraying, coating or infil~
trating. In case of treatment of paints, adhesives and pastes, etc., the ~;-
~, .
- composition is added to them and mixed. The amount of the active compound ~;-
. .
added is usually, about 0.01 to 0.1 percen~ by weight. The growth of bacteria,
fungi and algae on the bottom of ships can be prevented by coating the bottom
-. .
`~ with the active compound mixed with the paint. In the case of trea~ment of
water in circular water systems, the active compound is added to the water and
th0 amount of the active compound is usually, about 2 to 50 ppm, preferably ;~ ~
about 10 to 30 ppm. The most suitable industrial raw materials and products '
treated with the active compounds are organic matter.
The active compounds employed in the present invention have very
superior bactericidal, fungicidal and algicidal activity against bacteria,
,
fungi and algae which propagate on industrial raw materials and products and
in water in circular water systems, and have no irritative or offensive odor,
no color and very low toxicity. The value of acute oral toxicity of N~
dichlorovinyl) salicylamide against a mouse, which is represented by LD50, is
.. . .
~I more than 6000 mg/kg. The value shows that the toxicity of N-t~ dichloro-
; vinyl) salicylamide is very low. Accordingly, the compounds are safe to
~ 35 handle
i,.,
The preferable compounds employed in the present invention are
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N~ -dichlorovinyl) salicylamide and the metallic salts thereof in which
the valence of metal atom is one or two. The metallic salts are sodium salt,
potassium salt, zinc salt> copper salt and manganous salt etc. The most pre-
ferable compounds are N~ dichlorovinyl) salicylamide, sodium salt of
N-~,f~-dichlorovinyl) salicylamide and zinc salt of N-~,f~-dichlorovinyl)
salicylamide.
N-(~,~-dichlorovinyl) salicylamide is prepared by heating chloral -
with salicylamide, followed by treatment with a mixture of zinc and acetic
f acid. -
A metallic salt of N-(~ dichlorovinyl) salicylamide is pre-
pared by reacting a hydroxylmetal compound such as sodium hydroxide with
N-(~,~-dichlorovinyl) salicylamide.
~ Preparation of N-(~ dichlorovinyl) salicylamide ~Co~pound No.
: ~ lf:
The mixture of 27.4 g (Of.2 mole) of salicylamide and 32.45 g
- (0.22 mole) of chloral was heated at 90-lOO~C for 5 hours. The reaction ~-
product was washed with water and dried. Fifty-six point nine (56.9) g of
chloral-salicylamide (white crystals, m.p. 'L32-133C) were obtained. ;
;~ Twenty-eight point five (28.5) g (0.1 mole) of chloral-salicyl~
: 20 amide were mixed with 150 ml of acetic acid. Then 26 g (0.4 mole) of zinc
~ powder were added to this solution under agitation below 50C. After agit-
i` ation was continued for 30 minutes at 70-80C, the reaction mixture was
f
cooled at room temperature and filtrated. Water was added to the filtrate to ~-
precipitate the crystals of the reaction product. The crystals were separated
by filtration, washed with water and dried.
The yields of N-(~ dichlorovinyl) salicylamide (white crystals,
,.
m.p. 187-189C~ werfs 15.1 g (70%).
Analysis of elements:
Calculated ; C: 46.58%, H: 3.04%, N: 6.04%
~ound ; C: 46.57%, H: 2~87%, N: 6.22%
as C9 H7 N 2 C12
'
-- 4 --
~ ~387~ :
The prcparation of sodium salt of N~ dichlorovinyl) salicylamide
(Compound No. 2) :
~ o hundred thirty_~w~o (232) g
~1 mol) of ~-~E,~-dichlorovinyl) salicyamide were added under agitation to the
aqueous solution wherein 43 g (l mole) of 93~-sodium hydroxide were dissolved
in 300 ml of water and then agiated at room temperature for 3 hours.
Water was evaporated under reduced pressure. The yields of sodium
salt of N~ -dichlorovinyl) salicylamide was 255 gO The sodium salt was
~ pale light brown crystals and decomposed at 243C
; lO Analysis of elements
` Calculated ; C: 42.55%, H 2 38%, N 5.51%
Found : C: 42.32%, H: 2.40%, N: 5.40%
.;, . :
as Cg H6 C 2 N 2
--, The following metallic salts were prepared by the same method as ~ -
the sodium salts.
:.,:, ,
' Table 1 ~- ~
, . ~
_ . _~ , ! . . _ ,
;~ Compound No. Metallic Salt ~elting Point Appearance
. . . _ _
,. .. v.,.. _" ____._ , . . _, _
3 Potassium salt 243 pale light
(Decomposition) brown crystals
., . . . _ . ~ ~. _ ,, _
_ ~ Zinc salt l58-160 White crystals ;~
Cupric salt 135 Pale green
(Decomposition) crystals
6 Manganou~ salt 191 Yellow grey -
_ ~ - ~ (Decomposition) crystals
,.,, . ~, .
,...................................................................... .
The following are some illustrative examples which exhibit an excell-
ent antimicrobial and algicidal effect of the present in~ention and some
exarnples of compositions of compositions of the present invention. All parts
are by weight.
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Example 1.
An emulsifiable concentrate was prepared as follows:
Compound No. 1 10 parts ~ ~
Isophorone 40 " ~;
Xylene 31 "
Dimethylformamide 7 "
~- Surface active agents 12 "
The above ingredients were blended. An emulsifiable concentrate was obtained.
Before application, the emulsifiable concentrate was diluted with water up to
400-2000 times and an emulsion was formed. ~oods and fibers were soaked in
; the emulsion to control bacteria and fungi which propagate on them.
An emulsifiable concentrate containing compound No. 2, No. 3,
No. 4, No. 5 or No. 6 was prepared by the same method as mentloned above. ~-
Example 2.
- An oil soluble concentrate was prepared as follows:
1~ Compound No. 1 20 parts
;l 2-Ethoxyethanol 40
Dimethylformamide 10
Xylene 30 "
.:.-, ,
~ 20 The above ingredients were mixed. An oil soluble concentrate was obtained.
; In the form of the oil soluble concentrate, Compound No. 1 was added to paints
or the cutting oil in an amount of 0.1%.
~; The growth of fungi in the paints or the cutting oil was con-
trolled.
Example 3.
A wettable powder was prepared as follows:
,,
Compound No. 3 55 parts
Polyethyleneoxide 3 "
' Ligninsulfonic acid 5 "
Diatom earth 20 "
Clay 17 "
,:
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~ ,..................................................... .
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3L~1387S4
The above ingredients were blended. A wettable powder was obtained. Before
application, the wettable powder was suspended in water. The resultant
suspension was sprayed on the inside of sheds for animals by a sprayer to pre-
vent the growth of flmgi and bacteria in sheds for animals~
Example 4.
A water soluble concentrate was prepared as follows~ ~
Compound No. 2 lO parts ~` -
Eth~l cellosolve 40 '~
: .
Isophoron 38
Polyethyleneoxide lO
Al}~lbenzenesulfonic acid 2 "
The above ingredients were mi~ed~ A water soluble concentrate was obtained.
Before application~ the concentrate was diluted 500-lO00 times with
water and sprayed on ~he inside of cotes to prevent the growth of bacteria
and fungi.
The solution was added to water in circular water systems to inhibit
the growth of slime. The concentration of Compound No. 1 in the water was
10-20 ppm.
A~ amount from 0.0l_0.1% of Compound No. 1 as the solution was - ;
added to pastes or binding agents ~o prevent rottenness of them.
Bacteria, fungi and slime were inhibited for a long time.
Example 5.
Bacteriocidal activity and fungicidal activity of the active com-
pounds of the present invention were examined b~ [l~ potato-dextrose agar
dilution method7 [2] Waxman1s liquid medium dilution method or ~3] glucose
bouillDn medium dilution method. The results are shown in Table 2 below as
., ,
the minimum inhibitory concentration (the minimum concentration of active
compound found to produce 100~ control of the test bacteria and fungi).
",
375i91
- Table 2.
The minimum inhibitory concentration (mc g/ml)
' ~ ___ _ ._ _ _. r--_ _
Active No. 1No. 2 No. 3 No. 4 No. 5 No. 6
Compounds
.'~ ~ _ _ _ _ _ _ _ _ _ . _
Method of
Examination (1) (2) (1) (3) (1) (3) (1) (3) (1) (3) (1) (3) . _ _ _ _~ _ _ _ _ _
niger 10 10 10 _ 10 _ 1~ _ lo _ 10 _
,: ~ ~ _ _ . _ _ _ _ _ .,
U Penicillium 10 20 10 ~ 10 _ 10 _ 10 ~ 10 ~
N - _ _ _ _ _ _ _ _
~ I harbarum 10 5 205 _ 5 _ 2a5 _ 5 _ 5 _
: __ _ _ _ _ _ _ __ _ _ _ . I
Chaeton~um 5 10 _ _ _ ~ ~ _ _ _ _
.,~ ~ __ ~ _ _ ~_ _ _ _ _ _ _ _
candium 10 20 _ _ _ _ _ _ _ _ _ _
.,, ~ ~ . . . _ _ _ _ _ _
subtilis 2.5 5 _ 5 _ 5 _ 2.5 _ 5 _ 5
- B __ _ ~ _ _ _ _ ~ _ _ _ _ _ _
A taph~lococcus
CT aureus 2,5 2.5 6 5 ~ 10 ~ 5 ~ 5 ~ 5
.,, . _ _ _ _~ . . . _ _ . . _
I coli 80 80 _ 60 _ 60 _ 40 _ 60 _ 60
A , _ ~ _ _ _ _ _ _
:: ~ seudo onaa 40 40 ___ _ __ _ ~ _ _ _ j_
Example 6
Thirty grams (30 g) of milk casein, 270 ml of distilled water and
1 ml of 28% ammonia aqueous solution were mixed. A casein solution was ob-
tained, Five milliliters (5 ml) of rotten casein solution were added to the
' casein solution obtained. The water soluble concentrate, which was obtained
by Example 4 and contained Compound No. 1, was added to the resultant casein
solution, The casein solution maintained at 30C. The degree of rottenness
of the casein solution was examined on 10th day, 20th day and 30th day.
The results are shown in Table 3.
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Table 3
Amount of _
compound No 1 loth day 20th day 30th day
solution
. ~ .. . _--
; 0 Rottenness Rotterness Rottennes9
and yellow and yellow and yellow
(No treatment) coloratlon ~lorA~ coloration
0.05 % No No Slight
-., ~ ~
0.1 % No No No
rottenness rottenness rottenness
.: . . __._ _ , -- _
Example 7
The emulsifiable concen~rate which was prepared by Example 1 and
which contained 10% of Compound No. 1 was entered to three vessels. These
emulsifiable concentrates were diluted with water 500 times~ 1000 times and ;;
2000 times respectively. Emulsions were obtained~ Each of silk, cotton and
vinylon clothes was dipped into the three different concentrations of emul-
sions for 3 minutes and dried for 24 hours at room temperature. The clothes
dried were cut into a square of which a side was 1 cm long. Test bacteria
and fungi were inoculated on the whole surfaces of the plates of pOtato-
dextrose agar medium. The square clothes were placed on the plates of agar
culture medium of potato. The inoculated bacteria and fungi were incubated
at 28C for 4 days. The width of ~ones in which the growth of the test bac-
teria and fungi was inhibited in the en~ironment of the clothes was measured.
The results are shown in Table 4.
/
,
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,
.
.
Table 4
The width of growth in libition zones (mm)
Q~"~' ~ . Bacteria _ _
Q~ Bacillus Staphylo- Asper- Penicil-
~o ~o~ \ subtilis coccus gillu~s lium
\ \ aureus niger citrenum
_ ,~ . ~ _ __ _ _
Control 0 0 0 0
Silk 00005 3 5 5 4
0~01 6 8 7 6
000210 12 _ 3 7 _
Control 0 0 0 _ _
Cotton 0.0053 5 6 5
0~01 6 9 8 7
- _ 0.0210 13 11 9
Control 0 0 0 0
Vinylon 00 015 5 7 6 53
___________ 0.029 _ - 11 8 7
.. . _ . , _ .
., :
Example 7
The emulsifiable concentrates which were prepared by Example 1 were
diluted with water 400 times and 800 times to form emulsions.
The square plates of beach of which a side was 5 cm long and thickness
was 5 mm were dipped into the emulsion for 2 minutes and dried for 24 hours at
room temperature.
The square plates were placed on the surface of agar plates. The
suspensions which contained spores of Aspergillus nigerO Penicillium citrinum~
; Cladosporium harbarum and chaetomium globosum were respectively sprayed on the
.,
agar plates and the square plates.
The test fungi were cultivated in the incubator at the humidity of
95% and the temperature of 28C for 2 weeks.
The results are shown in Table 5~ The degree of growth inhibition is
de~ined in term of the following numerical ratings.
'
_10--
~L~3~S4
3 : 100% control o-f the test organism.
2 The part in which the test organisms propagated is less than
one third of the surface of ~he test plate.
1 Tha part in which the test organisms propagated is more than
one third of the surface of the test plateO
Table 5
: .
, ~_ ~ _ _ -.
The degree of growth inhibition
Acti w ~ 0.025 ~ 0,0125% treatment~ -
' ~ 3
_ ~ 3
Example 8
~:
The ~ulsifiable concentrates which were prepared by Example 1 were
diluted with water 1000 times to form an emulsion.
~; A cloth of cotton was soaked into each emulsion for 2 minutes. The
; ' ":~:` ~. -
clothes were dried at room temperature and cut into a square of which a side
was 1 cm long. Each kind of test bacteria and fungi was inoculated, separate~
ly on plates of potato-agar and one square cloth was placed on each o-f such ;
. .:
plates. Test bacteria and fungi were cultivated at 28C for 4 days. The
width of the region of growth-inhibition which was formed a circumference of
; the cloth was examined. The results are shown in Table 6.
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Table 6 ~3~754
. .. . ,, , . ~ "
The width of the growth inhibition ~one (mm)
Compo~d ~ e ~ A
Number _ ,,
Penicil- Staphylo-
~spergillus liumBacillus coccus
niger citrinum subtilis aureus
~ 6 - -~ - ''8 ' '
;~ 4 5 5 10 8 '
N~ tr~_5~t O O O
Exam,ple 9.
Zero point zero two (0.02~ part of active compounds in the form of
, ~
10% Water soluble concentrate which was prepared by Example 4 was added into ~'
' 100 parts of Waxman~s liquid medium. Pieces of wood and iron (hereafter
,,~ 10 referrçd to as the slime test boards~ were soaked into the Wax~ant~s liquid
.,
, medium. ,The bacteria which were gathered from circular water system were ,~
inoculated upon the Waxman"s liquid medium and incubated at 27C-34C by
shaking eultureO The degree of propagation of the bacteria on the slime
; test boards was examined. -~
The growth-inhibiting acti~ity of acti~e compounds against the
. ,
, fungi and the green algae was also examined by the same m~thod as mentioned
', above.
'' The results are shown in Table 7.
,:~
' The degree of propagation o the bacteria, fungi or green algae on
the glime test boards is defined in terms ofthe following symbols.
_ : no propagation
: t'he area of propagation is 1 - 25%
on the slime test boards.
+~ : the area of propagation is 26 - 50%
on the slime test boards.
,, ~+f : the area of propagation is 51 - ?5%
' on the slime test boards.
, " .
:
the area of propagation is 76 - 100%
on the slime test boards.
Table 7
: ~_ _ Ac = Degree of propagation
Compound . . ~ ~
Number 7th day14th day21st day ~-
.~ _ _ . . ~,
Bacteria 3 _ _ ~ :
No treatment +' III ++~+
Fungi _ ~ _ - - _ ~
No treatment - . +~ _ - : -
Green algae 3 _ _ _
.~ _,, , ~ +l_ +~ ~ ,
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