CA1038754A - Method for controlling the growth of bacteria, fungi and algae and the bactericidal, fungicidal and algicidal compositions for industry - Google Patents
Method for controlling the growth of bacteria, fungi and algae and the bactericidal, fungicidal and algicidal compositions for industryInfo
- Publication number
- CA1038754A CA1038754A CA231,558A CA231558A CA1038754A CA 1038754 A CA1038754 A CA 1038754A CA 231558 A CA231558 A CA 231558A CA 1038754 A CA1038754 A CA 1038754A
- Authority
- CA
- Canada
- Prior art keywords
- beta
- salicylamide
- dichlorovinyl
- fungi
- bacteria
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT
One or more compounds of N-(.beta.,.beta.-dichlorovinyl) salicylamide or metallic salts thereof are employed to control the growth of bacteria, fungi and algae which propagate on industrial raw materials and products or in water in circular water systems.
One or more compounds of N-(.beta.,.beta.-dichlorovinyl) salicylamide or metallic salts thereof are employed to control the growth of bacteria, fungi and algae which propagate on industrial raw materials and products or in water in circular water systems.
Description
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 , ~,`
, A~
~' '''' ' ~'', , , .
lff~3f~75~
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 ' ~ ~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.
~ "' :
~, ',;
s' ,, , ~IL0387e~
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 "
,:
" .
~ - 6 -~ ,..................................................... .
r 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.
~, ~'-~ -8-~, ~, 75~
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.
/
, _9_ , .
.
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.
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 , ~,`
, A~
~' '''' ' ~'', , , .
lff~3f~75~
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 ' ~ ~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.
~ "' :
~, ',;
s' ,, , ~IL0387e~
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 "
,:
" .
~ - 6 -~ ,..................................................... .
r 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.
~, ~'-~ -8-~, ~, 75~
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.
/
, _9_ , .
.
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.
..
`~
,~, ,:
"
_ 1 1 _ :
, ', , .
, , 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_ +~ ~ , '' ' ~ ' ~
~.
,, ~
'''', .
,' ;.
., , :
". :.
, .
~ ,:
_13-
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.
..
`~
,~, ,:
"
_ 1 1 _ :
, ', , .
, , 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_ +~ ~ , '' ' ~ ' ~
~.
,, ~
'''', .
,' ;.
., , :
". :.
, .
~ ,:
_13-
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1, The method for controlling the growth of bacteria, fungi and algae comprising applying to industrial raw materials, industrial products and water in circular water systems an effective amount of one or more compounds of N-(.beta.,.beta.-dichlorovinyl) salicylamide or a metallic salt thereof.
2. The method for controlling the growth of bacteria, fungi and algae according to claim 1 wherein the compounds are N-(.beta.,.beta.-dichlorovinyl) salicy-lamide and metallic salts thereof where valence of metallic atom is one or two.
3. The method for controlling the growth of bacteria, fungi and algae according to claim 1 wherein the compound is one of the compounds selected from the group consisting of N-(.beta.,.beta.-dichlorovinyl) salicylamide, sodium salt of N-(.beta.,.beta.-dichlorovinyl) salicylamide potassium salt of N-(.beta.,.beta.-dichloro-vinyl) salicylamide and zinc salt of N-(.beta.,.beta.-dichlorovinyl) salicylamide.
4. The method for controlling the growth of bacteria, fungi and algae according to claim 1 wherein the materials treated are organic industrial raw materials and products.
5. The bactericidal, fungicidal and algicidal composition comprising 99.5-5% by weight of a suitable adjuvant and 0.5-95% by weight of one or more compounds of metallic salts of N-(.beta.,.beta.-dichlorovinyl) salicylamide.
6. The bactericidal, fungicidal and algicidal composition as claimed in claim 5 wherein said compounds are N-(.beta.,.beta.-dichlorovinyl) salicylamide and metallic salts thereof where valence of metallic atom is one or two,
7. The bactericidal, fungicidal and algicidal composition as claimed in claim 5 wherein said compounds are at least one of the compounds selected from the group consisting of sodium salt of N-(.beta.,.beta.-dichlorovinyl) salicylamide, potassium salt of N-(.beta.,.beta.-dichlorovinyl) salicylamide and zinc salt of N-(.beta.,.beta.-dichlorovinyl) salicylamide.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8228274A JPS5112926A (en) | 1974-07-19 | 1974-07-19 | Kogyoyosatsukin bokabizai |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1038754A true CA1038754A (en) | 1978-09-19 |
Family
ID=13770146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA231,558A Expired CA1038754A (en) | 1974-07-19 | 1975-07-15 | Method for controlling the growth of bacteria, fungi and algae and the bactericidal, fungicidal and algicidal compositions for industry |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5112926A (en) |
| CA (1) | CA1038754A (en) |
| DE (1) | DE2531985A1 (en) |
| FR (1) | FR2278264A1 (en) |
| GB (1) | GB1473617A (en) |
| NL (1) | NL7508032A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5215823A (en) * | 1975-07-18 | 1977-02-05 | Nippon Kayaku Co Ltd | Germicide for agriculture and gardening |
| JPS5777265U (en) * | 1980-10-27 | 1982-05-13 | ||
| CN101746887B (en) * | 2008-12-19 | 2011-06-15 | 中国石化上海石油化工股份有限公司 | Compounded decoupling agent |
-
1974
- 1974-07-19 JP JP8228274A patent/JPS5112926A/en active Granted
-
1975
- 1975-07-03 GB GB2805775A patent/GB1473617A/en not_active Expired
- 1975-07-04 NL NL7508032A patent/NL7508032A/en not_active Application Discontinuation
- 1975-07-15 CA CA231,558A patent/CA1038754A/en not_active Expired
- 1975-07-17 DE DE19752531985 patent/DE2531985A1/en not_active Withdrawn
- 1975-07-18 FR FR7522586A patent/FR2278264A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS531820B2 (en) | 1978-01-23 |
| JPS5112926A (en) | 1976-01-31 |
| FR2278264B1 (en) | 1979-08-24 |
| GB1473617A (en) | 1977-05-18 |
| DE2531985A1 (en) | 1976-02-05 |
| FR2278264A1 (en) | 1976-02-13 |
| NL7508032A (en) | 1976-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69104593T2 (en) | Production and use of N-iodopropargyl-oxycarbonylamino acid esters as antimicrobial agents. | |
| FI62755C (en) | SAETT ATT SKYDDA ORGANIC ELLER ORGANIC MATERIAL MOT ANGREPP AV BAKTERIER OCH SVAMPAR | |
| US5464832A (en) | Substituted 3-thioacryloyl compounds and their use as antimicrobial agents | |
| CA1038754A (en) | Method for controlling the growth of bacteria, fungi and algae and the bactericidal, fungicidal and algicidal compositions for industry | |
| US4285971A (en) | Novel halogenated phenol esters, antimicrobial compositions containing them and their use | |
| US4055639A (en) | Derivatives of N-(2,2-dichlorovinyl) salicylamide and use thereof as bactericides, fungicides and algicides for industry | |
| US3366672A (en) | Microbiologically active quaternary ammonium compounds | |
| US4081267A (en) | Pyridyltriazinone herbicidal compositions | |
| US3223582A (en) | Antimicrobic compositions and use thereof | |
| US3361794A (en) | Microbiologically active quaternary ammonium compounds | |
| US5631277A (en) | (2-one (or thione)-1,3-dithiole 4,5-diyl) bis(thiocyanate) compounds, compositions containing the compounds and their use as an antimicrobial and marine antifouling agents | |
| US3251733A (en) | Antimicrobic compositions and process for protection of organic materials therewith | |
| US4301162A (en) | Antibacterial and antifungal composition | |
| US3299073A (en) | Quaternary ammonium aromatic amino sulfonates | |
| IL25982A (en) | 5-sulphonyl-1,2-dithiol-3-one compounds,their preparation | |
| KR960001204B1 (en) | N-alkylbenzenesulfonylcarbamoyl-5-chloroisothiazole derivatives | |
| US5633219A (en) | 5H-pyrrolo(3',4':5,6)(1,4)dithiino(2,3-C)(1,2,5)thiadiazole-5,7(6H)-dione, compositions containing them and their use as antimicrobial and marine antifouling agents | |
| US3764678A (en) | Organotin-substituted s-triazines for controlling insects, acarinal, fungi, bacteria, and mollusks | |
| US4055640A (en) | Compositions and methods for controlling the growth of bacteria, fungi and algae using certain derivatives of N-(2,2-dichlorovinyl)salicylamides | |
| US3578667A (en) | Quaternary ammonium alicyclic carboxylates | |
| US4017627A (en) | 7,8-Disubstituted-5-acetylquinolines and antimicrobial compositions containing them | |
| US3873591A (en) | Halo-substituted cyanomethyl benzenesulfonates | |
| US3551500A (en) | 2-hydroxy-4-halo-diphenyl sulfones | |
| US4366171A (en) | Fungicidal biphenyl esters, mixtures thereof and method of use | |
| US5703102A (en) | 1,2,5-thiadiazolo-1,3-dithiole-2-one (or thione) as antimicrobial and marine antifouling agents |