Abstract:
There are disclosed a controlling agent and an antifouling composition against harmful aquatic organisms, which include a particular N-phenylbenzoisothiazolone derivative of the formula: ##STR1## wherein R&#39;s are the same or different and are independently halogen, alkyl or alkoxy; n is an integer of 0 to 5; X&#39;s are the same or different and are independently halogen, nitro, alkyl or alkoxy; and m is an integer of 0 to 4; with the proviso that when the R&#39;s are all alkyl or all alkoxy, n is an integer of 1 to 3, and when all of the R&#39;s are different, n is an integer of 2 or 3. Also disclosed is a method for preventing or inhibiting the adhesion of harmful aquatic organisms to water-exposed articles, which includes applying the antifouling composition to the water-exposed articles.

Description:
FIELD OF THE INVENTION 
     The present invention relates to fouling control of harmful aquatic organisms which adhere to various water-exposed articles. The term &#34;water-exposed articles&#34; is used herein to cover marine vessels, buoys, littoral industrial plants, inlet channels for cooling water in thermal or nuclear power stations, drilling rigs for submarine oil fields, harbor facilities and sea pollution preventive bands for ocean civil engineering works, and the like. 
     BACKGROUND OF THE INVENTION 
     As there can be found many kinds of animals and plants living in the sea, various organisms may often adhere to water-exposed articles and have adverse effects thereon. The adhesion of such harmful aquatic organisms will cause a decrease in the service speed and an increase in the fuel consumption of marine vessels, and a decrease in the carrying capacity of inlet channels of cooling water. 
     To control these adhering organisms, various antifouling agents such as cuprous oxide have hitherto been used; however, their efficacy is not sufficient. 
     SUMMARY OF THE INVENTION 
     Under these circumstances, the present inventors have intensively studied to find methods of more effectively preventing and inhibiting various organisms adhering to water-exposed articles. As a result, they found that particular N-phenylbenzoisothiazolone derivatives have an effect on the prevention and inhibition of adhesion of harmful aquatic organisms, for example, harmful aquatic animals such as barnacles and sea mussels; harmful aquatic plants such as algae and diatoms; and harmful aquatic objects such as slime, thereby completing the present invention. 
     Thus, the present invention provides a controlling agent and an antifouling coating against harmful aquatic organisms, which comprise an N-phenylbenzoisothiazolone derivative of the formula: ##STR2## wherein R&#39;s are the same or different and are independently halogen, alkyl or alkoxy; n is an integer of 0 to 5; X&#39;s are the same or different and are independently halogen, nitro, alkyl or alkoxy; and m is an integer of 0 to 4; with the proviso that when R&#39;s are all alkyl or all alkoxy, n is an integer of 1 to 3, and when all of the R&#39;s are different, n is an integer of 2or 3. 
     The present invention also provides a method for preventing and inhibiting the adhesion of harmful aquatic organisms to water-exposed articles, which comprises applying the antifouling composition of the present invention to the water-exposed articles. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The controlling agent and antifouling coating of the present invention contain an N-phenylbenzoisothiazolone derivative of the formula (I), which is hereinafter referred to as the compound (I), as an active ingredient. Compound (I) is disclosed in the U.S. Pat. No. 3,012,039 and a process of producing this compound is disclosed in the Japanese Patent Publication No. 51-113/1976. 
     As used herein, the term &#34;halogen&#34; refers to chlorine, fluorine, bromine or iodine. The term &#34;alkyl&#34; refers to C 1  -C 10  alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, sec-butyl, tert-amyl, n-pentyl, n-hexyl and n-decyl. Preferred is C 1  -C 4  alkyl. The term &#34;alkoxy&#34; refers to C 1  -C 10  alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, tert-amyl oxy, n-pentyloxy, n-hexyloxy and n-decyloxy. Preferred is C 1  -C 4  alkoxy. 
     The compound (I) has an effect on the prevention and inhibition of harmful aquatic organisms adhering to water-exposed articles, and such an effect can be retained for a long period of time. Examples of the harmful aquatic organisms are aquatic animals such as barnacles (Balanomorpha), Serpula, polyzoans (Polyzoa), Ascidiacea, Hydrozoa and mollusks (Mollusca); aquatic plants such as Ulva, Enteromorpha, Ectocarpus and diatoms (Diatomaceae); and slime. 
     In case where the compound (I) is used for the purpose of preventing and inhibiting the adhesion and propagation of harmful aquatic organisms adhering to water-exposed articles, it may be applied in the form of a solution or emulsion. Preferably, it is applied in the form of a resin-containing composition. In particular, to water-exposed articles present in the sea, the antifouling composition of the present invention is applied. 
     The compound (I) can be made into an antifouling composition by ordinary formulation which is usually employed in the field of coatings. It is noted that the compound (I) has no adverse effect on the storage stability, such as viscosity increase and quality change. 
     The antifouling composition of the present invention contains the compound (I) in a mixture with a resin. Examples of the resin are vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl isobutyl ether copolymers, chlorinated rubber resins, chlorinated polyethylene resins, chlorinated polypropylene resins, acrylic resins, styrene-butadiene copolymers, polyester resins, epoxy resins, phenolic resins, synthetic rubbers, silicone rubbers, silicone resins, petroleum resins, oil resins, rosin ester resins, rosin soap and rosin. Preferred are vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl isobutyl ether copolymers, acrylic resins and styrene-butadiene copolymers. 
     The resin is mixed in an amount of 0.1% to 80% by weight, preferably 0.1% to 60% by weight, based on the total weight of the controlling agent or antifouling composition of the present invention. 
     The antifouling composition of the present invention may further contain various additives which are usually used in conventional compositions, for example, plasticizers such as chlorinated paraffin and trimetacresyl phosphate; color pigments such as red iron oxide and titanium dioxide; extender pigments such as zinc oxide and silica powder; and organic solvents such as xylene and methyl isobutyl ketone. 
     Preferably, a copper compound or a metallic copper is added to the control ling agent and antifouling composition of the present invention to obtain better controlling effects. Examples of the copper compound are cuprous oxide, copper rhodanide, oxine-copper, copper naphthenate, copper glycinate, cuprous chloride and cuprous carbonate. Preferred are cuprous oxide and copper rhodanide. 
     The controlling agent and antifouling composition of the present invention may further contain other conventional antifouling agents, if required. Examples of the antifouling agent are those which have been cited in the 2091th research meeting of the Japan Shipbuilding Research Association, such as zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine,2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyl-N&#39;-(3,4-dichlorophenyl)urea, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, N-(fluorodichloromethylthio)phthalimide, N,N-dimethyl-N&#39;-phenyl-N&#39;-(fluorodichloromethylthio)sulfamide, 2-pyridinethiol-1-oxide zinc salt, tetramethylthiuram disulfide, Cu-10% Ni solid solution alloy, N-(2,4,6-trichlorophenyl)-maleimide, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 3-iodo-2-propynylbutyl-carbamate, diiodomethyl-p-tolylsulfone, bisdimethyldithiocarbamoyl zinc ethylenebis-dithiocarbamate and tetraphenylborane pyridine salt. 
     The compound (I) is mixed in an amount of 0.1 to 60% by weight, preferably 0.1 to 40% by weight, based on the total weight of the controlling agent or antifouling composition of the present invention. When the amount is less than 0.1% by weight, no controlling effect will be expected. When the amount is greater than 60% by weight, defects such as cracks and peeling will readily occur on the coating film formed from the antifouling composition. 
     In case where a copper compound is to be added to the controlling agent or antifouling composition of the present invention, the proportion of the copper compound to the compound (I) may vary case by case, but it is preferably in the range of 0.1 to 100 parts by weight to one part by weight of the compound (I). The total amount of compound (I) and copper compound is preferably 0.1% to 80% by weight, based on the total weight of the controlling agent or antifouling composition of the present invention. When the total amount is less than 0.1% by weight, no controlling effect will be expected. When the total amount is greater than 80% by weight, defects such as cracks and peeling will readily occur on the coating film formed from the antifouling composition, which makes it difficult to attain the desired antifouling effect. 
     The compound (I) can safely be applied as the antifouling composition of the present invention by means of a spray or the like because of its low irritant action. 
     Some typical examples of the compound (I) are shown in Table 1 below, which are to be construed as mere illustrations and not limitations of the preceding disclosure in any way whatsoever. 
     
                       TABLE 1______________________________________CompoundNo.     Compound name______________________________________ (1)    N-phenylbenzoisothiazolone (2)    N-(2-chlorophenyl)benzoisothiazolone (3)    N-(3-chlorophenyl)benzoisothiazolone (4)    N-(4-chlorophenyl)benzoisothiazolone (5)    N-(4-bromophenyl)benzoisothiazolone (6)    N-(2-fluorophenyl)benzoisothiazolone (7)    N-(4-fluorophenyl)benzoisothiazolone (8)    N-(2-methylphenyl)benzoisothiazolone (9)    N-(3-methylphenyl)benzoisothiazolone(10)    N-(4-methylphenyl)benzoisothiazolone(11)    N-(2-ethylphenyl)benzoisothiazolone(12)    N-(3-ethylphenyl)benzoisothiazolone(13)    N-(4-ethylphenyl)benzoisothiazolone(14)    N-(2-isopropylphenyl)benzoisothiazolone(15)    N-(4-isopropylphenyl)benzoisothiazolone(16)    N-(2-methoxyphenyl)benzoisothiazolone(17)    N-(3-methoxyphenyl)benzoisothiazolone(18)    N-(4-methoxyphenyl)benzoisothiazolone(19)    N-(4-ethoxyphenyl)benzoisothiazolone(20)    N-(4-n-butoxyphenyl)benzoisothiazolone(21)    N-(2,4-dichlorophenyl)benzoisothiazolone(22)    N-(3,4-dichlorophenyl)benzoisothiazolone(23)    N-(3,5-dichlorophenyl)benzoisothiazolone(24)    N-(2,6-dichlorophenyl)benzoisothiazolone(25)    N-(2,4,6-trichlorophenyl)benzoisothiazolone(26)    N-(2,3,4,5,6-pentachlorophenyl)benzoisothiazolone(27)    N-(2,4-difluorophenyl)benzoisothiazolone(28)    N-(2,3,5,6-tetrafluorophenyl)benzoisothiazolone(29)    N-(2,3,4,5,6-pentafluorophenyl)benzoisothiazolone(30)    N-(2,4-dimethylphenyl)benzoisothiazolone(31)    N-(3,4-dimethylphenyl)benzoisothiazolone(32)    N-(3,5-dimethylphenyl)benzoisothiazolone(33)    N-(2,6-dimethylphenyl)benzoisothiazolone(34)    N-(2,4,6-trimethylphenyl)benzoisothiazolone(35)    N-(3,4-dimethoxyphenyl)benzoisothiazolone(36)    N-(3,5-dimethoxyphenyl)benzoisothiazolone(37)    N-(3,4,5-trimethoxyphenyl)benzoisothiazolone(38)    N-(2-chloro-4-methylphenyl)benzoisothiazolone(39)    N-(2-fluoro-4-chlorophenyl)benzoisothiazolone(40)    N-(2,6-dichloro-4-methylphenyl)benzoisothiazolone(41)    N-(t-butylphenyl)benzoisothiazolone(42)    N-(2,6-difluorophenyl)benzoisothiazolone(43)    N-(4-iodophenyl)benzoisothiazolone(44)    N-(4-chloro-2-methoxy-5-methylphenyl)benzoisothia-   zolone(45)    N-(2,4-dichloro-3-methylphenyl)benzoisothiazolone(46)    N-(4-ethoxy-3,5-dichlorophenyl)benzoisothiazolone(47)    N-(2-chloro-4-methoxy-3-methylphenyl)benzoisothia-   zolone(48)    N-(4-methoxy-3-chlorophenyl)benzoisothiazolone(49)    N-(3-chloro-2,4-difluorophenyl)benzoisothiazolone(50)    N-(3,4-diethoxyphenyl)benzoisothiazolone(51)    4-fluoro-N-phenylbenzoisothiazolone(52)    5-fluoro-N-phenylbenzoisothiazolone(53)    6-fluoro-N-phenylbenzoisothiazolone(54)    7-fluoro-N-phenylbenzoisothiazolone(55)    4-chloro-N-phenylbenzoisothiazolone(56)    5-chloro-N-phenylbenzoisothiazolone(57)    6-chloro-N-phenylbenzoisothiazolone(58)    7-chloro-N-phenylbenzoisothiazolone(59)    4-bromo-N-phenylbenzoisothiazolone(60)    5-bromo-N-phenylbenzoisothiazolone(61)    6-bromo-N-phenylbenzoisothiazolone(62)    7-bromo-N-phenylbenzoisothiazolone(63)    6-iodo-N-phenylbenzoisothiazolone(64)    4-methyl-N-phenylbenzoisothiazolone(65)    5-methyl-N-phenylbenzoisothiazolone(66)    6-methyl-N-phenylbenzoisothiazolone(67)    7-methyl-N-phenylbenzoisothiazolone(68)    6-ethyl-N-phenylbenzoisothiazolone(69)    7-propyl-N-phenylbenzoisothiazolone(70)    4-methoxy-N-phenylbenzoisothiazolone(71)    5-methoxy-N-phenylbenzoisothiazolone(72)    6-methoxy-N-phenylbenzoisothiazolone(73)    7-methoxy-N-phenylbenzoisothiazolone(74)    5-ethoxy-N-phenylbenzoisothiazolone(75)    7-isopropoxy-N-phenylbenzoisothiazolone(76)    4-nitro-N-phenylbenzoisothiazolone(77)    5-nitro-N-phenylbenzoisothiazolone(78)    6-nitro-N-phenylbenzoisothiazolone(79)    7-nitro-N-phenylbenzoisothiazolone(80)    5,7-dinitro-N-phenylbenzoisothiazolone(81)    4,5,6,7-tetrafluoro-N-phenylbenzoisothiazolone(82)    5-chloro-7-fluoro-N-phenylbenzoisothiazolone(83)    5-methoxy-7-chloro-N-phenylbenzoisothiazolone(84)    6-chloro-N-(4-chlorophenyl)benzoisothiazolone(85)    6-chloro-N-(2,3,4-trichlorophenyl)benzoisothiazolone(86)    5-methyl-N-(3-fluorophenyl)benzoisothiazolone(87)    6-methoxy-N-(4-chloro-2-methylphenyl)benzoisotia-   zolone(88)    6-methoxy-N-(2,3,4,5,6-pentachlorophenyl)benzoiso-   thiazolone(89)    7-methyl-N-(2-methyl-4-chloro-5-methoxyphenyl)-   benzoisothiazolone(90)    5,7-dimethyl-N-(2-methyl-4-chloro-5-methoxyphenyl)-   benzoisothiazolone______________________________________ 
    
    
    
     The present invention will be further illustrated by the following examples, test examples and comparative examples, which are not to be construed to limit the scope thereof. Unless otherwise indicated, the term &#34;part(s)&#34; refers to part(s) by weight. Specific examples of the compound (I) are designated by the respective compound numbers shown in Table 1. 
     EXAMPLES 1-9 and Comparative Examples 1 
     To each of the compound (1), (4), (8), (16), (57), (67), (72) and (80) were added the ingredients as shown in Table 2. These mixtures were independently mixed and dispersed with a paint conditioner, which afforded compositions of Examples 1-9. In the same manner, a composition of Comparative Example 1 was obtained. The trade names of the ingredients used are as follows: 
     LAROFLEX MP-45: vinyl chloride-vinyl isobutyl ether copolymer made by BASF A.G., in Germany 
     PLIOLITE S-5B: styrene-butadiene copolymer made by The Goodyear Co., in the U.S.A. 
     AEROZIL #200: silica powder made by Degsa A.G., in Germany. 
     
                                           TABLE 2__________________________________________________________________________       Examples                            Comparative       1   2   3   4   5   6   7   8   9   Example__________________________________________________________________________                                           1Compound (1)       30              30Compound (16)   30Compound (4)        30Compound (8)            30Compound (57)                   30Compound (67)                       30Compound (72)                           30Compound (80)                               30LAROFLEX MP-45       10  10  10  10      10  10  10  10  10PLIOLITE S-5B               10Copper rhodanide                                30Red iron oxide       5   5   5   5   5   5   5   5   5   5Zinc oxide  5   5   5   5   5   5   5   5   5   5AEROZIL #200       1   1   1   1   1   1   1   1   1   1Chlorinated paraffin       2   2   2   2   2   2   2   2   2   2Rosin       10  10  10  10  10  10  10  10  10  10Xylene      32  32  32  32  32  32  32  32  32  32Methyl isobutyl ketone       5   5   5   5   5   5   5   5   5   5Total       100 100 100 100 100 100 100 100 100 100__________________________________________________________________________ 
    
     Test Example 1 
     Each of the coatings obtained in Examples 1-9 and Comparative Example 1 was applied by means of an air spray to a sandblasted steel panel of 300×100×3.2 mm in size, which had been coated with a shop primer and an anti-corrosive paint of the vinyl tar type, in such a manner that a dry film of 100 μm in thickness was obtained. These sample panels were dried for 7 days, and immersed and left at rest in the sea off the coast of Miyajima in the Bay of Hiroshima at Hiroshima Prefecture, and examined for the adhesion of harmful aquatic animals and plants as well as the adhesion of slime. The results are shown in Table 3. The amount of adhering harmful aquatic animals and plants in the table was evaluated as the percentage (%) of area to which they adhered, and the amount of adhering slime in the table was evaluated by the following criteria: 
     0: no adhesion; 1: slight adhesion; 2: small adhesion; 3: moderate adhesion; 4: moderate to great adhesion; and 5: great adhesion. 
     
                                           TABLE 3__________________________________________________________________________  6 months  12 months 18 monthsImmersion  Harmful   Harmful   Harmfulperiod     aquatic   aquatic   aquaticAdhering   animals   animals   animalsobjects  Slime      and plants            Slime                and plants                      Slime                          and plants__________________________________________________________________________Example 1  0   0     1   0     2   0Example 2  1   0     2   5     2   5Example 3  2   0     2   5     3   15Example 4  0   0     1   5     1   10Example 5  1   0     1   0     2   0Example 6  2   0     2   10    3   30Example 7  1   0     2   5     2   15Example 8  0   0     1   0     1   5Example 9  1   0     1   5     2   5Comparative  5   10    5   60    5   100Example 1__________________________________________________________________________ 
    
     Examples 10-18 and Comparative Examples 2-4 
     Various compositions containing the ingredients as shown in Table 4 were obtained in the same manner as employed in Examples 1-9. For comparison, various compositions containing the ingredients as shown in Table 5 were obtained in the same manner. 
     
                                           TABLE 4__________________________________________________________________________               Examples               10  11  12  13  14  15  16  17  18__________________________________________________________________________Compound (1)        5Compound (16)           5Compound (4)                5Compound (8)                    5   5Compound (57)                           5Compound (67)                               5Compound (72)                                   5Compound (80)                                       5LAROFLEX MP-45      10      10  10      10  10  10  10PLIOLITE S-5B           10          10Cuprous oxide       30  30  20  20  20  30  30  30  30Zinc dimethyldithiocarbamate                       52,4,5,6-Tetrachloroisophthalonitrile                           5N,N-dimethyl-N&#39;-(3,4-dichlorophenyl)urea                               5Red iron oxide      5   5   5   5   5   5   5   5   5Zinc oxide          5   5   5   5   5   5   5   5   5AEROZIL #200        1   1   1   1   1   1   1   1   1Chlorinated paraffin               2   2   2   2   2   2   2   2   2Rosin               10  10  10  10  10  10  10  10  10Xylene              27  27  32  32  32  27  27  27  27Methyl isobutyl ketone               5   5   5   5   5   5   5   5   5TOTAL               100 100 100 100 100 100 100 100 100__________________________________________________________________________ 
    
     
                       TABLE 5______________________________________           Comparative Examples           2      3        4______________________________________LAROFLEX MP-45    10PLIOLITE S-5B              10       10Cuprous oxide     30       30copper rhodanide                    20Zinc dimethyldithiocarbamate        10Red iron oxide    5        5        5Zinc oxide        5        5        5AEROZIL #200      1        1        1Chlorinated paraffin             2        2        2Rosin             10       10       10Xylene            32       32       32Methyl isobutyl ketone             5        5        5Total             100      100      100______________________________________ 
    
     Test Example 2 
     The compositions obtained in Examples 10-18 and Comparative Examples 1-4 were examined in the same method as used in Test Example 1. The results are shown in Table 6. 
     
                                           TABLE 6__________________________________________________________________________  6 months  12 months 18 monthsImmersion  Harmful   Harmful   Harmfulperiod     aquatic   aquatic   aquaticAdhering   animals   animals   animalsobjects  Slime      and plants            Slime                and plants                      Slime                          and plants__________________________________________________________________________Example 10  1   0     1   0     2   0Example 11  1   0     1   0     2   0Example 12  2   0     3   0     3   5Example 13  1   0     2   0     2   0Example 14  0   0     1   0     2   0Example 15  2   0     3   0     3   10Example 16  1   0     2   0     2   0Example 17  0   0     1   0     2   0Example 18  1   0     1   0     2   0Comp. Ex. 1  5   10    5   60    5   100Comp. Ex. 2  5   0     5   10    5   30Comp. Ex. 3  5   0     5   10    5   30Comp. Ex. 4  3   0     5   30    5   60__________________________________________________________________________ 
    
     Test Examples 3 
     The compositions obtained in Examples 1-4, 10-13 and Comparative Examples 2-4 were used for the test in which they were actually applied in a patch on to the bottoms of small fishing boats working in three sea areas of Nagasaki Prefecture, Hiroshima Prefecture and Niigata Prefecture. After the lapse of 6 months, the adhesion of harmful aquatic animals and plants as well as the adhesion of slime were evaluated in the same manner as described in Test Example 1. The results are shown in Table 7. The symbol &#34;-&#34; in the table refers to no execution of the test. 
     
                                           TABLE 7__________________________________________________________________________  Nagasaki  Hiroshima NiigataImmersion  Harmful   Harmful   Harmfulplace      aquatic   aquatic   aquaticAdhering   animals   animals   animalsobjects  Slime      and plants            Slime                and plants                      Slime                          and plants__________________________________________________________________________Example 1  --  --    0   0     0   0Example 2  --  --    0   0     0   0Example 3  --  --    1   0     0   0Example 4  --  --    0   0     0   0Example 10  0   0     0   0     --  --Example 11  0   0     1   0     --  --Example 12  1   0     2   0     --  --Example 13  0   0     0   0     --  --Comp. Ex. 2  5   0     5   0     5   0Comp. Ex. 4  --  --    5   10    4   5__________________________________________________________________________ 
    
     As described above, the compound (I) has an excellent effect on the prevention and inhibition of harmful aquatic organisms adhering to water-exposed articles, and such an effect can be retained for a long period of time. Accordingly, the compound (I) can find various applications in the form of a controlling agent or antifouling composition against harmful aquatic organisms.