JPH06507661A - Marine composition with selective enrichment area of tin-free organic antifouling agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

NOTE This invention relates to marine antifouling coatings, and more particularly to novel low toxicity antifouling agents for coatings. Basic requirements regarding coating One of these is the marine environment, where early examples include steel and mercury compounds. It was mainly composed of known poisonous substances. Nineteenth century marine coatings typically used natural drying oils containing creosote and poisons. For ship bottom applications, antifouling compounds based on copper and tin are currently added to water-sensitive binders, thus progressively destroying the film and liberating the "toxins". It is something that can be enjoyed. This necessarily self-eroding nature results in the need for frequent repainting of the ship's bottom, depending on the location and severity of erosion. Current antifouling coatings are based on selected resin matrix types, i.e. There are two common leaching mechanisms, depending on whether they are soluble or insoluble. It will take a lot of time. In the insoluble matrix type, the toxic particles are dissolved in seawater and released, leaving the resin skeleton intact. This also means that toxic substances can migrate to the surface and enter solution by contact with seawater. It is said to be a contact type because it depends on The resin is somewhat permeable to water, so when one particle dissolves, another is exposed to seawater. This contact type is several times more toxic than the dissolved type. By thickening the toxic film, the antifouling top coat will last longer. As a general rule, insoluble matrix type coatings do not contain extender pigments and dry The shape of the dried film requires a high toxicant content (52% to 74% by volume). This is to ensure that the Cu,0 particles are in continuous contact with each other. cube backing Below the level of the hexagonal backing (52%), the resin wraps around the Cu2O particles and prevents the solution; above the level of the hexagonal backing (74%), the coating has too little resin to compromise film integrity. It becomes impossible to hold it. These characteristics actually vary somewhat. (e.g. by adding rosin or other natural resins) It is common to adjust the rate of leaching and the extent of toxic effect (by one In general practice, both natural resins and extender pigments are often used. high If high levels of rosin are used and severe erosion is expected, reinforcing agents such as ester gums, ethyl cellulose, and modified rubbers are added. (Literature: Pei (G, E, Weismantel, McGraw-Hi Il), New York, New York, pp. 14-43, 14-44 pages; and (R, J, Dick), Marine Paints, Chapter 14). Regarding toxic substances currently used in marine antifouling paints, recent U.S. law The use of tin stain inhibitors is strictly limited. Concerns regarding toxicity are highly dependent on this recent legislation. Previous proposals, for example, Japanese Patent Nos. 56156202 and 52117425, have reported the use of naphthoquinone and thiuram disulfide in combination to obtain antifouling activity; Patent No. 63 243067 proposes the use of diphenylamines. Despite these proposals, there is still a substantial need for new low-toxicity antifouling coatings, caulking, and other antifouling solutions. A curable compound consisting of a stopper and optionally known additives such as leaching agents, opacifying pigments, etc. The present invention relates to a marine antifouling composition that can be used as a marine antifouling composition. The antifouling agent is a selectively concentrated domain in the cured composition (hereinafter referred to as "PCD" or "PCDs"). These PCDs are The stems may be heterogeneous, phase separated, or incompatible. The technical terminology used to refer to the PCDs of antifouling agents is not intended to limit the invention as illustrated in this description. Preferably, the PCDs contain whole oligomeric adducts of the antifouling agent, the adducts being formed on the PCDs upon curing of the composition. It is generated by doing. The technology for forming PCDs as an antifouling agent is described here. The present invention also provides an LD50 value of greater than 200 mg/kg for rats or mice and an LD50 value of about 0.5 mg/kg. The present invention relates to the use of novel, low-toxicity antifouling agents consisting of insecticides or herbicides with a χ value of vinyl or aromatic compounds between OI and 0.08, a χ value between about 0.01 and 3. Such pesticides or aldicide compounds are widely used Terocyclic compounds, tetraatom-substituted aromatic compounds, various amino compounds, carbocyclic vinyl etherketones, certain phosphocompounds, certain polychlorinated carbocyclic and acyclic compounds, certain chlorinated carbocyclic carboxylates, antimony tartrate, boric acid, and cupric oleate. Examples of aromatic compounds include diaromatic compounds, condensed Included are fused aromatic rings, and mono-aromatic compounds. Advantages of the present invention include the ability to formulate marine antifouling compositions containing low toxicity antifouling agents. Another advantage is that this low toxicity antifouling agent can be formed into PCDs to form a low toxicity marine antifouling composition that exhibits improved efficacy. These and other advantages will be readily apparent to those skilled in the art based on this disclosure. Figure 1 shows 10% of the cured epoxy resin composition of Example 16 in which the organic poison was freely dispersed. Figure 2 is a scanning electron micrograph (SEM) of Example 16, in which the same organic toxicant was freely dispersed and contained a domain-forming polysulfide polymer. Figure 3 is a graphical representation of the SEM results of Figure 1 and Figure 2, where A is a discontinuous polysulfate resin composition. B is a continuous polysulfide/chloride environment and B is a continuous polysulfide/chloride environment. 250x SEM of the cured epoxy resin composition of Example 16: Figure 5 is an energy dispersive spectroscopy of chlorine contained in the organotoxic polymer region of Figure 4: Energy dispersive spectroscopic analysis of sulfur contained in Figures 7 and 8 show the domain structure formed in a continuous PvC binder by the domain forming acrylic polymer with the organic toxic monomer described in Example 17, with 500x and 2,500x SEMs, respectively. Figure 9 is a subsection of Figures 7 and 8. Figure 10 is a 1.500x energy dispersive spectroscopic analysis of oxygen contained in the samples of Figures 7-9. Figure 11 is a 2.000x optical micrograph of the samples of Figures 7 and 8; Figure 12 is a 2.000x energy-dispersive spectroscopic analysis of oxygen contained in the samples of Figures 7-9; 13 is a 200x optical micrograph showing the domain structure formed in a continuous epoxy resin by the LP-32 polysulfide resin of Example 18; and FIGS. 14-15 show the resin system of FIG. It is an energy dispersion spectroscopy diagram. Due to human toxicity, the acceptable use of organotin antifouling agents must be curtailed, and techniques are needed to obtain antifouling agents that exhibit low human toxicity. Such dirt The anti-corrosion agent must be compatible with the rest of the forming ingredients in the marine coating and other marine compositions. These low-toxicity stain repellents also make them practical. It must demonstrate the effectiveness of the project. The use of tin-free organic antifouling agents in marine compositions provides a slight, but not yet improved, long-term protection for the substrates to which the compositions are applied. is desired Ru. Unexpectedly, it has been found that by controlling the physical form in which the antifouling agent is present in the cured marine composition, good activity over long periods of time can be obtained. Phase separation is a term used to define physical shape and the like. “Selectively dark The term "contracted area" refers to the various techniques that have been developed to achieve the desired physical shape of the antifouling agent. In this way, the area, island, where the antifouling agent is concentrated , or pools, are created in the cured composition. Such areas are typically about 0.3μ to 500μ (micrometers) in size. It is. A technique for achieving antifouling PCDs is to chemically bond antifouling agents with phase-separated polymers or oligomers in the cured composition. This technology also has the advantage of preventing the stain release agent from prematurely leaching out of the cured composition, resulting in a loss of stain protection effectiveness. Other techniques include, for example, dispersing in the continuous phase of the composition an antifouling agent that is soluble (or compatible) with the compound itself or the region-forming compound. It is. Such incompatible compounds form discrete regions in the cured composition that are region-rich compared to the remaining continuous phase of the cured composition. Other than chemical bonding of oligomers or polymers with antifouling agents, The anti-blocking agent can be associated with or complexed with compounds that are incompatible with the continuous phase of the composition. As long as the antifouling PCDs are formed in a cured composition, the principles of the present invention are put into practice. Conventional tin-free organic stain repellants can be used in the present invention to form PCDs. It is possible to use it. Preferred tin-free organic soil inhibitors useful in the present invention, however, include compounds that exhibit broad terrestrial biological activity, such as selected from known herbicides and insecticides. In the present invention, herbicides are understood not only as compounds that broadly and/or selectively kill various plants; It contains a growth regulator, algicide, etc. Pesticides are also understood according to the invention as compounds selectively and/or broadly toxic to harmful plant pests, such as acaricides. These compounds, however, must exhibit low toxicity to humans. In the present invention, "low toxicity for humans" means that the LD50 value for rats or mice is greater than 200 mg/kg. The compounds also have a χ factor between about 0.01 and 3 and a vinyl or must have the Z value of an aromatic compound. This χ factor is based on the McGinniss predictive relationship as defined in the literature (Organic Coaching in Plastic Chemistry, Volumes 39 and 46, pages 529-534 and 214-223, respectively (1978 and 1982)). ) based on This is what I learned. The Manokuginis predictive relationship is The χ factor is defined as the weight fraction of peteroatoms contained in the monomer repeat unit or in the monomer. The Matsuku Ginis prediction relationship is In or in the monomer repeat unit of a oligomer or polymer The Z parameter is defined as the weight fraction of π electrons contained in the compound (e.g., the π electron density of aromatic or vinyl compounds). A biologically active compound having a χ factor and a Z parameter (as defined herein) within the above ranges and having a desired LD50 value is a compound that exhibits antifouling properties in marine coatings. Although such compounds exhibit antifouling properties, all are It may not be universally applicable to high-performance marine coatings such as coatings. Needless to say, this compound has low toxicity to humans and antifouling properties, making it an important alternative to traditional organotin antifouling agents. The following biologically active compounds can be used as organic antifouling agents/reactants of the present invention: LD50 value, χ factor and Z parameter are shown. 1 23-dichloro-1-4-naphthoquinone 1 4-allyl-2-methoxyphene Eugenol ○ 5, Diphenylamine Low mammalian toxicity χ factor (N) 0.083 Z parameter 0.071 6, Boric acid B-(OH')3 LD50 value 3000mg/kg (rat) 7.2- Chloro-N, N-dia Lylacetamide. LD50 value 700mg/kg (rat) χ factor (CI) 0.205 χ factor (0) 0.092 χ factor (N) 0.081 Z parameter 0.023 8. Cetyltrimethylammonium bromide LD50 value 500mg/kg ( La (rat) χ factor (N) 0.038 χ factor (Br) 0.22 9, 2-isopropylamino-4-chloro-6-dithylaminotriazine LD50 value 1869 mg/kg (rat) χ factor (N ) 0.325 χ factor (CI) 0.244 Z parameter 0.041 10. LD50 value of dimethoxythiophosphate derivative of diphenyl sulfide 2030 mg/kg (rat) 11. Ethyl 4-chloro-a (4-chloro LD50 value 5000mg/kg (rat) Z parameter 0.022 12. Methyl, diethylamino, and dimethoxythiophosphate derivatives of pyrimidine Conductor LD50 value 2000 mg/kg (rat) 13, Ethoxylated nonylphenol LD50 value 4000 χ factor (0) 0.25 Z parameter 0.0105 14, Asymmetric hydrazine derivative 4 of succinic acid LD50 value 8400 15, Dimethylbrobenyl Allyl, methyl hydride of cyclopropane carboxylic acid Roxy-substituted cyclopententone ester L I) 50 value 1000 χ factor (0) 0.11 Z parameter 0021 16.2.5-dichloro0.3-aminobenzoic acid LD50 value 5620 χ factor (0) 0.155 χ factor ( N) 0.068 177 C1) 0.345 Z parameter 0.015 17. Cinnamic acid Z parameter 0.054 22. Diphenyl ether of isobutyric acid ester of hydroxyacetonitrile, Lorophenyl derivative LD50 value 451 (Toxicity to fish) χ factor (0) 0.114 χ factor (N) 0.033 χ factor (C1) 0.085 Z parameter 0.043 23, Trihydroxybenzoic acid Z parameter 0.035 24, 3-indoleacetic acid χ factor (0) 0.198 χ factor (N) 0. o86 Z parameter 0.037 25.3.5-dichloro-N-(3,3-dimethylpropyne)benzamide LD50 value (skin) 8350 χ factor (0) 0.063 χ factor (N) 0.055 χ Factor (CI) 0.278 2 parameters 0.039 30, 7 talic acid l, r < lame - 0,036 Z parameter 0.040 32, N-phenyl, N-butynyl Chloroacetamide LD50 value 1177 χ factor (0 ) 0.072 χ factor (N) 0.063 Affactor (C1) 0.160 Z parameter 0.045 33, amine, chloro, phenyl derivative of azacyclohexamine LD 50 value 3030 χ factor (0) 0.073 χ Factor (N) 0.190 χ factor (CI) 0.161 Z parameter 0.036 :34 N,N~diallyl-2-chloroacetamide LD 50 value 750 Z parameter 0023 35 Aminoacetic acid derivative of methylphosphonate LD 50 Value 4300 χ factor (P) 0.183 36,3.5-dinitro,4-N,N-dipropylaminobenzene sulfur LD 50 value 10000 χ factor (0) 0.277 E factor (N) 0.162 Z Parameter 0.017 37, 2-chloro-2-propenyl diethylcarbamodithioate LD50 value 850 χ factor (N) 0.064 Z parameter 0.0092 As shown in the data in section E, the biologically active The compound is used as a stain repellent This shows the effect of The low toxicity to humans makes it effective compared to traditional organotin stain repellents. The low toxicity stain repellents of the present invention are based on biologically active compounds that are aromatic, heterocyclic, amino compounds with heteroatom substituents, and carbocyclic ketone vinyl ethers. The above compounds (t: eg, insecticides and herbicides) may be disclosed. Aromatic compounds may be further modified with carbon or divalent heteroatom substituents or with sigma bonds. It may also be a diaromatic compound, a mono-aromatic compound, or a fused aromatic ring compound. In addition to these cyclic compounds, biologically active and desired χ values and Z parameters Hetero-substituted aliphatic compounds with meter also find use as antifouling agents in the present invention. It can be used as Furthermore, not all regulations are necessarily consistent with the above provisions. Compounds are also included within the scope of the antifouling agents of the present invention. This includes It also contains boric acid, which is said to be active as a stain repellent, as evidenced by data. Additional compounds include, for example, antimony tartrate and ferric oleate. Examples of low toxicity stain repellents of the present invention are shown in Table 2 below. 5I Examples of low toxicity stain repellents Acrolein Phenylhydrazone Alkyl Dimethyl Benzene Ammonium Saccharate 2-allyl-4-hydride of dimethyl-3- (2-methylpropenyl cyclopropanecarboxylic acid) Roxy-3-methyl-2-cyclopenten-1-one ester 4-allyl-2-methoxyphenol 0-(allyloxy)phenyl 2-(allylthio)-2-thylcarbamate Azoline], 2,3,4.7.7-hexachloro-5,6-bis(chloromethyl)-2-norbornene 4-ethylamino-6-isoprobylamino-2-methylthio-1,3,5-to riazine 2-amino-3-chloro-1,4-naphthoquinone 3-amino-5-nitro-0-toluamide 3~amino-! , 2,4-) lyazole ammonium sulfamate antimony potassium tartrate 2-chloro-4-ethylamino-6-isopropylamino-S-triazine 4~ chloro-m-chlorocarbanilate 6-chlorobibenyl chloride Santemate N-butyl-N-ethyl-6,σ,α-trifluoro2-6-sinitro p-toluidine bis(p-chlorophenyl)-3-pyridine methanolbis(dialkylphosphinothioyl)disulfide bis(4-hydroxy iminomethyl viriditum -l-methyl)ether dichloride 2,4-bis(3-methoxylpropylamino)-6-methylthio-5-)ly Ajin Bis(pentachloro-2,4-cyclopentadien-1-yl)boric acid N-(4-bromo-3-chlorophenyl)-No-methoxy-No-methylurea 5-(bromomethyl)-1,2,3, 4,7,7-hexachloro-2-norbol Nene S-(0,O-diisopropyl phosphoro-dithionate N-(2-mercap toethyl)benzenesulfonamidebenzamidooxy-acetic acid 3-benzylideneamino-4-phenylthiazoline-2-thousand bis(p-chloro lophenoxy)methane Bis(4-chlorophenyl) disulfide 1.1-bis(p-chlorophenyl disulfide ethane 1,l-bis(p-chlorophenyl)-ethanolo,o-dimethyl-o-2,5-dichloro-4-bromophenylthionophosphate 0.0-dimethyl-2,2,2-trichloro-1- n-Butyryloxyethyl phosphonate N-butylacetanilide 2-t-Butylamino-4-chloro-6-ethyl Amino-5-triazine 2-

[-butylamino-4-ethylamino-6-methylmercapto S ~ triazine 4-[-butyl-2-chlorophenylmethyl methylphosphoraamicito o-(4-t-butyl-2-chlorophenyl)o-methyl phosphora Amidothionate 3,4-dihydro-2,2-dimethyl-4-oxo-1,2h-bilan-6-ka Butyl rubonate n-butyl-9-hydroxyfluorene-(9)-carboxylate 2-(p-t-butylphenoxy)cyclohexyl 2-propynyl sulfide m-chlorophenyl-carpamate 1-butyn-3-yl N-trichloro -Methi ruthio-4-cyclohexene-1,2-docarboximide I 1-naphthyl rhomethylcarbamate S-[[(p-chlorophenyl)thiol]methyl]0.0-diethylphosphoro dithioate 2-chloro-N, N -Diarylacetamidodiethyldithiocarbamic acid 2-Chloroallylbromidecetyldimethylethylammonium chloridecetylpyridinium Tetrachloro-p-benzoquinone 2-chloro-4,6-bis(diethylamino)-S-triazine p-chloroben Zyl p-chlorophenyl sulfide 1.2, 3.5, 6. -7.8.8-o Kutachloro-2,3,3a,4,7゜7a-hexahytoO-4,7-methanoin 1-(3-chloroallyl)-3,5,7-doriaza 1-azoniaada Manthane ethyl 4,4'-dichlorobenzilate 5-chloro-2-penzothiazolethio Zinc salt p-chlorobenzyl p-fluorophenyl sulfide l-chloro rho-N'-(3,4-dichlorophenyl)N,N-dimethylformamidine 4-chloro-3,5-dimethyl phenoxy-ethanol 1,4-dichloro-2,5-dimethoxybenzene 1-(chloro-2- norbornyl)-3,3-dimethy Luurea s-(p-chloro-a-phenylbenzyl)0.0-diethyl phosphoro dithioate p-chlorophenyl ester of benzene-sulfonic acid carbamate N-3-chloro lophenyl-1-(isobuwabi-carbamoyl-1)-ethyl 3-(p-chlorophenyl)-5-methyl rhodanine 4 (and 6)-chloro-2-phenylphenol sodium salt p-chlorophenyl phenyl sul 4-chlorophenyl 2,4.5-)chlorophenylazosulfide N-(5-chloro-5-thiazolyl)propionamide 2-[4-chloro-o-1lyl)oxy]propionanilide 2-chloro -1-(2,4,5-)lichloro -phenyl)vinyl dimethylphosphate N'-(4-chlorophenoxy)phenyl N, N-dimethylurea N-(3-chlorophenyl)carbamate isopropyleleate (secondary) ti4 copper 8-quinolyl-to 2- (2, 4-Dihydroxyphenyl)-1-cyclohexene-1-carboxylic acid-β-lactone-〇-diethylphosphothioate 2-chloro-4-dimethyla Mino-6-methylpyrimidine 3-(2-:/clopenten-1-yl)-2-methyl Chill-4-oxo-2-cyclobeadecy-1-yl chrysantheminate a-ne Chlorhexyl-σ-buenyl-3-pyridyl-methanol, hydrochloride N'--/Cl Low octyl-N, N-dimethylurea 3', 4°-dichlorocyclopropanka ruboxyanilide 2.4-dichlorophenoxyacetic acid 2.4d,a-chlorocrotyl ester 3.5-dimethyl-1,3,5,2H-tetrahydrothiadiazin-2-thousand, tetrahydro-3,5-dimethyl-2H- 1,3,5-thiadiazine-2 to 1,000 ions 4-(2,4-dichlorophenoxy)butyric acid 2.3.5.6--tetrachloro dimethyl terephthalate-liphenylphosphonium-bromochlorotri Phosphite 2-7 dihydroacetic acid (and its sodium salt) tris and bis(2,4-nochlorophenoxy) 4-isopropylamino-6-methylamino-5-triazine N , N-diisopropylcarbamate S-2,3-dichloroallyl 1.3-/'other 2.4-ink]pentadiene N,N-di-n-butyl-p-k lolobenzene-sulponamide 3.6-dimethylco-[)-anisic acid 0 (:F-ri1170-, -4-, neat[)-phenyl-)0.0-dimethyl phosphorothioate 2,6-dichlorobenzonitrile 2,3-dichloro-1,4-naphthoquinone 1,3-bis(l-hydroxy-2,2,2-trichloroethyl)urea 2,3-dichlorobenzyl methylcarbamate (20%) and 3,4-dichlorobenzyl methylcarbamate (80%) Product 1.1-dichloro-2,2-bis(p-ethylphenyl)ethane 2.4-dichloro-2,2-bis(p-ethylphenyl)ethane Lolo-6-(o-chloro-anilino)-s-1 riazine N-(dichlorofluoromethylthio)-N' N' -dimethyl-n-phenylsulfamide 4.4°-Dichloro-N-methylbenzene-sulfonate Anilide 2.3-dichloro-2-methylpropionic acid sodium salt 2.6-dichloro-4-nitroaniline 2.5-dichloro-3-nitrobenzoic acid 5.2'-dichloro-4'-nitrosa lysylanilide ethanolamine Salt 2',5'-dichloro-4'-nitrososalicylanilide 2,2'-dihydro xy-5,5°-dichlorophenylmethane1-(2,4-dichlorophenoxy acetyl)-3,5-dimethyl pyrazoN-3,4-dichlorophenyl N'-5-chloro-2-(2-sodium sulfonyl-4 -chlorophenoxy)pheni 2,4-dichlorophenyl ester of luureabenzenesulfonic acid Loroya 1-nyl methanesulfonate 2,4-dichlorophenyl 4-nitrophe Nyl ether 4-dichlorotetrahydrothiophene l,l-dioxide 4. 4′-dichloro-〇-trichloromethylbenzhytrol 3°, 4°-dichloro-2-methacrylanilide. -(jetoxyphosphinothioylthio), -butyrolactone 0.0-diethyl S-carboethoxymethyl phosphoro Thioate 0, 0--diethyl 0-naphutylamide Phosporothioate 0.0-diethyl 0 3. ',,l,6-dolychloro-2-pyridyl phos Holothiony 1.2.2゛-Dihydroxy-3.5,3°,5',4''-Pentachlorotrif Lni lumethane 2'-sodium sulfonate 0.0-diisopropyl S-die Tildithiocarbamoyl phosphorodithionite 2,2-dimethyl-:3-(2-methylpropenyl)cyclopropanecarboxylic acid 2,4-dimedylbenzyl 0.0-dimethyl-5-2-(acetylamino )-ethyl dithiophosphate N-dimethylamino succinamic acid 1.1-dimethyl-3[3-(nt-butyl-carbamoyloxy)phenyl 1-urea 0.0-dimethyl S-carboethoxymethyl phosphorothioate 0.0- Ji Methyl 0-(3-chloro-4-nitrophenyl)phosphorothioate 0.0-dimethyl-op-cyanophenyl phosphorothioate o,o-dimethyl Thyl-5-[5-ethoxy-1,3,4-thiadiazol-2(di()-onyl-(3)-methyl 1 phosphorodithioate N, N--dimethyl-N'-(2-methyl- 4-Chlorophenyl)-formamidecy hydrochloride 0,o-dimethyl 0-(4-nitro-m-1lyl)phosphorothioate 0,S-dimethyl tetrachloro thioterephthalate 4'-dimethyltriazenoacetate Toanilide dinitrocyclohexylphenol 2.4'-dinitro-4-trifluoromethyl diphenyl ether 2-(1-methyl-n-hebutyl)-4,6-cyanophenyl rirotonate N,N-dimethyl-2,2-diphenyl Acetamide diphenylacetonitrile diphenylamine 2.6-sinitro N,N-di-n-propyl-p-)kiidine di-n-propyl -2,5-pyridine-dicarboxylate dibromide 1.1°-ethylene-2,2 ゛-Dipyridinium 2,3-dicyano-1,4-dithia-anthraquinone 3-(3,4-dichlorophenyl)-1,1-dimethyl-urea n-dodecyl thiosyl Anate n-dodecylguanidine acetate N,N-dibropylthiolcarbamate ethyl 2-(2,4,5-tric chlorophenoxy)ethyl-2,2-dichloropropionate ethoxymethylbis(p-chlorophenyl)carbinol 1.2-dihydro-6-ethoxy2.2.4-)limethylquinonethiolcarbamate-N, N-diisobutylethylenebis(dithiocarbamado)zinc 3-phenyl-1,1-dimethylurea Trichloroayatate dimethyl-dithiocarbamate ferric acid 0.0-dimethyl 5-(N-formyl-N-methylcarbamoyl-methyl) Ho Sporodithioate 2-formyl-4-chlorophenoxyacetic acid 3-furfuryl-2-methyl-4-o xo-2-cyclopenten-1-ylchrysantheminate 2-heptadecyl-2-imidacillin 7-chloro-4,6-simethoxycoumaran-3-one-2-spiro-1゛-(2°-methoxy- 6'-Methylcyclobex-2'-en-4'-one)1, ], 1.3, 3.3. -Hexachloro-2-propanone 1.5a,6,9.9a,9b-hexahydro-4a(4H)-dibenzofuranka J Levoxialde Hydrode 9-(p-n-hexyloxyphenyl)-10-methyl-acridinium chloride 2-hydroxymethyl-4-chloro-phenoxyacetic acid N-hydroxy-methyl-2,6-cyclothiobenzamide N-phenylcarbamic acid Isopropylthio Isobornyl cyanoacetate Isobutyl Triphenylmethylamine 5-bromo-3-isopropyl-6-methane Tiluracil isoprovil-4,4'-dibromobenzilate isoprobil 4,4'-dichlorobenzylate isoprobil Mercaptophenyl-acetate, 0.0-dimethyl phosphorodithioate 3-cyclohexyl-6,7-cyhydro IH-cyclopentapyrimidine-2,4(3H,5H)-dione 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea S-[1,2-bis(ethoxy-carbonyl)ethyl]0 .0-dimethylphosphorodithioate ethylenebisdithiocarbamate manganese 4-chloro-2-methylphenoxy vinegar acid 2-(4/-chloro-2-methylphenoxy)propionic acid 4 (or 5) -chloro-2-methylcyclohexanecarboxylic acid 5ec-butyl s-[(4,6-diamitu-s-triazin-2-yl)methyl ]0.0-nme Dill phosphorodithioate 2-isopropylamino-4-(3-methoxypropylamino)-6-methylthioate o-5-) riazine 1,l,1-4lichloro2,2-bis(p-methoxyphenyl)ethane 2-methane Toxy-4-isopropylamino-6-diethylamino-5-)riazine 5-(N-methoxymethylcarbamoylmethyl)dimethyl phosphorothiolothio Nonate 3-(dimethoxy-phosphinyloxy)-cis-crotonic acid. -Methylbenzi Methyl-carbamic acid m-(1-methyl butyl)phenylmethyl-2-chloro-9-hydroxyfluorene-(9)-carboxylate 3.3'-methylenebis(4-hydroxycoramarine)2.2"- methylene bi S(3,4,6-1-dichlorophenol)6-methyl-2-oxo-1,3-dithio(4,5-b)quinosaline 0.0-dimethyl S-(2,5-dichlorophenol) phenyl-thio)-methyl phosphorodithioate 3 (2-methylpiperidino)propyl-3,4-dichlorobenzoate 4-(methylsulfonyl)-2,6-sinitro n,n-diprobylanilimethyl-2,3,5 ,6-tetrachloro n-methoxy n-methyl terephthalamate O-methyl O-(2,4,5-trichloro-phenyl)amide phosphorothiome 3-(1-bromophenyl)-1-methyl-1-methoxyurea 1,2-dihydro pyridazine-3,6-dione 3.3'-ethylenebis-(tetrahydro-4,6-cymethyl-2H-1゜3.5-thiacyacin-2-thione) S-ethyl hexahydro-L H-azepine-1-carbothioate 3-(p-10lophenyl)-1,1-dimethylurea trichloroacetic acid 3-(p-chloro phenyl)-1,1-dimethylurea disodium ethylene bisdithiocarba mate 1,2-dibromo-2,2-dichloroethyl dimethyl phosphate β-naphthoxyacetic acid 3-(3,4-dichlorophenyl)-1-methyl-1-n-butylurea 3-(hexahydro-4,7-methanoindan- 5-yl)-1,1-dimethylurea N-1-naphthyl-phthalamidic acid p-chlorophenyl p-phenyl 4-chlorobenzenesulfonate S-propylbutyl-ethylthiocarbamate, notiazine'-delmercapto-phenylacetate 0, 0-dimethyl-boshoroditi Oate n-phenyl-1-(ethylcarbamoyl-1)ethylcarbamate (d isomer) Phosphoric acid, 2-10rho-1-(2,4,5-)dichlorophenyl)vinyl dimethyl Tyl ester 4-amino-3,5,64-lichloropicolinate biveronylrubis(2-E2°-n-butoxyethoxy]ethyl)aceterbiveronyl butoxide a [2(2-n-butoxyethoxy)-ethoxy]4. 5-Methylenedioxy-2-pro-biltoluenebiperonyl cyclonene Polychlorobenzoic acid, dimethylamine salt 2.4-bis-(isopropylamine)-6-medoxys-4 riazine 2-methyl-mercapto-4 ,6-bis(i) Sopropylamino)-S-)Ryazine 2-Chloro-n-isopropylacetanilide 3',4'-dichloropropiona Lido 2-chloro-4,6-bis(isopropyl-amino)-s-4 riadine di-n-propyl-3-methyl-6,7-methylenedioxy-1,2,3°4-tetra-hydronaphthalene-1 ,2-dicarboxylate 5-amino-4-chloro-2-phenyl-3(2H) pyridazinone dimethyl 2,4.5-trichlorophenylene Phosphorothionate salicylanilide 1-(3,4-methylene-dioxyphenoxy)-3,6,9-)Lioxou Ndecane sodium 2-(2,4-dichlorophenoxy)ethyl sulfate 1-(2-methyl-cyclohexyl)-3-phenylurea 1-(2,4,5-1-dichlorophenoxy)propionic acid N''-chloro-2 -Methyl-p-valerotor Idide 1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl ]Benzene Methyl 3.4-Chlorocarbanilate 2.4.5-)Dichlorophenoxyacetic acid Trichlorobenzyl chloride 2.2-Bis(p-chlorophenyl)-1,1-dichloroethaneethylene-1,2-bis(thio Carbamoyl dimethylthio-carbamoyl disulfide) 3-t-butyl-5-chloro-6-methyluracil 2,6-di-t-butyl-p-h ruylmethylcarbamate 2.3,6.7-tetrachloro-4a, 8a −D poxy], 2,3,4゜4a,8a-hexahydro-1,4-methanonaphthalene N-5,8-dione N-(1,1,2,2-tetrachloro-ethyl-sulfenyl )-cis-low 4-cyclohexene-1,2-dicarboximide 2.4,5. 6-tetrachloroisophthalonitrile 1.2,4.5-tetrachloro-3-nitrobenzene p-chlorophenyl 2,4.5-)dichlorophenyl sulfo 5,6,7.8-Tetrahydro-1-naphthylcarbamate 3.4,5. 6-tetrahydrophthalimidomethyl 2,2-dimethyl-5-(2-methyl propenyl) cyclopropanecarboxylate o, o, o', o' -tetramethyl o, o'-thiodi p-phenylenephosphorodioate ], 3.6.8-tetranitrocarbazole 2-(4-thiazolyl)benzimine Dazole 2.2'-thiobis(4,6-dichlorophenol)2-thiocyanoyl Chil dodecanoate 2,3-quinosaline-dithiol cyclic trithi Ocarbonate tetramethylthiuram disulfide N-meta-tolyl phthalamic acid N,N-diisopropylthiolcarbamate S-2,3,3-)lichloro Allyl 0.0-dimethyl(1-hydroxy-2,2,2-)lichloroethyl)phosbone 2.3.61-Lichlorobenzoic acid Trichlorobenzoic acid, dimethylamine salt 4.5.7-Dolichlorobenzthiasia Zoro 2. L 32.3.6-Dolichloropenzyloxyprobanol N-trichloromethylthio-benzothiazolone N-trichloromethylthiobenzoxa zolone chloride 2.2.2-)lichloro n-(pentachloro-phenyl)a7toy Midryl 2-(2,4,5-1-lichlorophenoxy)ethyl sulfate, sodium salt N,N'-N"-trichloro-2,4,6-)lyamine-1.3.5-)lyazi 2-chloro-4-(di-ethylamino)-6-(ethylamino)-s-)riazi tert-butyl 4 (or 5)-chloro-2-methylcyclobexanecarboquine S-probyl diprobyl thiocarbamate ethylene bisdithiocarbamate Zinc Lead Dimethyldithiocarbamate 3,5-dinitro-o-)ylamide Coupling of the antifouling agent with oligomers or polymers can be achieved by various techniques, depending on the function of the antifouling agent. For example, ethylenically unsaturated bonds in antifouling agents are commonly combined with acrylates or other ethylenically unsaturated agents. Therefore, copolymerization is possible. For example, in the literature (“acrylic monomer”, Duct Literature, Dow Buddy Société Company, Form No. A-GB-101;”“Prevaluation, Properties & U.G. of Acrylic Polymers, Product Literature, Rohm A and US Patent No. No. 4.566.962). Antifouling agents having reactive hydroxyl or other active hydrogen functional groups (eg, -NHl-NH2, -3H, etc.) can be reacted with polyisocyanates to form antifouling adducts. For example, the literature ('Macromolecular synthesis', C, G, overbase Luker, vol. 1, pages 69-74, John Belay and Sons, Inc. New York, New York (1963)). Sara Depending on the reactivity function of the antifouling agent, the reaction may be difficult to understand for those skilled in the art, as described above. It will become clear easily. Further techniques for the formation of PCDs include, for example, combining antifouling agents with other ingredients. components, such as extender pigments, polymers or oligomer additives, etc. can be lost. In other technologies, antifouling agents are used in the continuous phase of the coating. It is noted that particles are relatively more miscible in the discontinuous phase (or particles). It will be done. Once again, PCDs are formed. The antifouling agent PCDs is used in the final printing process. As long as it is formed in the product, the antifouling activity will be improved for a long time. The formulation of marine compositions containing the antifouling agents of the invention is carried out in a manner known to those skilled in the art using suitable conventional film-forming binders. The marine compositions of the present invention broadly contain polymer structures suitable for marine surroundings, such as coatings, elastomers, sealants, caulks, topcoats, concrete, and the like. The form of the marine composition may be such as a coating, a rigid or elastic object, a sealant, or a three-dimensional structure on the exterior of a ship. Known adducts, organic solvents (including reactive solvents or diluents), etc. are included in the formulation. The proportion of anti-staining agent is generally about 1 and 1 in the formulation. and 20% by weight. The following examples are specific examples of the present invention, but are not limited thereto. Herein, all percentages and ratios are by weight and all units are in the metric system, unless otherwise indicated. Kanarashi Kanse Town To bind the organic antifouling agent to the polymer structure, a polysulfide polyamide was added to a three-necked reaction flask equipped with a mechanical stirrer, a thermometer, and a reflux condenser. mer (200 g, LP-3 polysulfide polymer, Thi. kol), ],]2-dicyanotetrachlorobenzene (100 g, Rand, Diamond Jamrock), potassium hydroxide (80g), and Methyl sulfoquinide (100 ml) was added. The reaction mixture was heated at 105°C for 3 hours. After heating and cooling to room temperature, it was washed and the solvent was removed under reduced pressure. The resulting polymer-structured antifouling agent-modified adduct was synthesized according to the following reaction formula. Toluene (LOOML) was placed in a round bottom flask, then hydroxyethyl methacrylate Toluene diisocyanate (17 ml) and toluene diisocyanate (17 ml) were added. The mixture was stirred at room temperature for 1 hour, then triethylamine catalyst (3 drops) was added. After 2 hours, 3,4-dichloroanaline (16 ml) was added to the solution and then The mixture was heated to 50° C. and held for 10 hours. The resulting solid product was filtered through #40 filter paper and washed with toluene and hexane. Infrared analysis showed a urethane-amide structure consistent with the desired reaction product 45701-3, with the structure shown below. A pressure reactor equipped with a pressure gauge was charged with 3-(3,4-cycloPphenyl)-1,1-dimethylurea (45 g) and propylene oxide (150 ml). The reactor was sealed, heated to 80°C (50 psi pressure) and held for 20 hours. It was. A sample taken from the reactor was analyzed by IR and a broad peak of NH bonds, hydroxyl groups and some polyether functional groups (1100 cm-') were detected. The preparation of this material is described in the literature (´° Journal The reaction product 45701-4 is similar to the preparation method disclosed in ``Polymer Science'', Vol. 15, pp. 427-446 (1955). reactable hydro Contains xyl group. Hydroxyethyl methacrylate (37 ml) was added to 1,4.5,6,7.7-hexachloro-5-norbolene-2,3-dicarboxylic acid anhydride (37 g). The reaction mixture was heated at 87° C. for 3 hours, producing reaction product 45701-5 shown below. A 10% ethanol solution of CuCI was added to a 10% solution of 8-hydroxyquinoline. Upon application, a dark brown complex was immediately formed. This complex 45701-6 was washed with hexane and then dried without further purification. The structure of this complex is shown below. Since 2.5-dichloroanaline was used instead of 3.4-dichloroanaline, Otherwise, the process of Example 2 was repeated. Reaction Block) 45701-7 is a reaction of 1,5-naphthalene diisocyanate (25 g) with 1,3-diaza-2°4-cyclopentadiene (14 g) and the urethane reaction shown in Example 2. made into a method and reacted. The resulting reaction product 45701-8 was prepared using DER331 epoxy resin (Dowe epoxy resin, approximately 300 molecular weight, 150 epoxy resin) as follows: 35 ml of toluene and phenothiazine (40 g) were added. This mixture The material was heated at 90° C. for 3 hours until a clear solution was obtained. This product was used without further purification. Reaction product 45701-8 is shown below. Two different modified polymer structures were prepared. Polymer construct 45701-10 was prepared using 2-mercaptobenzothiazole dissolved in toluene solvent (35 ml). (log) by adding DER331 resin (11 g). The reaction mixture was heated at 90° C. for 3 hours until a clear solution was obtained. The second polymer structure designated as 45701-11 is 2-mercaptobenzothi It was prepared by a similar reaction method using morpholine instead of azole. Both structures can be shown as follows. In order to illustrate the effectiveness of PCDs, an organic antifouling agent, an antifouling formulation (control agent) was used. Roll paint) was prepared as follows. 1 amount (parts by weight) Ingredients #l #2 Larofresox MP-45 copolymer of vinyl chloride and vinyl isobutyl ether (75/25), BASF Wyandsonod 330 Jin 1O]0 Epicoat 828X90 (Bisphenol A epoxy resin, Celanese Specialty Chemicals) 0.1 0.1 Red 55 Silica 20 20 (1,2-dicyano-tetrachlorobenzene) 20 20 Antifouling agent 4570 1-1 (Example 1) ----Bentone 34 1 1 Xylene 50 50 The test panel was 15.24cmX30.48cm (6inX12in) large It consists of a white plastic top surface and a black plastic bottom surface. Tess The top panel is coated on both sides with the above two formulations to a dry thickness of approximately 5 ml. The test panel was then exposed horizontally, with the white surface on top and the black surface on the bottom, to the ocean at Dydna Beach, Florida, USA. 12% by weight of triphenyltin hydroxide is added to the resinous vinyl binder (vinyl chloride polymer). A comparative panel consisted of methane, 80 parts by weight, VAGH brand, Union Carbide Corporation, New York, NY) dispersed in In ethyl ketone solvent it was reduced to 50% solids. The following results were obtained. Evaluation after test* Sample 1 4 462 days Control paint - no anti-fouling additive 00 Control paint - no addition of antifouling additive, 20% by weight OO control paint - polymer additive 4570 1-1-1 1-1-1 addition of 97% *10 Full Protection The above results showed good panel protection compared to when the polymeric antifouling agent was added neat to the marine paint formulation. As verified in later examples, the polymeric stain repellent was in the form of PCDs in the cured paint. The control paint of Kantane Kasumi Do Example 1O was formulated with additional polymers and antifouling additives and evaluated as in Example 10. The results are shown below. Sample Evaluation after test* 20 wt% i, added 4 462 days Control paint - no antifouling agent added 00 Control paint - 3,4-dichloroaniline OO Control paint - 2,5-dichloroaniline 00 Control paint - 2,6 -Dichloro-4-nitroaniline OO control paint- 3,4-dichloroaniline polymer of Example 2 5-6 5-6 control paint 2,5-dichloroaniline polymer of Example 8 1-2 1 Control Paint - 2,6-dichloroaniline-4-nitroaniline polymer similar to Example 6 - 7-9 7 The above results illustrate the unexpected efficacy of PCD organic antifouling shavings. The control paint of Example 10 was formulated with additional anti-stain additives. and was evaluated. The results are shown below. Table 4 Sample Evaluation after test * - Jin 23 and 1 kibaku 1 shadow σ Lil 4 months Control paint - No antifouling agent added 0 Control paint - Hexa Chloro-5-norborothi 2,3-dicarboxylic acid forging Ocon) Roll Pay 3-4 Control Paint - Phenothiazine 0 Control Paint - Phenothiazine Polymer of Example 8 - 50150 weight of 12-mercaptobenzothiazole and morpholine Mixture O 50150 weight mixture of the morpholine polymer of Example 11 and 2-mercaptobenzothiazole l The above results illustrate the efficacy of the PCD antifouling agent. The control paint of Example 1O was formulated with additional anti-stain additives. and was evaluated. The results are shown below. Sample Post-Test Evaluation* 20wt% addition 1 month 4 months - (3,3-dimethylproine)benzamide or proneamide, Example 10 00 Control Paint - 50150 Blonde polymerized with methyl methacrylate and butyl acrylate Amide 7750150 d-Trans-Arrethrin Polymerized with Methyl Methacrylate and Butyl Acrylate 77 The above results illustrate the efficacy of the PCD polymer antifouling agent. The control paint of Example 10 was formulated with additional anti-stain additives. and was evaluated. The results are shown below. Table 6 Evaluation rate after sample test Troll Paint 3- (3,4-dichlorophenyl)-1,1- (see Example 3) 90 Control Paint - The above urea (200 molecular weight ) 97 Control Paint - 1,5-Natsutashi-Ndiisocyat and 1,3-Diaza-2,4-Siku Reaction product of Lopentadiene (see Example 71) The present invention is confirmed from the results of 6-7 and 6-7L. Cold nose and top l Testing of several additive stain inhibitors in the paint formulation of Example 12 was carried out in 6 cases. The results were compared to several polymerized versions of the same antifouling agent. The results are shown below. 7 -□ Panel # Antifouling agent General evaluation =--” KoIL-RO1roux, 6 flI U-6II! Kawami 3-AI Yuge Nor** 9 3 0 613-A2 in Eugenol* 73061.4- Natsuttaquinone 7 6 0 51.4- Natsutaquinone 5 3 0 514-C I N, N-diallyl-2= chloroacetamide 5 4 0 4-614 ~ C2N , N-diallyl-2-chloroacetamide 5 4 0 4-6 salt 1--1-! 21-Jin and Ot↓pane Free radical polymerized version prepared as reported in Example 2.4, or 6, or as reported in Example 2, depending on the function of the antifouling agent. Prepared chives [tanbanyong]. ** Eugenol is 99% 4-allyl-2-methoxyphenol. In an epoxy resin system, the possibility of modification to selectively influence the location or concentration of an antifouling agent (Novocyto N-96, see Example 1) within its structure is recognized. Tested. A direct comparison is made with epoxy resin (EPON828 epoxy resin, diglycidyl ether of bisphenol A, shell chemical campa Polysulfide resin (LP-32 polysulfide resin, Thiokol Corporation) and similar epoxy resins containing domain-structured polymeric materials were used. The formulated composition is shown below. Epon828 9 6 9 LP-32--3-- Hexachlorophene 1.41 1.29 -Polymer of novoside N-96 and LP-32 polysulfide (3 parts LP-32 and 1.24 parts novoside) -- --1,7 Shion. Contains only hexachlorophene stain repellent and contains area-forming polymer (LP-32 polymer). Samples without lithulphide) distribute chlorine over the entire surface of the sample. It is something that Sample 1 also does not exhibit a regular region size structure, as shown in FIG. However, sample 2 was made of LP-32 polysulfide polymer. We would like to show the unique regular region size (smaller than 1μ) generated by the method (see Figure 2). Energy content of chlorine from hexachlorophene stain repellent on sample surface Dispersed spectroscopy (EDS) analysis shows that there are two distinct regions where chlorine can be detected. was shown. Chlorine shows that the sample has twin sea-like structures and small round island structures. It was confirmed by However, unexpectedly, the concentration of chlorine, i.e. The concentration of anti-corrosion agent was found to be lower (36%) in the oceanic region of the sample and higher (48%) in the round island region. A graphical illustration of these results is shown in FIG. 3. Similar results were observed in sample 3. Sample 3 has a larger area size. chlorine from the nobosite is located in the region or island. It was found only where it was placed. The area between the islands contained no chlorine. The chlorine or sulfur concentration map on the sample surface shows the real structure of the region. In embodiments, regions of continuous polymeric binder or other materials produced within the carrier The potential for selective enrichment in this region was evaluated. For example, certain types of acrylic copolymers dispersed in polyvinyl chloride (PVC) polymers can create discrete regions in which toxic molecules can be selectively concentrated. In this case, the poison is the 3,4-dichloroanaline-based acrylate monomer of Example 2 (80% by weight, melting point of 180°C) and the continuous phase is a VAGHPVC polymer (actual mfA10, 'l'@). The region-generating polymer is a polymer of aminocarbamate monomers. tacrylic acid]-ster (concentration 10% by weight, melting point above 300'C) and polyhydroxyethyl methacrylate (concentration 10% by weight, melting point below 250'C). Electron micrograph scans of PVC containing 20 to 30% by weight of the mixture shown in Table 11 are shown in FIGS. 7 and 8. Mixture of polymer and unreacted monomer in PVC The compounds are easily distinguishable. Surprisingly, the toxic monomer molecules selectively aggregate with the acrylic component creating domains in the PVC binder. film table The surface oxygen density diagram (which analyzes oxygen rather than chlorine due to the presence of chlorine in the binder) (see Figures 9-12) clearly shows that the only place where oxygen remains is within the area. It is shown that. Interestingly, oxygen is not distributed in the porous or sea-like regions of PVC. The oxygen diagram clearly shows only islands or areas where toxic molecules persist, not in the continuous phase or ocean of PVC. The bright areas in these figures are due to the presence of oxygen, and the dark areas are due to the absence of oxygen. It's a good thing. Cold application l The sample of Example 16 except that the hexachlorophene poison was replaced with Novocyto N-96. Pull 2 was prepared again. The formulation of Novocyto with the region-forming LP-32 polysulfide resin was evaluated for Novocyto's formation of PCDs. The cured epoxy resin system was analyzed by SEM and EDS analysis with the results shown in Figures 13-15. was analyzed. Figure 1314 is a 200x SEM micrograph of a section of cured epoxy resin. It is clear that the LP-32 polysulfide polymer forms discrete regions. Figure 14 is a 200x EDS analysis of chlorine, and Figure 15 is an EDS analysis of sulfur. From the comparison of the two EDS diagrams, both chlorine and sulfur are found to be present in the same location in the poxy resin system. The chlorine comes from the novocytotoxicant, while the sulfur comes from the LP-32 polysulfide resin. Contains no tin It can be said that the formation of PCDs of an organic antifouling agent has been achieved. Here, this This formation is due to the selective formation of regions by the LP-32 polysulfide polymer, which selectively agglomerates together with the polysulfide polymer and the poison. FIG, 7 FIG, 2 FIG, 4 FIG, 7 FIG, 8 FIG, 9 FIG, 10 FIG, 11 FIG, 12 FIG, 13 FIG, 74 FIG, 15 Submission of translation of amendment (Article 184 of the Patent Law 8) November 8, 1993]

Claims (1)

[Claims] 1. Organic stain repellent free of thermoplastic or thermosetting binders, solvents, and tin In a tin-free curable marine antifouling composition containing a tin-free antifouling agent, The anti-static agent forms selectively concentrated areas in the cured composition. An antifouling composition for ships, characterized by: 2. the antifouling agent is greater than 200 mg/kg for rats or mice; A high LD50 value and a Z parameter of vinyl or aromatic compounds between about 0.01 and 0.08. consisting of water-insoluble compounds having an x value of between about 0.01 and 0.5 , the composition of claim 1. 3. Is the x value in the group consisting of sulfur, oxygen, nitrogen, halogens, and mixtures thereof? Claim 2 characterized by said antifouling agent containing a heteroatom selected from The composition described in . 4. The antifouling agent is a heterocyclic compound, an aromatic compound having a heteroatom substituent selected from the group consisting of compounds, amino compounds, and carbocyclic ketone vinyl ethers. 2. The composition of claim 1. 5. The aromatic compound having said heteroatom substituent is a mono-aromatic compound; aromatic ring compounds; and divalent heteroaromatic groups, dialkylene groups, or sigma bonds; selected from the group consisting of: a diaromatic compound bonded by a combination; and mixtures thereof , a composition according to claim 4. 6. The antifouling agent is 4-allyl-2-toxyphenol Diphenylacetonitrile 2,3-dichloro-1,4-naphthoquinone cetylpyridinium chloride diphenylamine Boric acid 2-Chloro-N,N-diallylahitamide cetyltrimethylammonium bromide 2-isopropylamino-4-chloro-6-ethylaminotriazine diphenyl Dimethoxythiophosphate derivative of sulfide ethyl 4-chloro-α (4-chloride) lorophenyl) α-hydroxybenzene acetate Methyldiethylamino, dimethoxythiophosphate derivative ethoxy of pyrimidine Nonylphenol silicide Asymmetric hydrazine derivatives of succinic acid Allyl, methyl hydroxy substitution of dimethylpropenylcyclopropanecarboxylic acid cyclopententone ester 2,5-dichloro,3-aminobenzoic acid cinnamic acid 2,6-dichloro,4-nitroaniline dichloro, isopropenylanilide Dodecylguanidine monoacetate trichlorophenylacetic acid Diphenyl ether of isobutyric acid ester of hydroxyacetonitrile, chlorophyllate phenyl derivative trihydroxybenzoic acid 3-indole acetic acid 3,5-dichloro-N-(3,3-dimethylpropyne)benzamide dimethylpho Sphoramide ammonium salt naphthalene acetamide Dimethylethylphenoxy-cyclohexyl-2-provinyl sulfite o-phenylphenol phthalic acid Chlorophenyl-isopropyl, provinyl carbamate N-phenyl, N-butyl Thinylchloroacetamide azacyclohexamine amino, chloro, phenyl Derivative N,N-diallyl-2-chloroacetamidomethylphosphonate amino Acetic acid derivative 3,5-dinitro,4-N,N-dipropylaminobenzenesulfone Amide 2-chloro-2-propenyldiethylcarbamodithioate and mixtures thereof 2. The composition of claim 1, wherein the composition is selected from the group consisting of: 7. The antifouling agent is Acrolein phenylhydrazone Alkyldimethylbenzenammonium saccharide 2,2-dimethyl-3-(2-methyl 2-allyl-4-hydroxy-3 of tilpropenylcyclopropanecarboxylic acid) -Methyl-2-cyclopentyn-1-one ester 4-allyl-2-methoxyphenol Methylcarbamate o-(allyloxy)phenyl 2-(allylthio)-2-thi Azoline 1,2,3,4,7,7-hexachloro-5,6-bis(chloromethyl)-2- norbornene 4-ethylamino-6-isopropylamino-2-methylthio-1,3,5-t riazin 2-amino-3-chloro-1,4-naphthoquinone 3-amino-5-nitro-o- Toluamide 3-amino-1,2,4-triazole ammonium sulfamate antimony potassium tartrate 2-Chloro-4-ethylamino-6-isopropylamino-S-triazine 4- Chloro-m-chlorocarbanilate 6-chloropiperonyl chrysanthemate N -butyl-N-ethyl-α,σ,α-trifluoro-2-6-dinitro-p-t louisine Bis(p-chlorophenyl)-3-pyridinemethanolbis(dialkylphosph) dinotioyl) disulfide bis(4-hydroxyiminomethylpyridinum-1) -methyl)ether dichloride 2,4-bis(3-methoxylpropylamino)-6-methylthio-S-tria gin Bis(pentachloro-2,4-cyclopentadien-1-yl)boric acid N-(4-bromo-3-chlorophenyl)-N'-methoxy-N'-methylurea 5-(bromomethyl)-1,2,3,4,7,7-hexachloro-2-norbol Nen N-(2-mercapto of S-(O,O-diisopropylphosphoro-dithionate) ethyl)benzenesulfonamidebenzamideoxy-acetic acid 3-benzylideneamino-4-phenylthiazoline-2-thione bis(p-chloro lophenoxy)methane Bis(4-chlorophenyl) disulfide 1,1-bis(p-chlorophenyl) Ethane 1,1-bis(p-chlorophenyl)-ethanolo,o-dimethyl-o -2,5-dichloro-4-bromophenylthionophosphate O,O-dimethyl-2,2,2-trichloro-1-n-butyryloxyethylpho Suphonate N-butylacetanilide 2-t-butylamino-4-chloro-6-ethylamino-5-triazine 2-t -butylamino-4-ethylamino-6methylmercapto-S-triazine 4-tert-butyl-2-chlorophenylmethylmethylphosphoramidite o-(4- t-Butyl-2-chlorophenyl) o-methylphosphoramidothionate 3,4-dihydro-2,2-dimethyl-4-oxo-1,2h-pyran-6-ka Butyl rubonate n-Butyl-9-hydroxyfluorene-(9)-carboxylate 2-(p- t-Butylphenoxy) cyclohexyl 2-provinyl sulfite 1-Butyn-3-yl N-trichloro-methylate m-chlorophenyl-carbamate ruthio-4-cyclohexene-1,2-docarboximide 1-Naphthyl n-methylcarbamate S-[[(p-chlorophenyl)thiol]methyl]O,O-diethylphosphoro dithioate 2-Chloro-N,N-diallyl-acetamidodiethyl-dithiocarbamic acid 2 -chloroallyl cetyldimethylethylammonium bromide cetylpyridinium chloride Tetrachloro-p-benzoquinone 2-chloro-4,6-bis(diethylamino)-s-triazine p-chloroben Zyl p-chlorophenyl sulfide 1,2,3,5,6,-7,8,8-octa Chloro-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamane chloride Tan Ethyl 4,4'-dichlorobenzilate 5-chloro-2-benzothiazolethio zinc salt p-chlorobenzyl p-fluorophenyl sulfide 1-chloro-N' -(3,4-dichlorophenyl)N,N-dimethylformamidine 4-chloro-3,5-dimethylphenoxy-ethanol 1,4-dichloro-2, 5-dimethoxybenzene 1-(chloro-2-norbornyl)-3,3-dimethyl Urea S-(p-chloro-α-phenylbenzyl)O,O-diethylphosphoroditi oate p-chlorophenyl ester carbamate N-3-chloro of benzene-sulfonic acid Lophenyl-1-(isopropyl-carbamoyl-1)-ethyl 3-(p-chlorophenyl)-5-methylrhodanine 4(and 6)-chloro-2 -Phenylphenol sodium salt p-chlorophenylphenyl sulfone 4-chlorophenyl 2,4,5-trichloro-phenylazosulfide N-(5 -chloro-5-thiazolyl)propionamide 2-[4-chloro-o-tolyl) oxy]propionanilide 2-chloro-1-(2,4,5-trichloro-phene) vinyl) vinyl dimethyl phosphate N'-(4-chlorophenoxy)phenyl N,N-dimethylurea N-(3-chlorophenoxy) Lophenyl) carbamate isopropyl oleate (ferric) cupric acid Copper 8-quinolinolate 2-(2,4-dihydroxyphenyl)-1-cyclohexene-1-carboxylic acid -β-Lactone-O-diethylphosphothioate 2-chloro-4-dimethylamine Nor-6-methylpyrimidine 3-(2-cyclopentyn-1-yl)-2-methyl -4-Oxo-2-cyclopenten-1-yl chrysantheminate α-cyclohe Xyl-α-phenyl-3-pyridyl-methanol, hydrochloride N'-cyclooct Chil-N,N-dimethylurea 3',4'-dichlorocyclopropanecarboxya Nilide 2,4-dichlorophenoxyacetic acid 2.4-d,α-chlorocrotyl ester 3,5-dimethyl-1,3,5,2H -tetrahydrothiadiazine-2-thione, tetrahydro-3,5-dimethyl -2H-1,3,5-thiadiazine-2-thione 4-(2,4-dichlorophenoxy)butyric acid 2,3,5,6-tetrachlorotele Dimethyldecyltriphenylphosphonium phthalate-bromochlorotriphenyl Stanate dehydroacetic acid (and its sodium salt) tris and bis(2,4 -dichlorophenoxyethyl)phosphite 2-methyl-thio-4-isopropyl Ruamino-6-methylamino-s-triazine N,N-diisopropylthiolcarbamate S-2,3-dichloroallyl 1, 3-Diaza-2,4-cyclopentadiene N,N-di-n-butyl-p-chloro Benzene-sulfonamide 3,6-dichloro-o-anisic acid O-(2-chloro-4-nitrophenyl)O,O-dimethylphosphorothioate 2,6-dichlorobenzonitrile 2,3-dichloro-1,4-naphthoquinone 1,3-bis(1-hydroxy-2, 2,3-Dichlorobenzyl (2,2-trichloroethyl)urea methylcarbamate (20%) and 3,4-dichlorobenzyl methylcarbamate (80%) 1,1-dichloro-2,2-bis(p-ethylphenyl)ethane 2,4-dichloro-2,2-bis(p-ethylphenyl)ethane rolo-6-(o-chloro-anilino)-s-triazine N-(dichlorofluoro methylthio)-N'N'-dimethyl-n-phenylsulfamide 4,4'-dichloro-N-methylbenzene-sulfanilide 2,3-dichloro- 2-Methylpropionate sodium salt 2,6-dichloro-4-nitroaniline 2 , 5-dichloro-3-nitrobenzoic acid 5,2'-dichloro-4'-nitrosali Silanilide ethanolamine salt 2',5'-dichloro-4'-nitrososalicylanilide 2,2'-dihydroxy C-5,5'-dichlorophenylmethane 1-(2,4-dichlorophenoxyacetate) (chill)-3,5-dimethylpyrazole N-3,4-dichlorophenylN'-5-chloro-2-(2-sodium sulfonate) 2,4-dichlorophenol-4-chlorophenoxy)phenylureabenzenesulfonic acid Lorophenyl ester 2,4-dichlorophenyl methanesulfonate 2,4-di Chlorophenyl 4-nitrophenyl ether 4-dichlorotetrahydrothiophene 1,1-dioxide 4,4'-dichloro-α-trichloromethylbenzhyde Dorol 3',4'-dichloro-2-methacrylanilide α-(diethoxyfluor) Sphinothioylthio) γ-butyrolactone O,O-diethyl s-carboethyl dimethyl phosphorothioate O,O-diethyl O-naphthylamide phosphorothio ate O,O-diethyl O-3,5,6-trichloro-2-pyridylphosphorothi Oate 2,2'-dihydroxy-3,5,3',5',4''-pentachlorotriphe Nylmethane 2''-sodium sulfonate O,O-diisopropyl s-diethyl Rudithiocarbamoyl phosphorodithioate 2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylic acid 2 ,4-dimethylbenzyl O,O-dimethyl-S-2-(acetylamino)-ethyldithiophosphate N-dimethylaminoscinamic acid 1,1-dimethyl-3-[3-(nt-butyl-carbamoyloxy)phenylene ] Urea O,O-dimethyl s-carboethoxymethyl phosphorothioate O,O-dimethy L-O-(3-chloro-4-nitrophenyl)phosphorothioate O,O-dimethyl-op-cyanophenylphosphorothioate o,o-dimethyl Ru-s-[5-ethoxy-1,3,4-thiadiazole-2(3H)-onyl- (3)-Methyl]phosphorodithioate N,N-dimethyl-N'-(2-methyl -4-chlorophenyl)-formamidine hydrochloride O,O-dimethyl o-(4-nitro-m-tolyl)phosphorothioate o,s- Dimethyltetrachlorothioterephthalate 4'-dimethyltriazenoacetani Ridodinitrocyclohexylphenol 2,4'-dinitro-4-trifluoromethyl diphenyl ether 2-(1-mer) (Tyl-n-heptyl)-4,6-dinitrophenylcrotonate N,N-dimethyl-2,2-diphenylacetamidodiphenylacetonitrile diphenylamine 2,6-dinitro-N,N-di-n-propyl-p-toluidine di-n-propyl -2,5-pyridine-dicarboxylate dibromide 1,1'-ethylene-2,2 '-Dipyridinium 2,3-dicyano-1,4-dithiaanthraquinone 2,3 -dicyano-1,4-dithia-anthraquinone 3-(3,4-dichlorophenyl )-1,1-dimethyl-urea n-dodecyl thiocyanate n-dodecylguanidine acetate Ethyl N,N-dipropylthiolcarbamate 2-(2,4,5-trichloro phenoxy)ethyl-2,2-dichloropropionate Ethoxymethylbis(p-chlorophenyl)carbinol 1,2-dihydro-6 -ethoxy-2,2,4-trimethylquinonethiolcarbamate-N, N-diisobutylethylenebis(dithiocarbamato)zinc 3-phenyl-1,1 -dimethylurea trichloroacetate dimethyl-ferric dithiocarbamate O,O-dimethyl S-(N-formyl-N-methylcarbamoyl-methyl)phos Holodithioate 2-formyl-4-chlorophenoxyacetic acid 3-furfuryl-2-methyl-4-o Xo-2-cyclopentin-1-yl chrysantheminate 2-heptadecyl-2-imidazoline 7-chloro-4,6-dimethoxycoumaran-3-one-2-spiro-1'-( 2'-methoxy-6'-methylcyclohex-2'-en-4'-one) 1,1 ,1,3,3,3,-hexachloro-2-propanone 1,5a,6,9,9a, 9b-hexahydro-4a(4H)-dibenzofuran-carboxaldehyde 9-(p-n-hexyloxyphenyl)-10-methyl-acridinium chloride 2-Hydroxymethyl-4-chloro-phenoxyacetic acid N-hydroxy-methyl- 2,6-dichlorothiobenzamide N-phenylcarbamic acid isopropylthio Isobornyl cyanoacetate Isobutyltriphenylmethylamine 5-bromo-3-isopropyl-6-methyluracilisopropyl-4,4'- Isopropyl dibromobenzilate 4,4'-dichlorobenzilate isopropyl Lumercaptophenyl-acetate, O,O-dimethylphosphorodithioate 3-cyclohexyl-6,7-dihydro-1H-cyclopentapyrimidine-2, 4(3H,5H)-dione 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea S-[1, 2-bis(ethoxy-carbonyl)ethyl]O,O-dimethylphosphorodithioe root Ethylenebisdithiocarbamate manganese 4-chloro-2-methylphenoxy vinegar acid 2-(4-chloro-2-methylphenoxy)propionic acid 4(or 5)-chloride sec-butyl lolo-2-methylcyclohexanecarboxylate s-[(4,6-diamino-s-triazin-2-yl)methyl]O,O-dimethyl Tylphosphorodithioate 2-isopropylamino-4-(3-methoxypropylamino)-6-methylthi auto-s-triazine 1,1,1-trichloro-2,2-bis(p-methoxyphenyl)ethane 2-methane Toxy-4-isopropylamino-6-diethylamino-s-triaS-(N- Methoxymethylcarbamoylmethyl)dimethylphosphorothiolothiononate 3-(dimethoxy-phosphinyloxy)-cis-crotonic acid α-methylbenzi le Methyl-carbamic acid m-(1-methylbutyl)phenylmethyl-2-chloro- 9-Hydroxyfluorene-(9)-carboxylate 3,3'-methylenebis(4-hydroxycoumarin)2,2'-methylenebis (3,4,6-trichlorophenol)6-methyl-2-oxo-1,3-dithi O(4,5-b)quinosaline O,O-dimethyl S-(2,5-dichlorophenyl -thio)-methylphosphorodithioate 3(2-methylpiperidino)propyl-3,4-dichlorobenzoate 4-(meth) (tylsulfonyl)-2,6-dinitro-n,n-dipropylanilimethyl-2, 3,5,6-tetrachloro-n-methoxy-n-methylterephthalamate O-methyl O-(2,4,5-trichloro-phenyl)amide phosphorothiome to 3-(p-bromophenyl)-1-methyl-1-methoxyurea 1,2-dihydro Pyridazine-3,6-dione 3,3'-ethylenebis-(tetrahydro-4,6 -dimethyl-2H-1,3,5-thiadiazone-2-thione) S-Ethylhexahydro-1H-azevin-1-carbothioate 3-(p-k chlorophenyl)-1,1-dimethylurea trichloroacetic acid 3-(p-chlorophenyl) )-1,1-dimethylurea disodium ethylene bisdithiocarbamate 1, 2-dibromo-2,2-dichloroethyldimethylphosphate β-naphthoxy vinegar acid 3-(3,4-dichlorophenyl)-1-methyl-1-n-butylurea 3-(h (xahydro-4,7-methanoindan-5-yl)-1,1-dimethylurea N-1-naphthyl-phthalamic acid p-chlorophenyl p-phenyl 4-chlorobenzenesulfonate S-propyl Butyl-ethylthiocarbamate phenothiazine Ethyl mercapto phenyl acetate O. O-dimethyl-phosphorodithioate to n-phenyl-1-(ethylcarbamoyl-1)ethylcarbamate (d isomer ) Phosphoric acid, 2-chloro-1-(2,4,5-trichlorophenyl)bierdimethyl ester 4-amino-3,5,6-trichloropicolinate piperonyl-bis(2-[2' -n-butoxyethoxy]ethyl)acetal piperonyl butoxide α[2-(2-n-butoxyethoxy)-ethoxy]4, 5-methylenedioxy-2-propyltoluenepiperonylcyclonene Polychlorobenzoic acid, dimethylamine salt 2,4-bis-(isopropylamino) -6-Methoxy-s-triazine 2-methyl-mercapto-4,6-bis(iso propylamino)-s-triazine 2-Chloro-n-isopropylacetanilide 3',4'-dichloropropiona lido 2-chloro-4,6-bis(isopropyl-amino)-s-triazinedi-n- Propyl-3-methyl-6,7-methylenedioxy-1,2,3,4-tetler Hydronaphthalene-1,2-dicarboxylate 5-amino-4-chloro-2- Phenyl-3(2H)pyridazinone pyrethrin I 8-quinolinol Dimethyl 2,4,5-trichlorophenylphosphorothionate salicylanilide 1-(3,4-methylene-dioxyphenoxy)-3,6,9-trioxoun decan Sodium 2-(2,4-dichlorophenoxy)ethyl sulfate 1-(2- Methyl-cyclohexyl)-3-phenylurea 1-(2,4,5-trichloroph) (enoxy)propionic acid N'-chloro-2-methyl-p-valerotoluidide 1, 2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benze hmm Methyl 3,4-chlorocarbanilate 2,4,5-Trichlorophenoxyacetate trichlorobenzyl chloride 2,2-bis(p-chlorophenyl)-1,1-dichloroethaneethylene-1, 2-bis(thiocarbamoyldimethylthio-carbamoyl disulfide) 3-t-butyl-5-chloro-6-methyluracil 2,6-di-t-butyl-p -Tolylmethylcarbamate 2,3,6,7-tetrachloro-4a,8a-e Poxy-1,2,3,4,4a,8a-hexahydro-1,4-methanonaphthalene N-5,8-dione N-(1,1,2,2-tetrachloro-ethyl-sulfenyl )-cis-α-4-cyclohexene-1,2-dicarboximide 2,4,5 ,6-tetrachloroiso-phthalonitrile 1,2,4,5-tetrachloro-3- Nitrobenzene p-chlorophenyl 2,4,5-trichlorophenylsulfone Chylcarbamate 5,6,7,8-tetrahydro-1-naphthyl 3,4,5,6 -tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylprope cyclopropanecarboxylate O, O, O', O'-tetramethyl O, O'-thiodi-p-phenylene phosphorothioate 1,3,6,8-tetranitrocarbazole 2-(4-thiazolyl)benzimine Dazole 2,2'-thiobis(4,6-dichlorophenol)2-thiocyanoe Chilledodecanoate 2,3-quinosaline-dithiol cyclic trithiocarbonate tetramethy ruthiuram disulfide N-Meta-tolylphthalamic acid N,N-di-isopropyl-thiolcarbamate S-2,3,3-trichloro allyl O,O-dimethyl(1-hydroxy-2,2,2-trichloroethyl)phosphone root 2,3,6-trichlorobenzoic acid Trichlorobenzoic acid, dimethylamine salt 4,5,7-trichlorobenzthiasia Sol-2,1,32,3,6-trichlorobenzyloxypropanol N-t Lichloromethylthio-benzothiazolone N-trichloromethylthiobenzoxazo 2,2,2-trichloro-n-(pentachloro-phenyl)acetoimi chloride Drill 2-(2,4,5-trichlorophenoxy)ethyl sulfate, sodium salt N,N'-N''-trichloro-2,4,6-triamine-1,3,5-triamine gin 2-chloro-4-(di-ethylamino)-6-(ethylamino)-s-triazid hmm t-Butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate S-Propyldipropylthiocarbamate Zinc ethylenebisdithiocarbamate Zinc dimethyldithiocarbamate 3,5-dinitro-o-toluamide 2. The composition of claim 1, selected from the group consisting of: and mixtures thereof. 8. The antifouling agent is a reactive compound that reacts with monomers, oligomers, or polymers. The resulting product has a functional group that can be selected in the cured composition. 2. The composition of claim 1, wherein the composition forms a region of high concentration. 9. The monomer, oligomer, or polymer may contain nitrogen, sulfur, or both. 9. The composition of claim 8 containing a heteroatom substituent selected from the group consisting of thing. 10. 2. The composition of claim 1, comprising a film-forming coating composition. 11. The antifouling agent is a reactive compound that reacts with monomers, oligomers, or polymers. The resulting product contains selective functional groups in the cured composition. 7. The composition of claim 6, which forms selectively enriched regions. 12. The antifouling agent is a reactive compound that reacts with monomers, oligomers, or polymers. The resulting product contains selective functional groups in the cured composition. 8. The composition of claim 7, which forms selectively enriched regions. 13. The composition further comprises: forming discontinuous regions in the cured composition; the compound region is a selectively concentrated region of the antifouling agent. The composition according to claim 1, which is in the same area as . 14. Said region is between about 0.3 and 500 micrometers in size. The composition according to claim 1. 15. Organic stain repellent free of thermoplastic or thermosetting binders, solvents, and tin A method for formulating a tin-free curable marine antifouling composition containing a tin-containing agent wherein the antifouling agent is selectively concentrated in the cured composition. A method for formulating an antifouling composition, characterized in that it is supplied in the form of. 16. The antifouling agent is a reactive compound that reacts with monomers, oligomers, or polymers. The resulting product contains selective functional groups in the cured composition. 16. The method of claim 15, forming selectively enriched regions. 17. The composition further comprises: forming discontinuous regions in the cured composition; the compound region is a selectively concentrated region of the antifouling agent. 16. The method according to claim 15, wherein the method is the same area as .