JPS6361990B2 - - Google Patents

Description

[Detailed description of the invention] The present invention

[Formula] The active ingredient is a thiocarbamic acid derivative having a group, an organotin compound, and an organic or inorganic cuprous or cupric compound having a solubility in seawater from 0.0001 ppm to 10% at 25°C and 1 atm. The present invention relates to a composition for preventing the adhesion of marine organisms as a stain paint or an antifouling agent for fishing nets. Marine infestations such as barnacles, Kanthorn, Memboranipora, Sarcoptera, mussels, and sea squirts can be found on the bottoms and water lines of ships, on the inside surfaces of seawater intakes and cooling pipes in thermal or nuclear power plants, and on the surfaces of brine aquaculture facilities and aquaculture nets. Persistent animals and marine periphyton plants such as green laver, sea lettuce, and sea cucumber adhere to ships, causing damage such as reducing ship speed, reducing water absorption capacity, and slowing the growth of farmed fish. In order to prevent these damages, antifouling paints containing cuprous oxide, organic tin compounds, organic tin polymers, thiocarbamates, etc. as antifouling agents have been devised and used. These antifouling paints are sufficiently effective against sessile organisms that can be observed with the naked eye, such as the marine sessile animals and marine sessile plants that grow from a few millimeters to several tens of centimeters, and are widely used. It is put into practical use. However, recently, Achromobacter species, whose adult individuals are difficult to detect with the naked eye, have been introduced.
SP.), Bacillus subtilis
subtillis), Micrococcus sp.
SP.), Pseudomonas sp.
Marine bacteria such as Caulobacter SP., Saprospira SP., Sarcina SP., Flavobacterium SP.; Aspergillus SP. , Nigrospora sp., Penicillium sp.; Navicula sp., Melosira sp.
SP.), Nitzschia SP., Licmophora SP., Biddulphia SP., Thalassionema SP., Achnanthes SP., Asteromphalus sp. SP.), Diatoma SP., Phabdonema SP., Synedra SP.
There has been a growing demand for prevention of so-called marine microorganisms such as marine diatoms such as SP.), but no effective prevention technology has yet been established. The first stage of fouling by marine sessile organisms is the adhesion of these marine microorganisms, followed by the adhesion of larvae and larvae of large sessile organisms as the second stage. Preventing this will also prevent the subsequent adhesion of fouling organisms, making complete antifouling possible, but originally,
Marine microorganisms such as marine bacteria, marine molds, and marine diatoms have a much stronger resistance to various chemical substances than the larvae and larvae of barnacles, snail beetles, and blue laver, so they have traditionally been The antifouling paints were unable to prevent the adhesion of these marine microorganisms. The adhesion of these marine bacteria, marine molds, marine diatoms, etc. increases the frictional resistance on the hull surface, causes excessive fuel consumption, and increases the operating costs of the vessel. For power plant cooling water systems, the adhesion of these marine microorganisms reduces the heat exchange efficiency of heat exchangers. In addition, when these substances adhere to the net threads of aquaculture nets, the inflow and outflow of seawater into the aquaculture nets becomes poor, causing many problems such as slowing down the growth of fish due to a lack of oxygen. The present inventors previously filed an application for the use of cuprous substituted alkylene bisdithiocarbamic acid metal salts in antifouling paints, and disclosed the invention in Japanese Patent Publication No. 13976/1983. However, in the invention, it was clear that the compound was effective against so-called marine sessile organisms such as barnacles, staghorn beetles, and snail beetles.
Marine bacteria found in the early stages of fouling,
There was no knowledge that it was effective against marine molds and marine diatoms, and the technology available at the time was not able to prevent these attached microorganisms. In addition, the technology for using organic tin compounds in antifouling paints was published in Tokoku No. 40-21426, Tokoku No. 9579, Tok.
No. 46-13392, Special Publication No. 49-20491, Special Publication No. 1971-
No. 11647 and Japanese Patent Publication No. 52-48170, these inventions also show effective methods for preventing marine sessile organisms, but they do not claim to be particularly effective in preventing marine sessile microorganisms. It has not been. Furthermore, an aquatic organism repellent using a combination of a dithiocarbamate compound and an organotin compound is disclosed in JP-A No. 157824/1985, which also kills sessile flora and fauna such as barnacles, mussels, Ulva, and Shiomiduro. There is no knowledge that it is effective against marine adhering microorganisms. In response to this current situation, the present inventors have intensively researched the ecology of marine adhesion microorganisms such as marine bacteria, marine molds, and marine diatoms, and the mechanism of initial adhesion fouling. B and component C
It has been discovered that a composition for preventing the adhesion of marine organisms containing one or more of the following as active ingredients is extremely effective in preventing the adhesion of marine microorganisms, which is the initial stage of underwater fouling. That is, the present invention includes component A and component B shown below.
and Component C as active ingredients. Component A is

[Formula] Dithioka having a group Rubamic acid derivative. Component B is 1) General formula (1)

【formula】 and/or

[In the formula, R represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a cycloalkyl group, and X and Y represent a hydrogen atom or a methyl group. ]

Organotin-containing repeating unit (a) or (a)
and at least one monomer unit (b) selected from the group consisting of acrylic compounds and vinyl hydrocarbons, and/or 2) an organotin-containing polymer having general formula (2) R′ ₃ S _o Z or (R′ _{3 So} ) ₂ W …(2) [In the formula, R′ is an alkyl group, phenyl group, or cycloalkyl group, and Z is a halogen group or an ester group,
W is an acyl group, a monovalent characteristic group containing sulfur, a monovalent characteristic group containing oxygen, or an acyl group partially substituted with halogen, and W is a divalent characteristic group containing oxygen or a divalent characteristic group containing sulfur. shows. Note that Z and W were expressed according to the organic compound nomenclature according to IUPAC rules. That is, among Z, the monovalent characteristic group containing sulfur is methylthio, ethylthio, phenylthio, etc., and the monovalent characteristic group containing oxygen is hydroxy. Further, among W, a divalent characteristic group containing oxygen represents oxy, and a divalent characteristic group containing sulfur represents thio, sulfonyl, etc. ] An organotin compound that is a simple organotin compound represented by Component C is from 0.0001ppm at 25℃ and 1 atm.
It is an organic or inorganic cuprous or cupric compound having a solubility in seawater of up to 10%, and each of the three components is used alone or in combination of two or more. One of the active ingredients of the present invention

[Formula] Examples of dithiocarbamic acid derivatives having a group include the following.

Dithiocarbamate represented by the formula, [R'' is hydrogen, methyl, ethyl, propyl, butyl, phenyl, morpholine, piperazyl, etc. in which R'' and R'' are connected, M is Zn, Ni, Mn,
It represents Cu, Co, Pb, Fe, Sn, Ag, Hg, etc., and n represents the valence of M. ]

[A and M are the same as and may be one or more types]

A dithiocarbamic acid metal salt represented by [In the formula, R'', A, and M are the same as, a is 1 to 10
represents an integer. ]

Chiura shown by [formula] Mugisulfide. [R″ is the same as]

[R″ is the same as]

Further, compounds are illustrated to specifically explain the dithiocarbamic acid derivative of the present invention, but this is not intended to limit the scope of the present invention. As a group, as a group As a group, As a group, As a group, As a group, Production examples 2 and 3 of these components A are shown below. Production Example 1 First ethylene bisdithiocarbamate zinc salt
Copper Substituted Product Dissolve 1 mol of ethylene bisdithiocarbamate sodium salt in 5 water, dropwise add 1 mol zinc sulfate aqueous solution while stirring at room temperature, and then 6.4
g of cuprous chloride and 100 g of ammonium chloride were added and stirred, and the resulting precipitate was overdried to obtain 210 g of a cuprous substituted zinc salt of ethylene bisdithiocarbamate as a yellow solid. Production Example 2 Cuprous substituted product of zinc/nickel salt of ethylene/1,2-propylene bisdithiocarbamate 1 mole of potassium ethylene bisdithiocarbamate salt and 1 mole of potassium salt of 1,2-propylene bisdithiocarbamate were dissolved in 10 parts of water. 1.67 mol of zinc sulfate and 0.33 mol of nickel sulfate aqueous solution are added dropwise while stirring. Then, 9.4 g of cuprous chloride was added and stirred, and the resulting precipitate was overdried to obtain 510 g of a dark brown solid of the cuprous substituted ethylene/1,2-propylene bisdithiocarbamate zinc/nickel salt. obtain. Production Example 3 Cuprous salt of 1,2-n-butylene bisdithiocarbamate Dissolve 0.1 mol of ammonium salt of 1,2-n-butylene bisdithiocarbamate in 500 ml of water,
The precipitate obtained by adding 20 g of cuprous chloride is overdried to obtain 32 g of 1,2-n-butylene bisdithiocarbamic acid ammonium salt as a brown solid. In the organotin-containing polymer in component B, which is one of the active ingredients of the present invention, the triorganotin compound represented by (1)- in general formula (1) includes, for example, bis(tributyltin) malate, Bis(tricyclohexyltin) malate, bis(triphenyltin) maleate, bis(tributyltin) fumarate, bis(tricyclohexyltin) fumarate, bis(triphenyltin) fumarate, bis(tributyltin) citraconate, bis(tricyclohexyltin) Typical examples include citraconate, bis(triphenyltin) citraconate, bis(tributyltin) mesaconate, bis(tricyclohexyltin) mesaconate, and bis(triphenyltin) mesaconate. Typical examples of the organic tin compound include tributyltin methacrylate, tributyltin acrylate, tricyclohexyltin methacrylate, tricyclohexyltin acrylate, triphenyltin methacrylate, and triphenyltin acrylate. These compounds may be used alone or in combination of two or more. Examples of acrylic compounds, functional group-containing vinyl compounds, and vinyl hydrocarbon monomers that can be copolymerized with these triorganotin compounds include methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, ethyl acrylate, Acrylic compounds such as butyl acrylate, octyl acrylate, dodecyl acrylate, cyclohexyl acrylate, phenyl acrylate, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl butyrate, butyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, lauryl Examples include vinyl compounds having a functional group such as vinyl ether, and vinyl hydrocarbons such as ethylene, butadiene, and styrene. These monomers may be used alone or in combination of two or more. Examples of the organic tin element represented by the general formula (2) in component B of the present invention include tributyltin fluoride, tripropyltin chloride, triamyltin acetate, triphenyltin fluoride, bistriphenyltin α,α′-dibromo succinate,
Triphenyltin dimethyl dithiocarbamate, triphenyltin chloride, triphenyltin unitinate, triphenyltin versatate, tricyclohexyltin monochloroacetate, bis(tributyltin) oxide, bis(triphenyltin)
Examples include bis(tricyclohexyltin) sulfide, bis(tri-2-ethylbutyltin) oxide, and bis(tri-sec-butyltin) oxide. Component C, which is one of the active ingredients of the present invention, is heated at 25°C.
Organic and inorganic cuprous or cupric compounds having a solubility in seawater from 0.0001 ppm to 10% by weight at 1 atm, such as basic copper carbonate, cupric chromate, cupric citrate, ferocyanide. Cupric acid, cupric fluoride, cupric hydroxide, cupric quinoline, copper 8-hydroquinoline, cupric oleate, cupric oxalate, cupric oxide, cupric phosphate , cupric stearate, cupric sulfide, cupric tartrate, cupric tungstate, cuprous bromide, cuprous iodide, cuprous oxide, cuprous sulfide, cuprous sulfite, These include cuprous thiocyanate and copper naphthenate, and these copper compounds can be used alone or in combination of two or more. The proportion of component A in the composition of the present invention is 60% by weight or less, preferably 50% to 0.1% by weight, and the proportion of component B is 80% by weight or less, preferably
70% to 1% by weight, and the proportion of component C is up to 60% by weight, preferably from 50% to 1% by weight. If these upper limits are exceeded, the coating operation of the composition will be hindered, and if it is below the lower limits, the effect against marine microorganisms will be significantly reduced. The compositions of the present invention include organic or inorganic colored pigments such as titanium oxide, iron oxide, carbon black, cyanine blue, cyanine green, carmine, yellow lead, thiazole dyes, azo dyes, carbonium dyes, acridine dyes, and nitroso dyes. , indigoid dyes, anthraquinone dyes and other dyes,
Extending pigments such as talc, mica, calcium carbonate, magnesium carbonate, anti-settling agents, anti-sagging agents,
Additives such as leveling agents, color separation prevention agents, and ultraviolet absorbers can be used together. Other known antifouling agents may be added to the compositions of the present invention, such as benzene hexachloride, chlorine compounds such as 2,4 dichlorophenoxyacetic acid, 2-methylthio-4
-isopropylamino-6-ethylamino-S-
Triazine, 2-methylthio-4,6-bisethylamino-S-triazine, 2-methylthio-4
-Isopropylamino-6-methylamino-S-
Triazine compounds such as triazine, diethyl-
A phosphide such as P-nitro-m-tolyl-phosfluorothionate and dimethyl-S-(N-methylcarbamoylmethyl)phosfluorothiorothionate can be used in combination. In the composition of the present invention, natural resins such as rosin, silica gum, and ester gum, and processed resins or synthetic resins such as alkyd resins, acrylic resins, vinyl resins, epoxy resins, and chlorinated rubber resins can be used in combination. Solvents used in the compositions of the present invention include mineral spirits, solvent naphtha, toluene,
Optionally, one or more of ordinary organic solvents such as hydrocarbons such as xylene, ketones such as methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and alcohols such as n-butanol and isopropyl alcohol are optionally used. used. Next, examples of the present invention will be shown together with comparative examples, and their effects will be explained. Parts in Examples and Comparative Examples represent parts by weight. Production of antifouling paints and fishing net antifouling agents The antifouling paints of Examples were manufactured by charging raw materials into steel receivers and dispersing them with a dissolver based on the formulations shown in Tables 1-1 to 1-4. The properties of the obtained paint are shown in Tables 1-1 to 1-4. The antifouling paints of Comparative Examples were manufactured by charging raw materials into steel receivers, roughening them with a dissolver, and dispersing them with a sand grinder based on the formulations shown in Tables 1-5 and 1-6. The properties of the obtained paint are shown in Tables 5 and 6. The fishing net antifouling agents of Examples and Comparative Examples are shown in Table 1-
2. Based on the formulations shown in Tables 1-4 and 1-6, feed the raw materials into a steel receiver,
It was manufactured by dispersing and dissolving it using a high-speed dissolver. The properties of the obtained antifouling agents are shown in Tables 1-2, 1-4, and 1-6.

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[Table] Performance of coating and coating film 100 mm x 200 mm coated with the antifouling paints of Examples 1 to 6, Examples 8 to 18, Example 20, and Comparative Examples 1 to 9 with vinyl chloride resin rust prevention paint four times ×0.8
The total dry film thickness of the antifouling paint was
It was set to 100μ to 120μ. These test pieces were immersed in the sea from a test raft, and the adhesion area ratio of marine animals and plants and the adhesion area ratio of marine microorganisms were investigated over 24 months. The results were as shown in Table 2-1 and Table 2-2. In Table 2-1 and Table 2-2, the evaluation values for marine animals and plants are based on the front and back areas of the test piece being taken as 100, such as barnacles, snails, bulrushes, snails, memboranivora, sea squirts, mussels, sponges, etc. It represents the percentage of area covered by marine animals and marine plants such as blue laver, sea lettuce, seaweed, and kelp. Furthermore, the evaluation value for marine microorganisms represents the percentage of the area covered by marine microorganisms such as marine bacteria, marine molds, and marine diatoms as seen with the naked eye. * indicates that it was impossible to evaluate marine microorganisms because the area covered by marine animals and plants was large. Table 3-1 and Table 3-2 show the results of examining the types of marine microorganisms that adhered to the surface of the test piece after 12 months. Table 3-1 and Table 3-2 Evaluation values for marine bacteria and mold are determined by culturing a certain amount of the sample taken from the surface of the test piece using a conventional method, and determining the species and the degree of reproduction based on the condition of the colony. , evaluated on a five-point scale. To evaluate marine diatoms, a certain amount of the collected sample was placed under a 600x microscope to determine the species, the number of individuals within the field of view was counted, and the degree of reproduction was evaluated on a five-point scale. The number of evaluations is as follows. 5; There is no reproduction at all, and no individuals can be detected. 4; Reproduction is slight, and the number of individuals detected is less than 100 per ^cm2 . 3; Reproduction is moderate, and the number of individuals detected is 100 to 1000 per ^cm2 . 2; Reproduction is quite remarkable, and the number of individuals detected is 1,000 to 100,000 ^per cm2. 1; Reproduction is extremely rapid, and the number of detected individuals is over 100,000 ^per cm2.

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[Table] Regarding the fishing net antifouling agents of Examples 7 and 19 and Comparative Example 10, 30cm x 100cm polyethylene, 32 pieces,
Seven-node knotless nets were immersed in each antifouling agent for 3 minutes, pulled out, air-dried, and then immersed in the sea to examine the adhesion of marine animals and plants and marine microorganisms over a 12-month period. The results are shown in Table 4. The evaluation values in Table 4 represent the percentage of the area covered by marine animals and plants or marine microorganisms, when the area of the test net is taken as 100. Table 5 shows the type and amount of marine microorganisms that adhered to the test net after 6 months. The evaluation values in Table 5 are Examples 1 to 6, Examples 8 to 18, Example 20, and Comparative Example. This is the same as the evaluation used in 1 to 9.

【table】

[Table] As explained in detail above, the composition for preventing the adhesion of marine organisms of the present invention has excellent antifouling properties against marine microorganisms compared to conventional antifouling paints and fishing net antifouling agents. It is clear that it has excellent long-term antifouling performance as an inhibitor.

Claims (1)

[Scope of Claims] 1. A composition for preventing adhesion of marine organisms, characterized by containing component A, component B, and component C shown below as active ingredients. Component A is a dithiocarbamic acid derivative having a group [formula]. Component B is 1) General formula (1) [Formula] and/or [Formula] [In the formula, R is an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a cycloalkyl group, and X and Y are a hydrogen atom or Indicates a methyl group. ] Organotin-containing repeating unit (a) or (a) represented by
and at least one monomer unit (b) selected from the group consisting of acrylic compounds and vinyl hydrocarbons, and/or 2) an organotin-containing polymer having general formula (2) R′ ₃ S _o Z or (R′ _{3 So} ) ₂ W …(2) [In the formula, R′ is an alkyl group, phenyl group, or cycloalkyl group, and Z is a halogen group or an ester group,
W is an acyl group, a monovalent characteristic group containing sulfur, a monovalent characteristic group containing oxygen, or an acyl group partially substituted with halogen, and W is a divalent characteristic group containing oxygen or a divalent characteristic group containing sulfur. shows. ] An organotin compound that is a simple organotin compound represented by Component C is from 0.0001ppm at 25℃ and 1 atm.
Organic and inorganic cuprous or cupric compounds with a solubility in seawater of up to 10%.