CN103080249A - Antifouling coating composition, copolymer for antifouling coating composition, and coated article having surface that is provided with antifouling coating film which is formed using the composition - Google Patents
Antifouling coating composition, copolymer for antifouling coating composition, and coated article having surface that is provided with antifouling coating film which is formed using the composition Download PDFInfo
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- CN103080249A CN103080249A CN2011800405318A CN201180040531A CN103080249A CN 103080249 A CN103080249 A CN 103080249A CN 2011800405318 A CN2011800405318 A CN 2011800405318A CN 201180040531 A CN201180040531 A CN 201180040531A CN 103080249 A CN103080249 A CN 103080249A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
Abstract
Provided is an antifouling coating composition which has excellent long-term storage stability. Also provided is a copolymer having a specific structure, which is used in order to form an antifouling coating film that has high environmental safety and is capable of maintaining stable coating film solubility and antifouling performance without causing coating film defects such as cracks in seawater for a long period of time. The present invention specifically provides an antifouling coating composition, which contains a copolymer (A) that is obtained by copolymerizing 55-80% by mass of a t-butyldiphenylsilyl acrylate monomer (a) and 20-45% by mass of an ethylenically unsaturated monomer (b) other than the monomer (a), and wherein the monomer (b) is composed of at least one kind of monomer that is selected from the group consisting of methyl methacrylate, butyl (meth)acrylate and 2-methoxyethyl (meth)acrylate.
Description
[technical field]
The present invention relates to antifouling paint compositions, antifouling paint compositions have the antifouling coat that uses said composition formation with multipolymer, surface coated article.
[background technology]
Because the aquatic fouling organisms such as barnacle, imperial cyprid, Mytilus edulis, careless tongue worm, Ascidian, intestines Enteromorpha, sea lettuce, biological clay are attached in the water such as fishery apparatus, power house water pipe such as boats and ships (especially bottom of ship), fishing net class, fishing net accessory on the structures, the problem that exist the function of above-mentioned boats and ships etc. to be hindered, outward appearance suffers damage etc.
After the use of the organic stanniferous multipolymer that in the past used is forbidden, develop low and few to the load of the environment multipolymer that contains three Organosilyls (trisorganosilyl group) of toxicity, and be used for antifouling paint.
As the above-mentioned multipolymer that contains three Organosilyls, when using such the making of multipolymer that contains three normal-butyl silicomethane esters to contain the multipolymer that alkyl forms as the monomer copolymerization of the silicomethane ester of straight chain shape, because the hydrolysis rate of filming is very fast and water tolerance is also poor, has the problem (patent documentation 3) that is difficult to control the dissolution rate of filming.
In addition, as the above-mentioned multipolymer that contains three Organosilyls, when such the making of multipolymer that use contains triisopropyl silicomethane ester contains the multipolymer that alkyl forms for the monomer copolymerization of three organic silicomethane esters of a chain, although the starting stage dissolves with certain speed in seawater, but the dissolution rate of filming increases gradually, excessively increase through the dissolution rate of then filming for a long time, have the problem of coating difficult design.And, in seawater, passed through for a long time and filmed, cause that sometimes crackle etc. films unusual.And, for the coating of the multipolymer that contains triisopropyl silicomethane ester group, because the water that produces in the moisture that in starting material etc., contains in order to make coating or the manufacturing processed at coating, resinous principle is hydrolyzed easily in coating is preserved, and has the multiviscosisty of bringing out coating, aging etc. problem.In order to address this problem, proposed to cooperate the scheme of dewatering agent etc.But, although utilize dewatering agent to play certain effect, be not fully to solve, worry multiviscosisty, aging etc. in the prolonged preservation.And, also must be noted that moisture for raw-material operation, there is the poor problem of operation efficiency (patent documentation 1,2,4～7).
In addition, as the above-mentioned multipolymer that contains three organic silicomethane ester groups, also proposed to use the scheme of methacrylic acid tert-butyl diphenyl silicomethane ester copolymer, but because the dissolution rate of filming in the seawater is too small, can't obtain desired anti-fouling effect, and hardness of film excessively uprises, exist bad to the tackiness of structures in the water, cause the unusual problems of filming (patent documentation 1,2,4～7) such as crackle.
Like this, at present not the seawater midium or long term do not crack wait film unusual, continue appropriate water-disintegrable and antifouling paint compositions that long-term storing stability is good.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese kokai publication hei 7-102193 communique
[patent documentation 2] Japanese kokai publication hei 8-269390 communique
[patent documentation 3] Japanese kokai publication hei 9-194790 communique
[patent documentation 4] Japanese kokai publication hei 10-30071 communique
[patent documentation 5] TOHKEMY 2001-226440 communique
[patent documentation 6] TOHKEMY 2003-261816 communique
[patent documentation 7] TOHKEMY 2005-082725 communique
[summary of the invention]
[inventing problem to be solved]
Problem of the present invention is, provide long-term storing stability good antifouling paint compositions, and be provided for being formed on the seawater midium or long term the film unusual phenomenon and can keep the multipolymer with ad hoc structure of the stable high antifouling coat of solvability and antifouling property and environmental safety of filming such as crackle does not occur.
[technique means of dealing with problems]
According to the present invention, a kind of antifouling paint compositions is provided, contain the copolymer A by ethylene unsaturated monomer (b) 20～45 quality % copolymerization in addition of vinylformic acid tert-butyl diphenyl silicomethane ester monomer (a) 55～80 quality % and above-mentioned monomer (a) are obtained, above-mentioned monomer (b) is for to be selected from by at least a monomer in the group that methyl methacrylate, (methyl) butyl acrylate and (methyl) vinylformic acid-2-methoxyl group ethyl ester forms.
That the antifouling coat that uses the antifouling paint contain methacrylic acid tert-butyl diphenyl silicomethane ester copolymer to form has in order to solve, to the tackiness of structures in the water the unusual problem of filming such as bad and crackle, the inventor expects adopting the higher acrylate of flexibility to replace methacrylic ester.Therefore, use the antifouling paint that contains vinylformic acid tert-butyl diphenyl silicomethane ester copolymer to form antifouling coat, it is carried out performance evaluation.The result obtains very good result in tack test and pliability test.In addition, even to observing through the membrane stage that is coated with after long-time, do not find the unusual phenomenoies of filming such as crackle yet, by adopting acrylate to replace methacrylic ester, solved a plurality of problems that methacrylic acid tert-butyl diphenyl silicomethane ester copolymer has as can be known.
Yet the antifouling coat that use is contained the antifouling paint formation of vinylformic acid tert-butyl diphenyl silicomethane ester copolymer further studies rear discovery in great detail, and there is the problem that within a short period of time, antifouling property reduced in this antifouling coat.Do not recognize the problems referred to above, the reason that antifouling property reduces it be unclear that in the past.
In order to solve this problem, the inventor conducts in-depth research, the ratio that found that the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is closely related with long-term antifouling property, and find that the ratio by making the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is more than the 55 quality %, holding time of antifouling property significantly improves.55 quality % can access good like this effect when above reason still imperfectly understands.The dissolution rate of filming is tested rear discovery, the ratio of vinylformic acid tert-butyl diphenyl silicomethane ester is in the above situation of 55 quality %, and the dissolution rate of filming is long-term to keep certain, relative therewith, be that the dissolution rate of filming is passed in time and reduced in the following situation of 54 quality %.Foregoing provides following enlightenment, for vinylformic acid tert-butyl diphenyl silicomethane ester copolymer stably is hydrolyzed, must make the ratio of the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is more than the 55 quality %, the hydrolysis rate of vinylformic acid tert-butyl diphenyl silicomethane ester copolymer is unstable in than the low situation of this ratio, and antifouling property reduces within a short period of time as a result.
In addition, how the inventor can change the performance of antifouling coat in the situation of the ratio of the vinylformic acid tert-butyl diphenyl silicomethane ester in the further raising multipolymer is studied, the ratio of finding the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is can obtain good result in the situation of 55～80 quality %, but when surpassing 80 quality % the time length of antifouling property shorten.The inventor is studied its reason, and when the ratio of the vinylformic acid tert-butyl diphenyl silicomethane ester in the discovery multipolymer surpassed 80 quality %, the dissolution rate of filming was passed in time and risen, and the result becomes the reason that the medicament in filming disappears in early days.
By above opinion as can be known, contain by making the antifouling paint compositions of the copolymer A that ethylene unsaturated monomer (b) 20～45 quality % copolymerization in addition of vinylformic acid tert-butyl diphenyl silicomethane ester monomer (a) 55～80 quality % and above-mentioned monomer (a) obtain if use, can form can the long term maintenance antifouling property antifouling coat.
In addition, antifouling paint compositions of the present invention is compared with the existing antifouling paint compositions that comprises multipolymer of containing triisopropyl silicomethane ester etc., and the stability in storage of coating is good especially.Think that its reason is, monomer in the copolymer A (a) has near acidity hydrolysis rate fast specificity of hydrolysis rate slowly but under the alkaline condition more than the weakly alkaline (pH8～9) neutral, sneak into when the manufacturing of antifouling paint or when preserving in the situation of moisture and be difficult for being hydrolyzed, the having excellent storage stability of coating.On the other hand, the alkaline condition more than weakly alkaline (pH8～9), be in the seawater, the hydrolysis rate of performance appropriateness can be brought into play long-term good anti-fouling effect.
[invention effect]
According to the present invention, provide the antifouling paint compositions that can form the antifouling coat that has excellent storage stability and can the high antifouling property of long term maintenance.
[embodiment]
Below, the present invention is described in detail.
Antifouling paint compositions
Antifouling paint compositions of the present invention contains the copolymer A by ethylene unsaturated monomer (b) 20～45 quality % copolymerization in addition of vinylformic acid tert-butyl diphenyl silicomethane ester monomer (a) 55～80 quality % and above-mentioned monomer (a) are obtained.
＜copolymer A 〉
Copolymer A is by obtaining ethylene unsaturated monomer (b) 20～45 quality % copolymerization in addition of vinylformic acid tert-butyl diphenyl silicomethane ester monomer (a) 55～80 quality % and above-mentioned monomer (a).
Above-mentioned monomer (a) can obtain by the following method easily: namely, make the diphenyl dichlorosilane reaction of Grignard reagent etc. and easy acquisition, after reaction finishes, filtering reacting liquid, remove the magnesium salts of generation, make the tert-butyl diphenyl chlorosilane that obtains thus under alkaline condition with the reactions such as vinylformic acid, process according to conventional methods.Intermediate tert-butyl diphenyl chlorosilane and monomer (a) can be as required by the underpressure distillation rear use of purifying, in addition, in order to ensure stability in storage, monomer (a) can contain the common stoppers such as Resorcinol, hydroquinone monomethyl ether, BHT.
Above-mentioned monomer (a) ethylene unsaturated monomer (b) in addition is for to be selected from by at least a monomer in the group that methyl methacrylate, (methyl) butyl acrylate and (methyl) vinylformic acid-2-methoxyl group ethyl ester forms.
In addition, when using two or more monomers (b), preferred monomers (b) comprises methyl methacrylate, and the ratio of the methyl methacrylate in the ethylene unsaturated monomer is preferably 15～90 quality %, is more preferably 30～90 quality %.This ratio for example is 15 quality %, 20 quality %, 30 quality %, 40 quality %, 50 quality %, 60 quality %, 70 quality %, 80 quality %, 90 quality %, also can be in the scope between these illustrative any two numerical value.In addition, monomer (b) preferably also comprises (methyl) vinylformic acid-2-methoxyl group ethyl ester, is preferably 10～85 quality % in the ethylene unsaturated monomer, is more preferably 10～60 quality %.This ratio for example is 10 quality %, 20 quality %, 30 quality %, 40 quality %, 50 quality %, 60 quality %, 70 quality %, 80 quality %, 85 quality %, also can be in the scope between these illustrative any two numerical value.Monomer (b) can only comprise the one in vinylformic acid-2-methoxyl group ethyl ester and the methacrylic acid-2-methoxyl group ethyl ester, also can comprise both.Comprising in both situations, the total of vinylformic acid-2-methoxyl group ethyl ester and methacrylic acid-2-methoxyl group ethyl ester is made as in the situation of 100 mass parts, the ratio of methacrylic acid-2-methoxyl group ethyl ester is preferably 80～95 mass parts.This ratio can be 80 quality %, 85 quality %, 90 quality %, 95 quality %, also can be in the scope between these illustrative any two numerical value.
The preferred configuration of the copolymer A that contains in the composition of the present invention is vinylformic acid tert-butyl diphenyl silicomethane ester monomer (a) 55～80 quality % and is selected from by methyl methacrylate, (methyl) butyl acrylate, the multipolymer of at least a monomer (b) 20～45 quality % in the group that (methyl) vinylformic acid-2-methoxyl group ethyl ester forms, preferred form are vinylformic acid tert-butyl diphenyl silicomethane ester monomer (a) 55～70 quality % and are selected from by methyl methacrylate, (methyl) butyl acrylate, the multipolymer of at least a monomer (b) 30～45 quality % in the group that (methyl) vinylformic acid-2-methoxyl group ethyl ester forms.The ratio of the monomer in the multipolymer (a) for example can be 55 quality %, 58 quality %, 60 quality %, 65 quality %, 70 quality %, 75 quality %, 80 quality %, also can be in the scope between these illustrative any two numerical value.
The weight-average molecular weight of copolymer A (Mw) is preferably 10000～100000, is particularly preferably 20000～70000.Mw is that filming can not become fragile in 10000～100000 the situation, and the dissolving of filming appropriateness, therefore can effectively bring into play desired anti-fouling effect.As the measuring method of Mw, can enumerate example gel permeation chromatography (GPC).
Copolymer A can be any one multipolymer in random copolymers, alternating copolymer, periodic copolymer or the segmented copolymer of monomer (a) and monomer (b).Copolymer A for example can obtain by make monomer (a) and monomer (b) polymerization in the presence of polymerization starter.
As the polymerization starter that uses in the above-mentioned polyreaction, can separately or make up the two or more uses polymerization starter identical with above-mentioned illustrative polymerization starter.As above-mentioned polymerization starter, particularly preferably AIBN and peroxide-2-ethyl hexanoic acid tert-butyl.By the usage quantity of suitable setting polymerization starter, can adjust the molecular weight of copolymer A.
As polymerization process, can enumerate such as solution polymerization, block polymerization, letex polymerization, suspension polymerization etc.Wherein, for can be easy and accuracy obtain well the consideration of copolymer A, particularly preferably solution polymerization.
In above-mentioned polyreaction, as required can be with an organic solvent.As organic solvent, can enumerate such as aromatic hydrocarbon solvents such as dimethylbenzene, toluene; The aliphatic hydrocarbon such as hexane, heptane kind solvent; The esters solvents such as ethyl acetate, butylacetate, isobutyl acetate, acetic acid methoxyl group propyl ester; The alcoholic solvent such as Virahol, butanols; The ether solvents such as diox, diethyl ether, dibutyl ether; The ketones solvent such as methylethylketone, methyl iso-butyl ketone (MIBK) etc.Wherein, particularly preferably aromatic hydrocarbon solvent is more preferably dimethylbenzene.For these solvents, can separately or make up two or more the use.
For the temperature of reaction of polyreaction, suitably set according to the kind of polymerization starter etc. and to get final product, be generally 70～140 ℃, be preferably 80～120 ℃.For the reaction times of polyreaction, get final product according to suitable settings such as temperature of reaction, be generally about 4 hours～about 8 hours.Polyreaction is preferably carried out under the inert gas atmospheres such as nitrogen, argon gas.
The content of the copolymer A in the composition of the present invention is not particularly limited, and in the solids component of composition of the present invention, is generally 20～70 quality %, is preferably 40～60 quality %.The content of copolymer A is in the situation of 20 quality %～70 quality %, can obtain film dissolution rate and the Physical properties of coating film of the appropriateness in the seawater, can keep Surface Renewal steady in a long-term, can effectively bring into play desired anti-fouling effect.And, can bring into play the good recoat performance of filming.
In the antifouling paint compositions of the present invention, except above-mentioned copolymer A, can cooperate as required antifouling medicament B, stripping conditioning agent C, softening agent D, other resin E etc.Thus, can bring into play better anti-fouling effect.
＜antifouling medicament B 〉
As antifouling medicament B, have and kill and wound or the material of deterrent effect then is not particularly limited so long as fouling organism is given birth in the sea.Can enumerate for example inorganic medicament and organic medicament.
Cuprous rhodanide), corronel, copper powder etc. as inorganic medicament, can enumerate such as: Red copper oxide, cuprous thiocyanate (generic name:.Wherein, particularly preferably Red copper oxide and cuprous rhodanide.
Copper pyrithione) as organic medicament, can enumerate such as: 2-mercaptopyridine-N-cupric oxide (generic name: the organocopper compound such as; Zinc Pyrithione), the two zinc thiocarbamates of ethylene (generic name: zineb), two (dimethyl thiocarbamate) zinc (the U.S. zinc of generic name: Fu), two (dimethyl dithiocarbamic acid base) ethylenebis (dithiocarbamic acid) two zinc (generic name: the organic zinc compound such as polycarbamate) 2-mercaptopyridine-N-zinc oxide (generic name:; The organoboron compounds such as pyridine triphenylborane, 4-isopropyl pyridine base-diphenyl methyl borine, 4-phenylpyridyl-phenylbenzene borine, triphenyl-boron octadecyl amine, triphenyl [3-(2-ethyl hexyl oxy) propylamine] boron; 2,4,6-trichlorine maleimide, N-(2,6 diethyl phenyl) 2, the maleimide compounds such as 3-dichloro maleimide; And other 4,5-two chloro-2-n-octyl-3-isothiazolones (generic names: Sea nine 211), 3,4-dichlorophenyl-N-N-dimethyl urea (generic name: Diuron Tech), 2-methylthio group-4-tertiary butyl amino-6-cyclopropylamino-s-triazine (generic name: Irgarol 1051), 2,4,5,6-daconil M (generic name: m-tetrachlorophthalodinitrile), N-dichloro fluorine methylthio group-N ', N '-dimethyl-N-p-methylphenyl sulphonamide (generic name: tolylfluanid), N-dichloro thiomethyl-N ', N '-dimethyl-N-benzsulfamide (generic name: Pecudin), 2-(4-thiazolyl) benzoglyoxaline (generic name: thiabendazole), 3-(benzo (b) thiophene-2-yl)-5,6-dihydro-1,4,2-Evil thiazine-4-oxide compound (generic name: bethoxazin), 2-(rubigan)-3-cyano group-4-bromo-5-trifluoromethyl pyrpole (generic name: ECONEA 028) etc.Wherein, particularly preferably Zinc Pyrithione, copper pyrithione, pyridine triphenylborane, 4-isopropyl pyridine base-diphenyl methyl borine, bethoxazin, zineb, Sea nine 211 and Irgarol 1051 are more preferably copper pyrithione, Zinc Pyrithione, pyridine triphenylborane and bethoxazin.
As antifouling medicament B, preferential oxidation is cuprous, cuprous rhodanide, Zinc Pyrithione, copper pyrithione, pyridine triphenylborane, 4-isopropyl pyridine base-diphenyl methyl borine, bethoxazin, zineb, Sea nine 211 and Irgarol 1051, tolylfluanid, Pecudin, is more preferably Red copper oxide, copper pyrithione, Zinc Pyrithione, pyridine triphenylborane and bethoxazin.
Can use a kind of or and with two or more above-mentioned antifouling medicaments.
The content of antifouling medicament B in the composition of the present invention is not particularly limited, and in the solids component of composition of the present invention, is generally 0.1～75 quality %, is preferably 1～60 quality %.The content of antifouling medicament B possibly can't obtain sufficient anti-fouling effect during less than 0.1 quality %.When the content of antifouling medicament B surpasses 75 quality %, the fragility of filming of formation, and for the tackiness of the formation of being filmed also a little less than, can't fully realize the function as antifouling coat.
＜stripping conditioning agent C 〉
As above-mentioned stripping conditioning agent C, can enumerate such as rosin, rosin derivative and their metal-salt, monocarboxylic acid and salt thereof or ester ring type hydrocarbon resin etc.
As above-mentioned rosin, can enumerate: starex, gum resin, wood rosin etc.As above-mentioned rosin derivative, can enumerate: staybelite, nilox resin, maleated rosin, formylation rosin, polymerized rosin etc.As the metal-salt of rosin and the metal-salt of rosin derivative, can use the reaction product of metallic compound and rosin, as the metal-salt of rosin, can enumerate such as gum resin zinc (or copper) salt, wood rosin zinc (or copper) salt, starex zinc (or copper) salt etc.As the metal-salt of rosin derivative, can enumerate: staybelite zinc (or copper) salt, nilox resin zinc (or copper) salt, maleated rosin zinc (or copper) salt, formylation rosin zinc (or copper) salt, polymerized rosin zinc (or copper) salt etc.
As described monocarboxylic acid, can enumerate such as: carbonatoms is about 5～about 30 lipid acid, synthetic fatty acid, naphthenic acid etc.As the salt of monocarboxylic acid, can enumerate such as mantoquita, zinc salt, magnesium salts, calcium salt etc.
As above-mentioned ester ring type hydrocarbon resin, can enumerate such as Quintone 1500,1525 L, 1700 (trade(brand)name, Nippon Zeon Co., Ltd.'s system) etc. as commercially available product.
In particular, promote the aspect of property from the stripping that can give composition appropriateness of the present invention, composition of the present invention preferably contains and is selected from least a as above-mentioned stripping conditioning agent C in the group that is comprised of rosin, rosin derivative and their metal-salt, from improving the aspect of resistance to cracking line and water tolerance, composition of the present invention particularly preferably contains the mantoquita of rosin or rosin derivative or zinc salt as above-mentioned stripping conditioning agent C.
The content of stripping conditioning agent C in the composition of the present invention with respect to described copolymer A 100 weight parts, is generally 1～80 weight part, is preferably 10～50 weight parts.Stripping conditioning agent C is during less than 1 weight part, and the little aquatic fouling organism that can the aquatic fouling organism of expectation adheres to during preventing effectiveness, the particularly equipment is adhered to preventing effectiveness.When the content of stripping conditioning agent C surpassed 80 weight part, the defective such as crackle occurs easily, peel off of filming possibly can't be given full play to aquatic fouling organism and adhere to preventing effectiveness.The content of stripping conditioning agent C for example is 1 weight part, 5 weight parts, 10 weight parts, 15 weight parts, 20 weight parts, 25 weight parts, 30 weight parts, 35 weight parts, 40 weight parts, 45 weight parts, 50 weight parts, 55 weight parts, 60 weight parts, 65 weight parts, 70 weight parts, 75 weight parts, 80 weight parts with respect to above-mentioned copolymer A 100 weight parts, also can be in the scope of these illustrative any two numerical value.
＜softening agent D 〉
By making antifouling paint compositions of the present invention contain softening agent D, the plasticity of described composition is improved, consequently can be suitable for forming tough filming.
As above-mentioned softening agent D, for example can enumerate: Tritolyl Phosphate, trioctyl phosphate, the phosphoric acid esters such as triphenylphosphate, dibutyl phthalate, the phthalates such as dioctyl phthalate (DOP), Polycizer W 260, the adipic acid ester classes such as Octyl adipate, Uniflex DBS, the sebacic acid esters such as dioctyl sebacate, epoxidised soybean oil, the epoxidized oil lipids such as epoxidised linseed oil, the methyl ethylene ether polymer, the alkyl vinyl ether polymers such as ethyl vinyl ether polymer, polyoxyethylene glycol, the polyethylene glycols such as polypropylene glycol, uncle's nonyl pentasulfide, Vaseline, polybutene, tri trimellitate (2-ethylhexyl) ester, silicone oil, whiteruss, clorafin etc.These can use separately or use two or more.
The content of softening agent D in the composition of the present invention is generally 0.1～20 weight part with respect to described copolymer A 100 weight parts, is preferably 0.5～10 weight part.
＜other resins E 〉
By in antifouling paint compositions of the present invention, containing other resins E, can reduce cost on the basis of not damaging effect of the present invention, and can obtain the synergy of the physical property that has with resin E.
As other resins E, can enumerate such as: contain the polymkeric substance of carboxylate metal ester, the polymkeric substance that contains trialkyl silicomethane ester group, other (methyl) acrylic resin, Synolac, vibrin, chlorinated rubber resin, polyvinyl resin etc.
As the polymkeric substance that contains the carboxylate metal ester, can enumerate and have at least one in the molecule by the polymkeric substance of the carboxylate metal ester group shown in the general formula (1) etc.
-COO-M-Y ···(1)
[in the formula, M is the metal that is selected among Cu, Zn, Ca and the Mg.Y is organic acid residue.]
By in antifouling paint compositions of the present invention, containing the above-mentioned polymkeric substance that contains the carboxylate metal ester, can reduce cost on the basis that does not affect effect of the present invention, and can obtain the good anti-fouling effect at initial stage by the polymkeric substance that contains the carboxylate metal ester.
In the above-mentioned polymkeric substance that contains the carboxylate metal ester, particularly preferably M is Cu or Zn, and Y is for being selected from the organic acid residue in naphthenic acid, rosin (derivative) class and (methyl) vinylformic acid.
As the polymkeric substance that contains trialkyl silicomethane ester group, can enumerate (methyl) vinylformic acid triisopropyl silicomethane ester, (methyl) vinylformic acid tributyl silicomethane ester etc.
Other resins E in the composition of the present invention can contain in the scope of film dissolution rate and the Physical properties of coating film that do not damage the appropriateness in the seawater, and its content is 1～200 weight part with respect to above-mentioned copolymer A 100 weight parts, is preferably 20～100 weight parts.
＜other additive 〉
And, can in antifouling paint compositions of the present invention, add pigment, dyestuff, defoamer, anti-sagging agent, dispersion agent, antisettling agent, dewatering agent, organic solvent etc. as required.
As pigment, can enumerate such as zinc oxide, Indian red, talcum, titanium oxide, silicon-dioxide, calcium carbonate, barium sulfate, calcium oxide, magnesium oxide etc.These pigment can be separately with or make up two or more the use.
As dyestuff, can enumerate various organic dye that dissolve in organic solvent etc.
As defoamer, can enumerate: silicone resin defoamer, acrylic resin defoamer etc.
As anti-sagging agent, dispersion agent or antisettling agent, can enumerate fatty acid amide wax, oxidic polyethylene etc.
As dewatering agent, can enumerate such as the silicates such as dehydrated gyp-, synthetic zeolite class sorbent material, ortho ester class, tetraethoxysilane or isocyanates etc.These dewatering agents can be separately with or make up two or more the use.
As organic solvent, can enumerate such as: aliphatic category solvent, aromatic series kind solvent, ketones solvent, esters solvent, ether solvent etc. are blended in the organic solvent in the antifouling paint usually.These organic solvents can be separately with or make up two or more the use.
The manufacture method of antifouling paint compositions
Antifouling paint compositions of the present invention for example can be by using dispersion machine, and the mixed solution blending dispersion that will contain described copolymer A etc. is made.
Can suitably adjust the content of described copolymer A in the described mixed solution etc., so that they reach the content of above-mentioned copolymer A in the above-mentioned antifouling paint compositions etc. separately.
As described mixed solution, be preferably various material dissolves such as making above-mentioned copolymer A or be distributed in the solvent and mixed solution.As described solvent, can use the solvent identical with above-mentioned organic solvent.
As described dispersion machine, for example can be preferably with the dispersion machine that can use as pulverizer.For example, can use commercially available homogeneous mixer, sand mill, ball mill etc.In addition, also can use and in having the container of stirrer, add the device of blending dispersion with granulated glass sphere etc., come described mixed solution is carried out blending dispersion.
Anti-fouling treatment method, antifouling coat and coated article
Anti-fouling treatment method of the present invention is to use above-mentioned antifouling paint compositions to form antifouling coat at body surface of filming to be formed.According to anti-fouling treatment method of the present invention, thereby because described antifouling coat dissolves gradually from the surface film coated surface is constantly updated, therefore can be realized preventing adhering to of aquatic fouling organism.In addition, film after the dissolving, can continue to bring into play anti-fouling effect by again applying above-mentioned composition.
As object of filming to be formed, can enumerate such as structures etc. in boats and ships (particularly hull bottom), fishery apparatus, the water.As the fishery apparatus, can enumerate such as: cultivation with or fixing fishing net accessory with fishing net, the buoy that is used for this fishing net, rope etc. etc.As structures in the water, can enumerate such as power house water pipe, bridge, bay equipment etc.
Antifouling coat can form by above-mentioned antifouling paint compositions being coated to body surface of filming to be formed (in whole or in part).
As coating method, can enumerate such as spread coating, spraying method, pickling process, flow coat method, spin-coating method etc.These coating methods can separately or and use with two or more.
After the coating, make its drying.Drying temperature is that room temperature gets final product.Can suitably set time of drying according to thickness of filming etc.
The antifouling coat of the present invention that uses above-mentioned antifouling paint compositions to form, film dissolution rate and the Physical properties of coating film of the appropriateness of performance in seawater can be kept Surface Renewal steady in a long-term, can effectively bring into play desired anti-fouling effect.In addition, has the advantage that to bring into play the good recoat performance of filming.
The thickness of described antifouling coat can suitably be set according to the route speed of the kind of object of filming to be formed, boats and ships, seawater temperature etc.For example, when object of filming to be formed was the hull bottom of boats and ships, the thickness of antifouling coat was generally 50～500 μ m, was preferably 100～400 μ m.
Antifouling coat of the present invention has the hardness of appropriateness.That is, antifouling coat of the present invention has the hardness that the unusual degree of filming such as cold deformation (cold flow) do not occur.
Coated article of the present invention has described antifouling coat on its surface.Coated article of the present invention can have described antifouling coat on its whole surface, also can have described antifouling coat at its part surface.
Thereby coated article of the present invention is owing to have by improving film dissolution rate and Physical properties of coating film Surface Renewal and good the filming of recoatability steady in a long-term of appropriateness in the seawater, thereby is preferably used as in above-mentioned boats and ships (particularly hull bottom), fishery apparatus, the water structures etc.
For example, when having formed above-mentioned antifouling coat on the hull bottom surface of boats and ships, thereby because described antifouling coat dissolves gradually from the surface film coated surface is constantly updated, therefore can be realized preventing adhering to of aquatic fouling organism.
And described antifouling coat can suitably suppress hydrolysis rate.Therefore, these boats and ships can be kept antifouling property for a long time, for example, even under the stationary state in berthing, during the equipment etc., also can occur hardly adhering to and accumulating of aquatic fouling organism, therefore can bring into play for a long time anti-fouling effect.
In addition, even through crackle still substantially not occurring on the antifouling coat of long-time rear surface or peeling off.Therefore, there is no need to remove fully and newly again after filming form the operation of filming etc.Therefore, by directly again applying above-mentioned antifouling coat composition, can effectively form antifouling coat.Thus, can continue to keep anti-fouling effect with low cost easily.
[embodiment]
Below, embodiment is shown waits further clear and definite feature of the present invention.But the present invention is not subjected to the restriction of these embodiment.
% in each Production Example, comparison Production Example, embodiment and the comparative example represents quality %.Viscosity is the measured value under 25 ℃, the value of being obtained by B shape viscometer.The value (polystyrene conversion value) of weight-average molecular weight (Mw) for obtaining by GPC.The condition of GPC is as described below.
The device HLC-8220GPC processed of TOSOH Co., Ltd
2 of chromatographic column TSKgel SuperHZM-M (TOSOH Co., Ltd's system)
Flow 0.35mL/ minute
Detector RI
40 ℃ of chromatographic column thermostatic bath temperature
Elutriant THF
The heating lingering section is the value of obtaining after 1 hour 125 ℃ of lower heating.
In addition, the unit of the use level of each composition in the table 1 is g.
Production Example 1 (manufacturing of copolymer solution A-1)
Dimethylbenzene 230g packs in the flask with thermometer, reflux exchanger, stirrer and dropping funnel, under nitrogen atmosphere, in 100 ± 2 ℃ of lower stirrings, with the mixed solution of 1 hour dropping vinylformic acid tert-butyl diphenyl silicomethane ester 275g, methyl methacrylate 175g, vinylformic acid-2-methoxyl group ethyl ester 50g and peroxide-2-ethyl hexanoic acid tert-butyl 4g (initial stage interpolation).Then, after 2 hours, added peroxide-2-ethyl hexanoic acid tert-butyl 1g (the rear interpolation) 3 times in per 2 hours, after the end polyreaction in synthermal lower stirring, add dimethylbenzene 270g and make its dissolving, obtain thus containing the copolymer solution A-1 of three organic silicomethane esters.
Viscosity, heating lingering section, the Mw of A-1 are shown in table 1.
Production Example 2～6 (manufacturing of copolymer solution A-2～A-6)
Use organic solvent, monomer and polymerization starter shown in the table 1, carry out polyreaction with the operation identical with Production Example 1, obtain thus copolymer solution A-2～A-6.Viscosity, heating lingering section, the Mw of resulting each copolymer solution are shown in table 1.
[table 1]
Production Example 7 (manufacturing of copolymer solution A-7)
PGM (propylene glycol monomethyl ether) 50g and dimethylbenzene 130g pack in the four-hole boiling flask with thermometer, reflux exchanger, stirrer and dropping funnel, then, under nitrogen atmosphere, in 100 ± 2 ℃ of lower stirrings, with the mixed solution of 1 hour dropping PGM25g, dimethylbenzene 25g, vinylformic acid tert-butyl diphenyl silicomethane ester 275g, methyl methacrylate 125g, methacrylic acid-2-methoxyl group ethyl ester 75g, zinc methacrylate 25g and peroxide-2-ethyl hexanoic acid tert-butyl 4g (initial stage interpolation).After the dropping, under 100 ± 2 ℃, carry out 2 hours polyreactions.Then, under 100 ± 2 ℃ temperature in the stirring reaction liquid, adding peroxide-2-ethyl hexanoic acid tert-butyl 1g (the rear interpolation) in per 2 hours carries out polyreaction 3 times, then, add dimethylbenzene 270g and make its dissolving, obtain thus containing the copolymer solution A-7 of carboxylate metal ester.The heating lingering section of resulting varnish is 51.7%, viscosity is 490cps/25 ℃.
Production Example 8 (manufacturing of copolymer solution A-8)
Add dimethylbenzene 325g and propyl carbinol 100g in the four-hole boiling flask with thermometer, reflux exchanger, stirrer and dropping funnel and heat after 100～110 ℃, under nitrogen atmosphere with the mixing solutions of 4 hours dropping vinylformic acid tert-butyl diphenyl silicomethane ester 275g, vinylformic acid 10g, ethyl propenoate 75g, cyclohexyl methacrylate 90g, Diisopropyl azodicarboxylate 12g (initial stage interpolation).After drip finishing, 110 ℃ of insulations to through 30 minutes, with the mixing solutions that dripped dimethylbenzene 50g, propyl carbinol 25g and Diisopropyl azodicarboxylate 2.5g (the rear interpolation) in 1 hour, insulation to the dropping through 2 hours.
Then, dropping funnel is replaced with decanting vessel, add venus crystals 25.2g, naphthenic acid 50g and deionized water 50g, be heated to 100 ℃, except acetic acid and the water that dereaction generates, obtain containing the copolymer solution A-8 of carboxylate metal ester.The heating lingering section of resulting varnish is 51.5%, viscosity is 330cps/25 ℃.
Production Example 9
In the flask with thermometer, reflux exchanger, stirrer and dropping funnel, add dimethylbenzene 100g and propyl carbinol 20g, heat after 100～110 ℃, under nitrogen atmosphere with the mixing solutions that dripped vinylformic acid 25.7g, ethyl propenoate 57.8g, methyl methacrylate 16.5g and Diisopropyl azodicarboxylate 3g in 4 hours.110 ℃ of insulations after drip to finish through 30 minutes, with the mixing solutions that dripped dimethylbenzene 20g, propyl carbinol 10g and Diisopropyl azodicarboxylate 0.5g in 1 hour, insulation to the dropping through 2 hours.
Then, dropping funnel is replaced with decanting vessel, add propionic acid copper 74.9g, naphthenic acid 91.1g and deionized water 50g, be heated to 100 ℃, except propionic acid and water that dereaction generates, reaction end is determined by the acetic acid that quantitatively distillates in the solvent.After reaction finishes, add dimethylbenzene and regulate solids component, obtain containing the copolymer solution B-1 of carboxylate metal ester.The heating residual component of resulting varnish is 50.3%, weight-average molecular weight is 8000, viscosity is 185cps/25 ℃.
Compare Production Example 1～4
Use organic solvent, monomer and the polymerization starter shown in the table 1, carry out polyreaction with the operation identical with Production Example 1, obtain thus copolymer solution C-1～C-4.Viscosity, heating lingering section, the Mw of resulting each copolymer solution are shown in table 1.
Embodiment 1～19 and comparative example 1～4 (manufacturing of coating composition)
Cooperate the composition shown in the table 2 with the ratio shown in the table 2 (quality %), by making coating composition with the granulated glass sphere blending dispersion of diameter 1.5～2.5mm.
[table 2]
Test example 1 (stability test of coating)
Pack in the zinc-plated iron flask of wide-mouth of 100ml the coating composition that obtains in embodiment 1～19 and the comparative example 1～4 and sealing, in 45 ℃ thermostatted, preserved 3 months, then, with the viscosity of this coating composition of B shape viscometer determining.
Estimate by following method.
◎: the viscosity of coating changes the situation (the coating state is unconverted situation basically) less than 500mPas/25 ℃
Zero: the viscosity of coating is changed to 500～5000mPas/25 ℃ situation (a little situation of tackify)
△: the viscosity of coating changes the situation (the greatly situation of tackify) greater than 5000mPas/25 ℃～100000mPas/25 ℃
*: be changed to the unmeasured situation of dope viscosity (becoming the situation of gelatinous situation or curing)
Show the result in table 3.
As shown in Table 3, use the storage stability of the coating that coating composition of the present invention (embodiment 1～19) forms good.
And on the other hand, the coating that the coating composition of usage comparison example 4 forms is larger tackify after preserving 3 months under 45 ℃.
[table 3]
Test example 2 (the tack test of filming)
Test according to the tack that the regulation of JIS K-5600-5-6 is filmed.Particularly, so that the thickness of dry coating is the mode of about 100 μ m, latten after blast finishing (coating composition that 75 * 150 * 2mm) coatings are obtained by embodiment 1～19 and comparative example 1～4, and after making its dry 1 day under 40 ℃, carry out the tack test.
Estimate by following method.
On dried filming, mark in length and breadth each 11 piece cuts of reaching substrate (latten) with the I-go board reticulation with cutter, make 100 grid that 2mm is square.Paste scotch tape (the glue bandwidth 24mm of Mi Qibang Co., Ltd.) in bubble-free mode at these 100 grid, an end that pinches adhesive tape with hand is peeled off fast, the attachment state that visual investigation is filmed.
◎: the number of the I-go board grid of peeling off is 70～100 situation
Zero: the number of the I-go board grid of peeling off is 40～69 situation
△: the number of the I-go board grid of peeling off is 20～39 situation
*: the number of the I-go board grid of peeling off is 0～19 situation
Show the result in table 3.
As shown in Table 3, use filming of coating composition of the present invention (embodiment 1～19) formation gluing securely for latten.
Test example 3 (pliability test of filming)
So that the thickness of dry coating is the mode of about 100 μ m, latten after the blast finishing (coating composition that 75 * 150 * 2mm) coatings are obtained by embodiment 1～19 and comparative example 1～4, and after making its dry 1 day under 40 ℃, confirm that by visual inspection bending is the state of filming of 90 degree.
Estimate by following method.
◎: situation about substantially not cracking
Zero: the situation that produces fine crack
△: the situation that produces larger crackle
*: the situation that a part of filming is peeled off easily
Show the result in table 3.
As shown in Table 3, use filming of coating composition of the present invention (embodiment 1～19) formation in pliability test, substantially not crack.In addition, for the embodiment 5 that the ratio of the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is 80 quality %, compare a little variation of bendability with other embodiment.
Test example 4 (whirl test)
In the central authorities of tank so that the swing roller of diameter 515mm, height 440mm can be installed by the mode that engine rotates.In addition, the constant pH two-position controller of pH that is used for the constant refrigerating unit of maintenance seawater temperature and is used for keeping seawater also has been installed.
Make two test boards according to following method.
At first, so that dried thickness is that (75 * 150 * 1mm) coating rust proof paints (polyethylene kind A/C) also make its drying, form thus anti-rust coating at the hard vinyl chloride plate for the mode of about 50 μ m.Then, so that the coating composition that dried thickness is the mode of about 300 μ m to be obtained by embodiment 1～19 and comparative example 1～4 in above-mentioned anti-rust coating coating respectively.The resulting application that is coated with was descended dry 3 days at 40 ℃, and making has the test board that thickness is about the dry coating of 300 μ m thus.
A slice in the test board that makes so that the mode of itself and contact with sea water is fixed on the swing roller of swivel arrangement of said apparatus, is made rotary drum rotating with 20 nautical miles/hour speed., the temperature of seawater is remained on 25 ℃ therebetween, pH is remained on 8.0～8.2, change weekly seawater one time.
By the laser focusing displacement gauge to the initial film thickness of each test board and after on-test per 3 months residual thickness measure, calculate the coating thickness that has dissolved by its difference, and obtain thus the meltage of filming (the μ m/ month) of each month.Need to prove that described mensuration was carried out 24 months, every through carrying out the calculating of the described meltage of filming in 12 months.
In addition, the test board of (after 24 months) after dry whirl test finishes, then each film coated surface of visual inspection is estimated the state of filming.
Estimate by following method.
◎: complete N/R situation
Zero: the situation of slightly visible hair crackings
△: visible hair crackings on whole filming
*: the upper visible larger crackle of filming, steep or the unusual situation such as peel off
Show the result in table 4.
As shown in Table 4, the meltage in seawater of filming that uses that coating composition of the present invention (embodiment 1～19) forms is about per 1 month 3～5 μ m (annual).And as can be known, the dissolution rate of filming of filming of using coating composition of the present invention to form is suppressed to a certain extent, therefore steadily in the long term dissolving.And, use that coating composition of the present invention forms film have excellent water-resistance, do not crack with hair crackings etc., therefore can the long term maintenance antifouling property.In addition, for the embodiment 5 that the ratio of the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is 80 quality %, compare with other embodiment and to be coated with a little variation of membrane stage after 24 months.
On the other hand, the dissolution rate of filming of filming that the coating composition of usage comparison example 3 forms is very little, therefore can not bring into play sufficient antifouling property.And really up to the mark owing to filming, poor water resistance, crack in the test and peeling off etc. filmed unusually.The dissolution rate of filming in the seawater of filming that the coating composition of usage comparison example 4 forms is passed in time and is become large, therefore can not bring into play for a long time antifouling property.And, with regard to the comparative example 1 that the ratio of the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is 54 quality %, although after 24 months to be coated with membrane stage good, but the meltage of on average filming of on average film meltage and initial stage～12 month after 12～24 months is compared largely and is reduced, and the dissolution rate of filming as can be known is unstable.And, with regard to the comparative example 2 that the ratio of the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is 85 quality %, the state difference of filming after 24 months, and the meltage of on average filming of on average film meltage and initial stage～12 month after 12～24 months is compared largely and is increased, and the dissolution rate of filming as can be known is unstable.
[table 4]
Test example 5 (antifouling test)
So that the thickness of dry coating is the mode of about 200 μ m, will be coated to by the coating composition that embodiment 1～19 and comparative example 1～4 obtain hard vinyl chloride plate (two surfaces of 100 * 200 * 2mm).Has the test board that thickness is about the dry coating of 200 μ m by the resulting application that is coated with being descended dry 3 days in room temperature (25 ℃), making thus.This test board is impregnated into 1.5m place under the sea in owase city, triple county, and to the stained observation of carrying out 24 months of the test board that caused by dirt settling.
State by the visual observation film coated surface is estimated, and judges according to following standard.
◎: do not have adhering to of the fouling organisms such as shellfish and algae, and substantially do not have biological clay.
Zero: do not have adhering to of the fouling organisms such as shellfish and algae, although and biological clay thinner (can see the degree of coated surface) adhere to and can enough bristles dab the level of removing.
△: do not have adhering to of the fouling organisms such as shellfish and algae, but degree thicker adhere to of biological clay can not see coated surface, namely use bristle to exert oneself level that wiping can not remove.
*: the level that the fouling organisms such as shellfish and algae adhere to,
Show the result in table 5.
As shown in Table 5, use on the filming that coating composition of the present invention (embodiment 1～19) forms, do not have adhering to of the fouling organisms such as shellfish and algae after the test in 36 months.Wherein, the ratio of the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is embodiment 1 and embodiment a little reduction of antifouling property after 5,36 months of 55 quality % or 80 quality %.On the other hand, this ratio is the embodiment of 60～70 quality %, and antifouling property does not reduce after 36 months.In addition, comprise embodiment 7～8 and embodiment a little reduction of antifouling property after 18～19,36 months of the multipolymer that contains the carboxylate metal ester.On the other hand, do not comprise the embodiment of the multipolymer that contains the carboxylate metal ester, antifouling property does not reduce after 36 months.
In addition, the ratio of using the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer be the coating composition of the comparative example 1 of 54 quality % form film on, after 24 months with thinner degree settled organism foundry loam, 36 months postadhesion fouling organisms.In addition, the ratio of the vinylformic acid tert-butyl diphenyl silicomethane ester in the multipolymer is 2,24 months thinner biological clays of postadhesion of comparative example of 85 quality %, 36 months thicker biological clays of postadhesion.In addition, usage comparison example 3 and 4 coating composition form film on, flood after 24 months, the fouling organisms such as shellfish and algae adhere to severity.
[table 5]
Claims (4)
1. an antifouling paint compositions contains the copolymer A by ethylene unsaturated monomer (b) 20～45 quality % copolymerization in addition of vinylformic acid tert-butyl diphenyl silicomethane ester monomer (a) 55～80 quality % and described monomer (a) are obtained,
Described monomer (b) is for to be selected from by at least a monomer in the group that methyl methacrylate, (methyl) butyl acrylate and (methyl) vinylformic acid-2-methoxyl group ethyl ester forms.
2. antifouling paint compositions as claimed in claim 1 also contains and is selected from least a in the group that is comprised of rosin, rosin derivative and their metal-salt.
3. an antifouling paint compositions multipolymer obtains by making ethylene unsaturated monomer (b) 20～45 quality % copolymerization in addition of vinylformic acid tert-butyl diphenyl silicomethane ester monomer (a) 55～80 quality % and described monomer (a),
Described monomer (b) is for to be selected from by at least a monomer in the group that methyl methacrylate, (methyl) butyl acrylate and (methyl) vinylformic acid-2-methoxyl group ethyl ester forms.
4. coated article, its surface have the antifouling coat that right to use requires 1 described antifouling paint compositions to form.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010188583A JP4769331B1 (en) | 2010-08-25 | 2010-08-25 | Antifouling paint composition, copolymer for antifouling paint composition, and coated article having antifouling coating film formed on the surface using the composition |
| JP2010-188583 | 2010-08-25 | ||
| PCT/JP2011/066155 WO2012026237A1 (en) | 2010-08-25 | 2011-07-14 | Antifouling coating composition, copolymer for antifouling coating composition, and coated article having surface that is provided with antifouling coating film which is formed using the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103080249A true CN103080249A (en) | 2013-05-01 |
| CN103080249B CN103080249B (en) | 2015-08-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180040531.8A Expired - Fee Related CN103080249B (en) | 2010-08-25 | 2011-07-14 | Antifouling paint compositions, antifouling paint compositions multipolymer, surface have the coated article of the antifouling coat using said composition to be formed |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4769331B1 (en) |
| CN (1) | CN103080249B (en) |
| SG (1) | SG187606A1 (en) |
| WO (1) | WO2012026237A1 (en) |
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| CN110891990A (en) * | 2018-07-03 | 2020-03-17 | 日本油漆船舶涂料公司 | Copolymer and antifouling coating composition comprising the same |
| CN111171678A (en) * | 2020-02-24 | 2020-05-19 | 中环海化(厦门)船舶智能涂料有限公司 | Copper powder-based contact type antifouling paint containing copper and copper alloy powder and preparation method thereof |
| CN111886304A (en) * | 2018-04-20 | 2020-11-03 | 日东化成株式会社 | Antifouling coating composition |
| CN113498426A (en) * | 2019-03-15 | 2021-10-12 | 日东化成株式会社 | Antifouling coating composition |
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| JP5916490B2 (en) | 2012-04-09 | 2016-05-11 | 中国塗料株式会社 | Friction resistance prediction method for ship bottom coating film, coating film performance evaluation method and coating film performance evaluation apparatus using the method |
| KR20150104114A (en) | 2012-12-19 | 2015-09-14 | 요툰 에이/에스 | Silyl ester copolymer |
| MY182675A (en) * | 2013-04-24 | 2021-01-29 | Nitto Kasei Co Ltd | Antifouling paint composition, copolymer for antifouling paint composition and method for manufacturing same, and painted object having on surface antifouling paint film formed using said composition |
| JP2016033210A (en) * | 2014-07-28 | 2016-03-10 | 日本曹達株式会社 | Coating agent |
| WO2016151957A1 (en) * | 2015-03-23 | 2016-09-29 | 関西ペイント株式会社 | Antifouling coating composition and article coated therewith |
| GB201703457D0 (en) * | 2017-03-03 | 2017-04-19 | Jotun As | Composition |
| GB2592921B (en) | 2020-03-09 | 2024-04-17 | Jotun As | Hull cleaning robot |
| JP2024514449A (en) | 2021-03-23 | 2024-04-02 | ヨツン アクティーゼルスカブ | Monitoring the cleanliness of the surfaces of stationary objects in water |
| GB202107159D0 (en) | 2021-03-23 | 2021-06-30 | Jotun As | Monitoring a vessel |
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| US11111406B2 (en) | 2018-07-03 | 2021-09-07 | Nippon Paint Marine Coatings Co., Ltd. | Copolymer and antifouling coating composition containing the same |
| CN110891990B (en) * | 2018-07-03 | 2021-09-21 | 日本油漆船舶涂料公司 | Copolymer and antifouling coating composition comprising the same |
| CN113498426A (en) * | 2019-03-15 | 2021-10-12 | 日东化成株式会社 | Antifouling coating composition |
| CN111171678A (en) * | 2020-02-24 | 2020-05-19 | 中环海化(厦门)船舶智能涂料有限公司 | Copper powder-based contact type antifouling paint containing copper and copper alloy powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| SG187606A1 (en) | 2013-03-28 |
| JP4769331B1 (en) | 2011-09-07 |
| WO2012026237A1 (en) | 2012-03-01 |
| JP2012046600A (en) | 2012-03-08 |
| CN103080249B (en) | 2015-08-05 |
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