CN103080249B - Antifouling paint compositions, antifouling paint compositions multipolymer, surface have the coated article of the antifouling coat using said composition to be formed - Google Patents
Antifouling paint compositions, antifouling paint compositions multipolymer, surface have the coated article of the antifouling coat using said composition to be formed Download PDFInfo
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- CN103080249B CN103080249B CN201180040531.8A CN201180040531A CN103080249B CN 103080249 B CN103080249 B CN 103080249B CN 201180040531 A CN201180040531 A CN 201180040531A CN 103080249 B CN103080249 B CN 103080249B
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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
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Abstract
The invention provides the antifouling paint compositions that long-term storing stability is excellent, and be provided for being formed in seawater medium-term and long-term do not occur the films such as crackle abnormal, stable film solvability and antifouling property can be maintained and the multipolymer with ad hoc structure of the high antifouling coat of environmental safety.According to the present invention, a kind of antifouling paint compositions is provided, containing the copolymer A that obtains by making ethylene unsaturated monomer (b) 20 ~ 45 quality % copolymerization beyond vinylformic acid t-butyidiphenylsilyl ester monomer (a) 55 ~ 80 quality % and described monomer (a), described monomer (b) is for being selected from least one monomer in the group that is made up of methyl methacrylate, (methyl) butyl acrylate and (methyl) vinylformic acid-2-methoxy acrylate.
Description
[technical field]
The present invention relates to antifouling paint compositions, coated article that antifouling paint compositions multipolymer, surface have the antifouling coat using said composition to be formed.
[background technology]
Because the aquatic fouling organisms such as barnacle, imperial cyprid, Mytilus edulis, careless tongue worm, Ascidian, intestines Enteromorpha, sea lettuce, biological clay to be 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 structures, the problem that the function that there are above-mentioned boats and ships etc. is subject to hindering, outward appearance suffers damage etc.
After the use of the organic stanniferous multipolymer in the past used is forbidden, develop the multipolymer containing three Organosilyls (trisorganosilyl group) that toxicity is low and few to the load of environment, and for antifouling paint.
As the above-mentioned multipolymer containing three Organosilyls, use the monomer copolymerization containing the such silicomethane ester that to make containing alkyl be straight-chain of the multipolymer of three normal-butyl silicomethane esters and formed multipolymer time, due to film hydrolysis rate quickly and water tolerance is also poor, there is the problem (patent documentation 3) being difficult to the dissolution rate controlling film.
In addition, as the above-mentioned multipolymer containing three Organosilyls, use the monomer copolymerization containing the such three organic silicomethane esters that to make containing alkyl be branched of the multipolymer of triisopropyl silicomethane ester and formed multipolymer time, although the starting stage dissolves with certain speed in the seawater, but the dissolution rate of film increases gradually, dissolution rate through long-time then film excessively increases, and there is the problem of coating difficult design.And, have passed through long film in the seawater, sometimes cause the films such as crackle abnormal.And, for the coating of the multipolymer containing triisopropyl silicomethane ester group, due in order to manufacture coating and the water produced in the moisture contained in starting material etc. or the manufacturing processed at coating, in coating is preserved, resinous principle is easily hydrolyzed, and there is the multiviscosisty bringing out coating, aging etc. problem.In order to solve this problem, propose the scheme coordinating dewatering agent etc.But although utilize dewatering agent to play certain effect, and not fully solves, long-term preserve in worry multiviscosisty, aging etc.And, also moisture be must be noted that for raw-material operation, there is the problem (patent documentation 1,2,4 ~ 7) of operation efficiency difference.
In addition, as the above-mentioned multipolymer containing three organic silicomethane ester groups, it is also proposed the scheme using methacrylic acid t-butyidiphenylsilyl ester copolymer, but because the film dissolution rate in seawater is too small, desired anti-fouling effect cannot be obtained, and hardness of film excessively uprises, there is bad to the tackiness of structures in water, to cause the film exceptions such as crackle problem (patent documentation 1,2,4 ~ 7).
Like this, the water-disintegrable of abnormal, the lasting appropriateness of film such as not cracking for a long time is not in the seawater had at present and the antifouling paint compositions that long-term storing stability is excellent.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Unexamined Patent Publication 7-102193 publication
[patent documentation 2] Japanese Unexamined Patent Publication 8-269390 publication
[patent documentation 3] Japanese Unexamined Patent Publication 9-194790 publication
[patent documentation 4] Japanese Unexamined Patent Publication 10-30071 publication
[patent documentation 5] Japanese Unexamined Patent Publication 2001-226440 publication
[patent documentation 6] Japanese Unexamined Patent Publication 2003-261816 publication
[patent documentation 7] Japanese Unexamined Patent Publication 2005-082725 publication
[summary of the invention]
[inventing problem to be solved]
Problem of the present invention is, the antifouling paint compositions that long-term storing stability is excellent is provided, and is provided for being formed in that seawater is medium-term and long-term the film unusual phenomenoies such as crackle does not occur and can maintain stable film solvability and antifouling property and the multipolymer with ad hoc structure of the high antifouling coat of environmental safety.
[technique means of dealing with problems]
According to the present invention, a kind of antifouling paint compositions is provided, containing the copolymer A that obtains by making ethylene unsaturated monomer (b) 20 ~ 45 quality % copolymerization beyond vinylformic acid t-butyidiphenylsilyl ester monomer (a) 55 ~ 80 quality % and above-mentioned monomer (a), above-mentioned monomer (b) is for being selected from least one monomer in the group that is made up of methyl methacrylate, (methyl) butyl acrylate and (methyl) vinylformic acid-2-methoxy acrylate.
In order to solve problem that the antifouling coat that uses antifouling paint containing methacrylic acid t-butyidiphenylsilyl ester copolymer to be formed has, the film exception such as bad and crackle to the tackiness of structures in water, the present inventor expects that acrylate that employing flexibility is higher is to replace methacrylic ester.Therefore, use the antifouling paint containing vinylformic acid t-butyidiphenylsilyl ester copolymer to form antifouling coat, performance evaluation is carried out to it.Result obtains very excellent result in tack test and pliability test.In addition, even if observe the painting membrane stage after long-time, also the film unusual phenomenoies such as crackle are not found, known by adopting acrylate to replace methacrylic ester, solve multiple problems that methacrylic acid t-butyidiphenylsilyl ester copolymer has.
But studying rear discovery further in great detail to the antifouling coat using the antifouling paint containing vinylformic acid t-butyidiphenylsilyl ester copolymer to be formed, 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, present inventor has performed further investigation, found that ratio and the long-term antifouling property of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer are closely related, and find by making the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer be more than 55 quality %, holding time of antifouling property significantly improves.The reason that can obtain effect excellent like this during more than 55 quality % still imperfectly understands.Rear discovery is tested to the dissolution rate of film, when the ratio of vinylformic acid t-butyidiphenylsilyl ester is more than 55 quality %, the dissolution rate of film keeps certain for a long time, on the other hand, when being below 54 quality %, the dissolution rate of film is passed in time and reduces.Foregoing provides following enlightenment, stably be hydrolyzed to make vinylformic acid t-butyidiphenylsilyl ester copolymer, the ratio that must make the vinylformic acid t-butyidiphenylsilyl ester in multipolymer is more than 55 quality %, when lower than this ratio, the hydrolysis rate of vinylformic acid t-butyidiphenylsilyl ester copolymer is unstable, and result antifouling property reduces within a short period of time.
In addition, how the present inventor can change the performance of antifouling coat when improving further the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer is studied, the ratio finding the vinylformic acid t-butyidiphenylsilyl ester in multipolymer can obtain excellent result when being 55 ~ 80 quality %, but more than the decreased duration of antifouling property during 80 quality %.The present inventor is studied its reason, and when finding the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer more than 80 quality %, the dissolution rate of film is passed in time and rises, and result becomes the reason that the medicament in film disappears in early days.
From above opinion, if use the antifouling paint compositions of copolymer A containing obtaining by making ethylene unsaturated monomer (b) 20 ~ 45 quality % copolymerization beyond vinylformic acid t-butyidiphenylsilyl ester monomer (a) 55 ~ 80 quality % and above-mentioned monomer (a), can be formed can the antifouling coat of long term maintenance antifouling property.
In addition, antifouling paint compositions of the present invention is compared with the existing antifouling paint compositions of the multipolymer comprised containing triisopropyl silicomethane ester etc., and the stability in storage of coating is excellent especially.Think that its reason is, monomer (a) in copolymer A has slow near neutral hydrolysis rate in acidity but more than weakly alkaline (pH8 ~ 9) the fireballing specificity of hydrolyzed under basic conditions, not easily be hydrolyzed when the manufacture of antifouling paint or when being mixed into moisture when preserving, having excellent storage stability of coating.On the other hand, in alkaline condition, i.e. seawater more than weakly alkaline (pH8 ~ 9), play the hydrolysis rate of appropriateness, anti-fouling effect excellent for a long time can be played.
[invention effect]
According to the present invention, provide to be formed and to have excellent storage stability and can the antifouling paint compositions of antifouling coat of long term maintenance height antifouling property.
[embodiment]
Below, the present invention is described in detail.
antifouling paint compositions
Antifouling paint compositions of the present invention contains the copolymer A obtained by making ethylene unsaturated monomer (b) 20 ~ 45 quality % copolymerization beyond vinylformic acid t-butyidiphenylsilyl ester monomer (a) 55 ~ 80 quality % and above-mentioned monomer (a).
< copolymer A >
Copolymer A obtains by making ethylene unsaturated monomer (b) 20 ~ 45 quality % copolymerization beyond vinylformic acid t-butyidiphenylsilyl ester monomer (a) 55 ~ 80 quality % and above-mentioned monomer (a).
Above-mentioned monomer (a) can obtain by the following method easily: namely, Grignard reagent etc. is reacted with the diphenyl dichlorosilane easily obtained, after reaction terminates, filtering reacting liquid, the magnesium salts that removing generates, make the tert-butyl diphenyl chlorosilane that obtains thus in the basic conditions with the reactions such as vinylformic acid, process according to conventional methods.Intermediate tert-butyl diphenyl chlorosilane and monomer (a) are used after can being purified by underpressure distillation as required, in addition, in order to ensure stability in storage, monomer (a) can contain the common stoppers such as Resorcinol, hydroquinone monomethyl ether, BHT.
Ethylene unsaturated monomer (b) beyond above-mentioned monomer (a) is for being selected from least one monomer in the group that is made up of methyl methacrylate, (methyl) butyl acrylate and (methyl) vinylformic acid-2-methoxy acrylate.
In addition, when using two or more monomers (b), preferred monomers (b) comprises methyl methacrylate, and the ratio of the methyl methacrylate in ethylene unsaturated monomer is preferably 15 ~ 90 quality %, is more preferably 30 ~ 90 quality %.This ratio is such as 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-methoxy acrylate, is preferably 10 ~ 85 quality % in ethylene unsaturated monomer, is more preferably 10 ~ 60 quality %.This ratio is such as 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) only can comprise the one in vinylformic acid-2-methoxy acrylate and methacrylic acid-2-methoxy acrylate, also can comprise both.When comprising both, when the total of vinylformic acid-2-methoxy acrylate and methacrylic acid-2-methoxy acrylate is set to 100 mass parts, the ratio of methacrylic acid-2-methoxy acrylate 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 contained in composition of the present invention is vinylformic acid t-butyidiphenylsilyl ester monomer (a) 55 ~ 80 quality % and is selected from by methyl methacrylate, (methyl) butyl acrylate, the multipolymer of at least one monomer (b) 20 ~ 45 quality % in the group of (methyl) vinylformic acid-2-methoxy acrylate composition, preferred form is vinylformic acid t-butyidiphenylsilyl ester monomer (a) 55 ~ 70 quality % and is selected from by methyl methacrylate, (methyl) butyl acrylate, the multipolymer of at least one monomer (b) 30 ~ 45 quality % in the group of (methyl) vinylformic acid-2-methoxy acrylate composition.The ratio of the monomer (a) in multipolymer can be such as 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 (Mw) of copolymer A is preferably 10000 ~ 100000, is particularly preferably 20000 ~ 70000.When Mw is 10000 ~ 100000, film can not become fragile, and the dissolving appropriateness of film, therefore, it is possible to the anti-fouling effect desired by effectively playing.As the measuring method of Mw, example gel permeation chromatography (GPC) can be enumerated.
Copolymer A can be monomer (a) and any one multipolymer in the random copolymers of monomer (b), alternating copolymer, periodic copolymer or segmented copolymer.Copolymer A such as can by making monomer (a) be polymerized with monomer (b) and obtaining under the existence of polymerization starter.
As the polymerization starter used in above-mentioned polyreaction, separately or the polymerization starter identical with above-mentioned illustrative polymerization starter can be used in combination of two or more.As above-mentioned polymerization starter, particularly preferably AIBN and peroxide-2-ethyl hexanoic acid tert-butyl.By suitably setting the usage quantity of polymerization starter, the molecular weight of copolymer A can be adjusted.
As polymerization process, can enumerate such as: solution polymerization, block polymerization, letex polymerization, suspension polymerization etc.Wherein, for easy and accuracy obtaining the consideration of copolymer A, particularly preferably solution polymerization well.
In above-mentioned polyreaction, as required can be with an organic solvent.As organic solvent, can enumerate such as: the aromatic hydrocarbon solvent such as dimethylbenzene, toluene; The Aliphatic hydrocarbon solvents such as hexane, heptane; 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, two or more use separately or can be combined.
For the temperature of reaction of polyreaction, the kind etc. according to polymerization starter suitably sets, and is generally 70 ~ 140 DEG C, is preferably 80 ~ 120 DEG C.For the reaction times of polyreaction, suitably set according to temperature of reaction etc., be generally about 4 hours ~ about 8 hours.Polyreaction is preferably carried out under the inert gas atmosphere such as nitrogen, argon gas.
The content of the copolymer A in 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 %.When the content of copolymer A is 20 quality % ~ 70 quality %, film dissolution rate and the Physical properties of coating film of the appropriateness in seawater can be obtained, Surface Renewal steady in a long-term can be maintained, can effectively play desired anti-fouling effect.Further, the excellent recoat performance of film can be played.
In antifouling paint compositions of the present invention, except above-mentioned copolymer A, antifouling medicament B, stripping conditioning agent C, softening agent D, other resin E etc. can be coordinated as required.Thereby, it is possible to play more excellent anti-fouling effect.
The antifouling medicament B> of <
As antifouling medicament B, to kill and wound or the material of deterrent effect is not particularly limited as long as have the raw fouling organism in sea.Such as inorganic medicament and organic medicament can be enumerated.
As inorganic medicament, can enumerate such as: Red copper oxide, cuprous thiocyanate (generic name: cuprous rhodanide), corronel, copper powder etc.Wherein, particularly preferably Red copper oxide and cuprous rhodanide.
As organic medicament, can enumerate such as: the organocopper compounds such as 2-mercaptopyridine-N-cupric oxide (generic name: copper pyrithione), the two zinc thiocarbamate (generic name: zineb) of 2-mercaptopyridine-N-zinc oxide (generic name: Zinc Pyrithione), ethylene, two (dimethyl-thiocarbamic acid) zinc (the U.S. zinc of generic name: Fu), two (dimethyl dithiocarbamic acid base) ethylenebis (dithiocarbamic acid) two organic zinc compound such as zinc (generic name: polycarbamate), the organoboron compounds such as triphenylboron pyridine alkane, 4-isopropyl pyridine base-diphenyl methyl borine, 4-phenylpyridyl-phenylbenzene borine, triphenyl-boron octadecyl amine, triphenyl [3-(2-ethyl hexyl oxy) propylamine] boron, the maleimide compounds such as 2,4,6-trichlorine maleimide, N-(2,6 diethyl phenyl) 2,3-dichloro maleimides, and other 4, the chloro-2-n-octyl of 5-bis--3-isothiazolones (generic name: Sea nine 211), 3, 4-dichlorophenyl-N-N-dimethyl urea (generic name: Diuron Tech), 2-methylthio group-4-tert-butylamino-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-base)-5, 6-dihydro-1, 4, 2-Evil thiazine-4-oxide compound (generic name: bethoxazin), the bromo-5-trifluoromethyl pyrpole of 2-(rubigan)-3-cyano group-4-(generic name: ECONEA 028) etc.Wherein, particularly preferably Zinc Pyrithione, copper pyrithione, triphenylboron pyridine alkane, 4-isopropyl pyridine base-diphenyl methyl borine, bethoxazin, zineb, Sea nine 211 and Irgarol 1051, be more preferably copper pyrithione, Zinc Pyrithione, triphenylboron pyridine alkane and bethoxazin.
As antifouling medicament B, preferential oxidation is cuprous, cuprous rhodanide, Zinc Pyrithione, copper pyrithione, triphenylboron pyridine alkane, 4-isopropyl pyridine base-diphenyl methyl borine, bethoxazin, zineb, Sea nine 211 and Irgarol1051, tolylfluanid, Pecudin, is more preferably Red copper oxide, copper pyrithione, Zinc Pyrithione, triphenylboron pyridine alkane and bethoxazin.
One can be used or and with two or more above-mentioned antifouling medicament.
The content of the antifouling medicament B in 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 %.When the content of antifouling medicament B is less than 0.1 quality %, possibly cannot obtain sufficient anti-fouling effect.When the content of antifouling medicament B is more than 75 quality %, the film of formation is fragile, and for also weak by the tackiness of film formation, fully cannot 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, formylated rosin, polymerized rosin etc.As the metal-salt of rosin and the metal-salt of rosin derivative, the reaction product of metallic compound and rosin can be used, 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, formylated rosin zinc (or copper) salt, polymerized rosin zinc (or copper) salt etc.
As described monocarboxylic acid, can enumerate such as: carbonatoms is the lipid acid, synthetic fatty acid, naphthenic acid etc. of about 5 ~ about 30.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 commercially available product: Quintone 1500,1525 L, 1700 (trade(brand)name, Nippon Zeon Co., Ltd.'s systems) etc.
In particular, from can give composition appropriateness of the present invention stripping promote property aspect, composition of the present invention preferably containing at least one be selected from the group that is made up of rosin, rosin derivative and their metal-salt as above-mentioned stripping conditioning agent C, from the aspect improving resistance to anti-thread breakage and water tolerance, the mantoquita of composition of the present invention particularly preferably containing rosin or rosin derivative or zinc salt are as above-mentioned stripping conditioning agent C.
The content of the stripping conditioning agent C in composition of the present invention, relative to described copolymer A 100 weight part, is generally 1 ~ 80 weight part, is preferably 10 ~ 50 weight parts.When stripping conditioning agent C is less than 1 weight part, not quite will can expect the aquatic fouling organism attachment preventing effectiveness during aquatic fouling organism attachment preventing effectiveness, particularly equipment.When the content of stripping conditioning agent C is more than 80 weight part, easily there is the defect such as crackle, stripping in film, possibly cannot give full play to aquatic fouling organism attachment preventing effectiveness.The content of stripping conditioning agent C is such as 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 relative to above-mentioned copolymer A 100 weight part, 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 can be made to improve, consequently can be suitable for forming tough film.
As above-mentioned softening agent D, can enumerate such as: 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, methyl ethylene ether polymer, the alkyl vinyl ether polymers such as ethyl vinyl ether polymer, polyoxyethylene glycol, the polyethylene glycols such as polypropylene glycol, tertiary nonyl pentasulfide, Vaseline, polybutene, tri trimellitate (2-ethylhexyl) ester, silicone oil, whiteruss, clorafin etc.These can be used alone or use two or more.
The content of the softening agent D in composition of the present invention, is generally 0.1 ~ 20 weight part relative to described copolymer A 100 weight part, is preferably 0.5 ~ 10 weight part.
Other resins of < E>
By containing other resins E in antifouling paint compositions of the present invention, can reduce costs on the basis not damaging effect of the present invention, and the synergy of the physical property had with resin E can be obtained.
As other resins E, can enumerate such as: the polymkeric substance containing carboxylate metal ester, polymkeric substance containing trialkylsilyl ester group, other (methyl) acrylic resin, Synolac, vibrin, chlorinated rubber resin, polyvinyl resin etc.
As the polymkeric substance containing carboxylate metal ester, can enumerate in molecule and at least there is a polymkeric substance etc. by the carboxylate metal ester group shown in general formula (1).
-COO-M-Y ···(1)
[in formula, M is the metal be selected from Cu, Zn, Ca and Mg.Y is organic acid residue.]
By containing the above-mentioned polymkeric substance containing carboxylate metal ester in antifouling paint compositions of the present invention, can reduce costs on the basis not affecting effect of the present invention, and the excellent anti-fouling effect at initial stage can be obtained by the polymkeric substance containing carboxylate metal ester.
Above-mentioned containing in the polymkeric substance of 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 containing trialkylsilyl ester group, (methyl) vinylformic acid triisopropyl silicomethane ester, (methyl) vinylformic acid tributylsilyl ester etc. can be enumerated.
Other resins E in composition of the present invention can contain in the scope of the film dissolution rate and Physical properties of coating film of not damaging the appropriateness in seawater, and its content is 1 ~ 200 weight part relative to above-mentioned copolymer A 100 weight part, is preferably 20 ~ 100 weight parts.
Other additive > of <
And, pigment, dyestuff, defoamer, anti-sagging agent, dispersion agent, antisettling agent, dewatering agent, organic solvent etc. can be added in antifouling paint compositions of the present invention 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 used alone or combine two or more use.
As dyestuff, the various organic dye etc. dissolving in organic solvent can be enumerated.
As defoamer, can enumerate: silicone resin defoamer, acrylic resin defoamer etc.
As anti-sagging agent, dispersion agent or antisettling agent, fatty acid amide wax, oxidic polyethylene etc. can be enumerated.
As dewatering agent, can enumerate such as: silicates or the isocyanates etc. such as dehydrated gyp-, synthetic zeolite class sorbent material, ortho ester class, tetraethoxysilane.These dewatering agents can be used alone or combine two or more 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 antifouling paint usually.These organic solvents can be used alone or combine two or more use.
the manufacture method of antifouling paint compositions
Antifouling paint compositions of the present invention, such as, by using dispersion machine, can manufacture the mixed solution blending dispersion containing described copolymer A etc.
Suitably can adjust the content of the described copolymer A in described mixed solution etc., with the content making them reach above-mentioned copolymer A in above-mentioned antifouling paint compositions etc. separately.
As described mixed solution, preferably make the various material dissolves such as above-mentioned copolymer A or be distributed to the mixed solution obtained in solvent.As described solvent, the solvent identical with above-mentioned organic solvent can be used.
As described dispersion machine, such as, preferably can use the dispersion machine that can use as pulverizer.Such as, commercially available homogeneous mixer, sand mill, ball mill etc. can be used.In addition, also can be used in the device that with the addition of blending dispersion granulated glass sphere etc. in the container with stirrer, blending dispersion is carried out to described mixed solution.
anti-fouling treatment method, antifouling coat and coated article
Anti-fouling treatment method of the present invention uses above-mentioned antifouling paint compositions to form antifouling coat at the body surface of film to be formed.According to anti-fouling treatment method of the present invention, to dissolve gradually from surface due to described antifouling coat thus film coated surface is constantly updated, therefore, it is possible to realize the attachment preventing aquatic fouling organism.In addition, after film dissolves, anti-fouling effect can be played by again applying above-mentioned composition to continue.
As the object of film to be formed, can enumerate such as: structures etc. in boats and ships (particularly hull bottom), fishery apparatus, water.As fishery apparatus, can enumerate such as: cultivation with or fixing fishing net, fishing net accessory etc. for the buoy, rope etc. of this fishing net.As structures in water, can enumerate such as: power house water pipe, bridge, bay equipment etc.
Antifouling coat can be formed by the body surface (in whole or in part) above-mentioned antifouling paint compositions being coated to film to be formed.
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 coating, make it dry.Drying temperature is room temperature.Time of drying suitably can set according to the thickness etc. of film.
Use the antifouling coat of the present invention that above-mentioned antifouling paint compositions is formed, play film dissolution rate and the Physical properties of coating film of appropriateness in the seawater, Surface Renewal steady in a long-term can be maintained, can effectively play desired anti-fouling effect.In addition, there is the advantage of the excellent recoat performance that can play film.
The thickness of described antifouling coat suitably can set according to the route speed of the kind of the object of film to be formed, boats and ships, seawater temperature etc.Such as, when the object of film to be formed is the hull bottom of boats and ships, the thickness of antifouling coat is generally 50 ~ 500 μm, is preferably 100 ~ 400 μm.
Antifouling coat of the present invention has the hardness of appropriateness.That is, antifouling coat of the present invention has the hardness of the degree that the film exceptions 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.
Coated article of the present invention, owing to having film dissolution rate by improving the appropriateness in seawater and Physical properties of coating film thus the Surface Renewal of long-term stability and the excellent film of recoatability, is thus preferably used as structures etc. in above-mentioned boats and ships (particularly hull bottom), fishery apparatus, water.
Such as, when the hull bottom surface of boats and ships defines above-mentioned antifouling coat, to dissolve gradually from surface due to described antifouling coat thus film coated surface is constantly updated, therefore, it is possible to realize the attachment preventing aquatic fouling organism.
And described antifouling coat can suitably suppress hydrolysis rate.Therefore, these boats and ships can maintain antifouling property for a long time, such as, even if in berthing, equipment during etc. stationary state under, also there is attachment and the accumulation of aquatic fouling organism hardly, therefore, it is possible to play anti-fouling effect for a long time.
In addition, even if still substantially do not occur crackle or peel off on the antifouling coat of long-time rear surface.Therefore, the operation of film etc. is newly formed after there is no need to remove film completely again.Therefore, by directly again applying above-mentioned antifouling coat composition, effectively antifouling coat can be formed.Thereby, it is possible to continue to maintain anti-fouling effect with low cost easily.
[embodiment]
Below, the further feature clearly of the present invention such as embodiment is shown.But the present invention is not by the restriction of these embodiments.
Each Production Example, the % compared in Production Example, embodiment and comparative example represent quality %.Viscosity is the measured value at 25 DEG C, the value obtained by B shape viscometer.Weight-average molecular weight (Mw) is the value (polystyrene conversion value) obtained by GPC.The condition of GPC is as described below.
Device TOSOH Co., Ltd HLC-8220GPC
Chromatographic column TSKgel SuperHZM-M (TOSOH Co., Ltd's system) 2
Flow 0.35mL/ minute
Detector RI
Chromatographic column thermostatic bath temperature 40 DEG C
Elutriant THF
Heating lingering section is at 125 DEG C, heat the value obtained after 1 hour.
In addition, the unit of the use level of each composition in table 1 is g.
production Example 1 (manufacture of copolymer solution A-1)
Dimethylbenzene 230g is loaded in the flask with thermometer, reflux exchanger, stirrer and dropping funnel, in a nitrogen atmosphere, stir at 100 ± 2 DEG C while, with the mixed solution of 1 hour dropping vinylformic acid t-butyidiphenylsilyl ester 275g, methyl methacrylate 175g, vinylformic acid-2-methoxy acrylate 50g and peroxide-2-ethyl hexanoic acid tert-butyl 4g (initial stage interpolation).Then, in synthermal lower stirring after 2 hours, within every 2 hours, add peroxide-2-ethyl hexanoic acid tert-butyl 1g (adding afterwards) 3 times, after terminating polyreaction, add dimethylbenzene 270g and make it dissolve, obtaining the copolymer solution A-1 containing three organic silicomethane esters thus.
The viscosity of A-1, heating lingering section, Mw are shown in table 1.
production Example 2 ~ 6 (manufacture of copolymer solution A-2 ~ A-6)
Use organic solvent, monomer and polymerization starter shown in table 1, carry out polyreaction with the operation identical with Production Example 1, obtain copolymer solution A-2 ~ A-6 thus.The viscosity of obtained each copolymer solution, heating lingering section, Mw are shown in table 1.
[table 1]
production Example 7 (manufacture of copolymer solution A-7)
PGM (propylene glycol monomethyl ether) 50g and dimethylbenzene 130g is loaded in the four-hole boiling flask with thermometer, reflux exchanger, stirrer and dropping funnel, then, in a nitrogen atmosphere, stir at 100 ± 2 DEG C while, with the mixed solution of 1 hour dropping PGM25g, dimethylbenzene 25g, vinylformic acid t-butyidiphenylsilyl ester 275g, methyl methacrylate 125g, methacrylic acid-2-methoxy acrylate 75g, zinc methacrylate 25g and peroxide-2-ethyl hexanoic acid tert-butyl 4g (initial stage interpolation).After dropping, at 100 ± 2 DEG C, carry out 2 hours polyreactions.Then, at the temperature of 100 ± 2 DEG C while stirring reaction liquid, within every 2 hours, add peroxide-2-ethyl hexanoic acid tert-butyl 1g (adding afterwards) and carry out polyreaction 3 times, then, add dimethylbenzene 270g and make it dissolve, obtaining the copolymer solution A-7 containing carboxylate metal ester thus.The heating lingering section of the varnish obtained is 51.7%, viscosity is 490cps/25 DEG C.
production Example 8 (manufacture of copolymer solution A-8)
In the four-hole boiling flask with thermometer, reflux exchanger, stirrer and dropping funnel, add dimethylbenzene 325g and propyl carbinol 100g and heat after 100 ~ 110 DEG C, dripping the mixing solutions of vinylformic acid t-butyidiphenylsilyl ester 275g, vinylformic acid 10g, ethyl propenoate 75g, cyclohexyl methacrylate 90g, Diisopropyl azodicarboxylate 12g (initial stage interpolation) in a nitrogen atmosphere with 4 hours.After dropping terminates, 110 DEG C of insulations extremely through 30 minutes, dripped the mixing solutions of dimethylbenzene 50g, propyl carbinol 25g and Diisopropyl azodicarboxylate 2.5g (adding afterwards) with 1 hour, through 2 hours after insulation to dropping.
Then, dropping funnel is replaced with decanting vessel, add venus crystals 25.2g, naphthenic acid 50g and deionized water 50g, be heated to 100 DEG C, the acetic acid generated except dereaction and water, obtain the copolymer solution A-8 containing carboxylate metal ester.The heating lingering section of the varnish obtained is 51.5%, viscosity is 330cps/25 DEG C.
production Example 9
Dimethylbenzene 100g and propyl carbinol 20g is added in the flask with thermometer, reflux exchanger, stirrer and dropping funnel, heat after 100 ~ 110 DEG C, in a nitrogen atmosphere with the mixing solutions dripping vinylformic acid 25.7g, ethyl propenoate 57.8g, methyl methacrylate 16.5g and Diisopropyl azodicarboxylate 3g for 4 hours.110 DEG C of insulations to drip terminate after through 30 minutes, dripped the mixing solutions of dimethylbenzene 20g, propyl carbinol 10g and Diisopropyl azodicarboxylate 0.5g with 1 hour, through 2 hours after insulation to dropping.
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 DEG C, the propionic acid generated except dereaction and water, reaction end is determined by the acetic acid quantitatively distillated in solvent.After reaction terminates, add dimethylbenzene to regulate solids component, obtain the copolymer solution B-1 containing carboxylate metal ester.The heating residual component of the varnish obtained is 50.3%, weight-average molecular weight is 8000, viscosity is 185cps/25 DEG C.
relatively Production Example 1 ~ 4
Use the organic solvent shown in table 1, monomer and polymerization starter, carry out polyreaction with the operation identical with Production Example 1, obtain copolymer solution C-1 ~ C-4 thus.The viscosity of obtained each copolymer solution, heating lingering section, Mw are shown in table 1.
embodiment 1 ~ 19 and comparative example 1 ~ 4 (manufacture of coating composition)
The composition shown in table 2 is coordinated, by manufacturing coating composition with the granulated glass sphere blending dispersion of diameter 1.5 ~ 2.5mm with the ratio (quality %) shown in table 2.
[table 2]
test example 1 (stability test of coating)
By the coating composition obtained in embodiment 1 ~ 19 and comparative example 1 ~ 4 load 100ml the zinc-plated iron flask of wide-mouth in and seal, in the thermostatted of 45 DEG C preserve 3 months, then, by the viscosity of this coating composition of B shape viscometer determining.
Evaluated by following method.
◎: the situation (coating state is unconverted situation substantially) that the viscosity B coefficent of coating is less than 500mPas/25 DEG C
Zero: the viscosity B coefficent of coating is the situation (a little the situation of thickening) of 500 ~ 5000mPas/25 DEG C
△: the viscosity B coefficent of coating is greater than the situation (situation of larger thickening) of 5000mPas/25 DEG C ~ 100000mPas/25 DEG C
×: be changed to the unmeasured situation of dope viscosity (becoming the situation of gelatinous situation or solidification)
Show the result in table 3.
As shown in Table 3, the storage stability of the coating using coating composition of the present invention (embodiment 1 ~ 19) to be formed is excellent.
And on the other hand, the coating using the coating composition of comparative example 4 to be formed preserves larger thickening after 3 months at 45 DEG C.
[table 3]
[table 3]
test example 2 (the tack test of film)
The tack test of film is carried out according to the regulation of JIS K-5600-5-6.Specifically, in the mode making the thickness of dry coating be about 100 μm, latten (75 × 150 × 2mm) after blast finishing above applies the coating composition obtained by embodiment 1 ~ 19 and comparative example 1 ~ 4, and at 40 DEG C, make it after dry 1 day, carries out tack test.
Evaluated by following method.
Mark with I-go board reticulation each in length and breadth 11 cuts reaching substrate (latten) with on cutter film after the drying, make the grid that 100 2mm are square.On these 100 grid, paste scotch tape (meter Qi Bang Co., Ltd. glue bandwidth 24mm) in bubble-free mode, the one end pinching adhesive tape with hand is peeled off fast, the attachment state of visual investigation film.
◎: the number of the I-go board grid of stripping is the situation of 70 ~ 100
Zero: the number of the I-go board grid of stripping is the situation of 40 ~ 69
△: the number of the I-go board grid of stripping is the situation of 20 ~ 39
×: the number of the I-go board grid of stripping is the situation of 0 ~ 19
Show the result in table 3.
As shown in Table 3, the film using coating composition of the present invention (embodiment 1 ~ 19) to be formed is gluing securely for latten.
test example 3 (pliability test of film)
In the mode making the thickness of dry coating be about 100 μm, latten (75 × 150 × 2mm) after blast finishing above applies the coating composition obtained by embodiment 1 ~ 19 and comparative example 1 ~ 4, and at 40 DEG C, make it after dry 1 day, confirm that bending is the state of the film of 90 degree by visual inspection.
Evaluated by following method.
◎: situation about substantially not cracking
Zero: the situation producing fine crack
△: the situation producing larger crackle
×: the situation that the part of film is easily peeled off
Show the result in table 3.
As shown in Table 3, the film using coating composition of the present invention (embodiment 1 ~ 19) to be formed substantially does not crack in pliability test.In addition, be that for the embodiment 5 of 80 quality %, bendability is deteriorated a little compared with other embodiment for the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer.
test example 4 (whirl test)
Tank central authorities with the mode that can be rotated by engine install diameter 515mm, height 440mm swing roller.In addition, there is also mounted the refrigerating unit for keeping seawater temperature constant and the pH two-position controller for keeping the pH of seawater constant.
Two panels test board is made according to following method.
First, the mode being about 50 μm to make dried thickness applies rust proof paint (polyethylene kind A/C) and makes it dry on hard vinyl chloride plate (75 × 150 × 1mm), forms anti-rust coating thus.Then, on above-mentioned anti-rust coating respectively, the coating composition obtained by embodiment 1 ~ 19 and comparative example 1 ~ 4 is applied in the mode making dried thickness be about 300 μm.Make obtained coating at 40 DEG C dry 3 days, make the test board that there is thickness and be about the dry coating of 300 μm thus.
A slice in obtained test board is fixed on the swing roller of the swivel arrangement of said apparatus to make the mode of itself and contact with sea water, makes rotary drum rotating with the speed of 20 nautical miles/hour.Therebetween, the temperature of seawater is remained on 25 DEG C, pH is remained on 8.0 ~ 8.2, change a seawater weekly.
By laser focusing displacement gauge to the initial film thickness of each test board and after on-test the residual thickness of every 3 months measure, the coating thickness dissolved by its mathematic interpolation, and the film meltage (μm/month) obtaining each month thus.It should be noted that, described mensuration was carried out 24 months, often carried out the calculating of described film meltage through 12 months.
In addition, dry whirl test terminates the test board of rear (after 24 months), the then each film coated surface of visual inspection, evaluates the state of film.
Evaluated by following method.
◎: complete N/R situation
Zero: the situation of slightly visible hair crackings
△: visible hair crackings on whole film
×: visible larger crackle on film, steep or the abnormal situation such as to peel off
Show the result in table 4.
As shown in Table 4, the film meltage in the seawater using coating composition of the present invention (embodiment 1 ~ 19) to be formed is every 1 month about 3 ~ 5 μm (annual).And known, the film dissolution rate of the film using coating composition of the present invention to be formed is suppressed to a certain extent, therefore dissolves steadily in the long term.And having excellent water-resistance of the film using coating composition of the present invention to be formed, does not crack and hair crackings etc., therefore, it is possible to long term maintenance antifouling property.In addition, be that for the embodiment 5 of 80 quality %, the painting membrane stage compared with other embodiments after 24 months is deteriorated a little for the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer.
On the other hand, the film dissolution rate of the film using the coating composition of comparative example 3 to be formed is very little, therefore can not play sufficient antifouling property.And due to film really up to the mark, poor water resistance, the film such as to crack and peel off abnormal in test.Film dissolution rate in the seawater of the film using the coating composition of comparative example 4 to be formed is passed in time and is become large, therefore can not play antifouling property for a long time.And, be with regard to the comparative example 1 of 54 quality % with regard to the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer, although the painting membrane stage after 24 months is excellent, but the average film meltage after 12 ~ 24 months with initial stage ~ the average film meltage of 12 months compared with reduce largely, known film dissolution rate is unstable.And, be with regard to the comparative example 2 of 85 quality % with regard to the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer, film state difference after 24 months, and the average film meltage after 12 ~ 24 months with initial stage ~ the average film meltage of 12 months compared with increase largely, known film dissolution rate is unstable.
[table 4]
[table 4]
test example 5 (antifouling test)
In the mode making the thickness of dry coating be about 200 μm, the coating composition obtained is coated to two surfaces of hard vinyl chloride plate (100 × 200 × 2mm) by embodiment 1 ~ 19 and comparative example 1 ~ 4.By making obtained coating under room temperature (25 DEG C) dry 3 days, make the test board that there is thickness and be about the dry coating of 200 μm thus.This test board is impregnated into 1.5m place under the sea in owase city of triple county, and the stained observation carrying out 24 months to the test board caused by dirt settling.
Evaluated by the state of visual observation film coated surface, judge according to following standard.
◎: the attachment not having the fouling organism such as shellfish and algae, and substantially there is no biological clay.
Zero: the attachment not having the fouling organism such as shellfish and algae, although and biological clay thinner (can see the degree of coated surface) adheres to the level that can dab removing with bristle.
△: the attachment not having the fouling organism such as shellfish and algae, but biological clay is can not see the thicker attachment of the degree of coated surface, namely use bristle to exert oneself level that wiping can not remove.
×: the level of the fouling organism such as shellfish and algae attachment,
Show the result in table 5.
As shown in Table 5, on the film using coating composition of the present invention (embodiment 1 ~ 19) to be formed, after test in 36 months, there is no the attachment of the fouling organism such as shellfish and algae.Wherein, the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer be the embodiment 1 of 55 quality % or 80 quality % and embodiment after 5,36 months antifouling property reduce a little.On the other hand, this ratio is the embodiment of 60 ~ 70 quality %, and after 36 months, antifouling property does not reduce.In addition, comprise the embodiment 7 ~ 8 of the multipolymer containing carboxylate metal ester and embodiment after 18 ~ 19,36 months antifouling property reduce a little.On the other hand, do not comprise the embodiment of the multipolymer containing carboxylate metal ester, after 36 months, antifouling property does not reduce.
In addition, the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer is used to be on the film of coating composition formation of the comparative example 1 of 54 quality %, with thinner degree settled organism foundry loam after 24 months, 36 months postadhesion fouling organisms.In addition, the ratio of the vinylformic acid t-butyidiphenylsilyl ester in multipolymer is comparative example 2,24 biological clays that month postadhesion is thinner of 85 quality %, the biological clay that 36 months postadhesion are thicker.In addition, on the film using the coating composition of comparative example 3 and 4 to be formed, flood after 24 months, the attachment of the fouling organism such as shellfish and algae is severe.
[table 5]
[table 5]
Claims (4)
1. an antifouling paint compositions, containing the multipolymer that obtains by making ethylene unsaturated monomer (b) 20 ~ 45 quality % copolymerization beyond vinylformic acid t-butyidiphenylsilyl ester monomer (a) 55 ~ 80 quality % and described monomer (a), described monomer (b) is for being selected from least one monomer in the group that is made up of methyl methacrylate, (methyl) butyl acrylate and (methyl) vinylformic acid-2-methoxy acrylate.
2. antifouling paint compositions as claimed in claim 1, also containing at least one be selected from the group that is made up of rosin, rosin derivative and their metal-salt.
3. an antifouling paint compositions multipolymer, obtain by making ethylene unsaturated monomer (b) 20 ~ 45 quality % copolymerization beyond vinylformic acid t-butyidiphenylsilyl ester monomer (a) 55 ~ 80 quality % and described monomer (a), described monomer (b) is for being selected from least one monomer in the group that is made up of methyl methacrylate, (methyl) butyl acrylate and (methyl) vinylformic acid-2-methoxy acrylate.
4. a coated article, its surface has the antifouling coat using the antifouling paint compositions described in claim 1 to be formed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-188583 | 2010-08-25 | ||
| 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 |
| 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 |
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| CN103080249A CN103080249A (en) | 2013-05-01 |
| CN103080249B true CN103080249B (en) | 2015-08-05 |
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| Country | Link |
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| JP (1) | JP4769331B1 (en) |
| CN (1) | CN103080249B (en) |
| SG (1) | SG187606A1 (en) |
| WO (1) | WO2012026237A1 (en) |
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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 |
| EP2935288B1 (en) | 2012-12-19 | 2016-10-19 | Jotun A/S | 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 |
| JP6690780B2 (en) | 2017-03-27 | 2020-04-28 | 三菱ケミカル株式会社 | Porous membrane, membrane module, water treatment device, and method for producing porous membrane |
| CN111886304B (en) * | 2018-04-20 | 2022-02-01 | 日东化成株式会社 | Antifouling coating composition |
| JP6472562B1 (en) * | 2018-07-03 | 2019-02-20 | 日本ペイントマリン株式会社 | Vehicle resin for antifouling paint composition and antifouling paint composition containing the same |
| JP7287648B2 (en) * | 2019-03-15 | 2023-06-06 | 日東化成株式会社 | antifouling paint 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 |
| GB2592921B (en) | 2020-03-09 | 2024-04-17 | Jotun As | Hull cleaning robot |
| GB202107159D0 (en) | 2021-03-23 | 2021-06-30 | Jotun As | Monitoring a vessel |
| 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 |
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| JPH11116857A (en) * | 1997-10-17 | 1999-04-27 | Nof Corp | Coating materiel composition |
| JP3455671B2 (en) * | 1998-03-30 | 2003-10-14 | 日東化成株式会社 | Antifouling paint composition |
| JP3693501B2 (en) * | 1998-07-06 | 2005-09-07 | 日東化成株式会社 | Antifouling paint composition |
| WO2001081489A1 (en) * | 2000-04-24 | 2001-11-01 | Basf Nof Coatings Co., Ltd. | Antifouling coating material, antifouling coating film, submerged structure, and antifouling method |
| JP4064100B2 (en) * | 2001-12-13 | 2008-03-19 | 日東化成株式会社 | Anti-fouling composition for fishing nets, fishing nets coated with the anti-fouling composition for fishing nets, and anti-fouling method for fishing nets using the anti-fouling composition for fishing nets |
| EP1539861A1 (en) * | 2002-07-10 | 2005-06-15 | Sigmakalon Services B.V. | Process for the preparation of polyorganosilylated carboxylate monomers or polymers thereof |
| RU2476469C2 (en) * | 2008-12-19 | 2013-02-27 | Нитто Касей Ко., Лтд. | Antifouling coating composition, antifouling film coating obtained from said composition, coated article having film coating on surface, and treatment method for imparting antifouling properties by forming film coating |
| JP4521589B2 (en) * | 2008-12-19 | 2010-08-11 | 日東化成株式会社 | Antifouling paint composition, antifouling coating film formed using the composition, coated product having the coating film on the surface, and antifouling treatment method for forming the coating film |
-
2010
- 2010-08-25 JP JP2010188583A patent/JP4769331B1/en not_active Expired - Fee Related
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2011
- 2011-07-14 WO PCT/JP2011/066155 patent/WO2012026237A1/en active Application Filing
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| JP4769331B1 (en) | 2011-09-07 |
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| SG187606A1 (en) | 2013-03-28 |
| JP2012046600A (en) | 2012-03-08 |
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