CN101415330A - Anti-biofouling agent, anti-fouling coating, anti-fouling treatment method, and anti-foulingly treated material - Google Patents
Anti-biofouling agent, anti-fouling coating, anti-fouling treatment method, and anti-foulingly treated material Download PDFInfo
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- CN101415330A CN101415330A CNA2007800126065A CN200780012606A CN101415330A CN 101415330 A CN101415330 A CN 101415330A CN A2007800126065 A CNA2007800126065 A CN A2007800126065A CN 200780012606 A CN200780012606 A CN 200780012606A CN 101415330 A CN101415330 A CN 101415330A
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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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
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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
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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
- A01N25/12—Powders or granules
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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
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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Abstract
The object is to provide an anti-biofouling agent, an anti-fouling coating, an anti-fouling treatment method and an anti-foulingly treated material, each of which utilizes a polymer particle having an anti-biofouling group. Disclosed is a novel anti-fouling particle (an anti-biofouling agent) which is innoxious to the environment and edible marine products and has an excellent anti-fouling effect. Also disclosed are: an anti-fouling coating, a method for anti-fouling treatment of a substrate and an anti-foulingly treated material, each of which utilizes the anti-fouling particle.
Description
Technical field
The present invention relates to biological antifouling composition, antifouling paint, anti-fouling treatment method and antifouling processing article, in more detail, the anti-fouling treatment method and the antifouling processing article that relate to the antifouling treatment agent that constitutes by the polymer particle with aquatic biological soil resistance (preventing the character of aquatic biological attachment) (following only be called sometimes " soil resistance particle "), the antifouling paint that uses this antifouling treatment agent, base material.
Background technology
For marine vessel etc., under sail, the biology of perching in the seawater can be attached on the hull bottom face and shipboard face in seawater not.Therefore various disadvantages are arranged: because these biologies that adhere to and the frictional resistance between seawater, the headway of boats and ships reduces, and the consumption of fuel also increases, and in addition, the repairing frequency of hull bottom etc. also increases, and also produces very big loss etc. economically.In addition, even in the plants of marine fishes, equally also adhering to marine organisms on the separation net that use the there, because the peristome of net reduces, the inflow of fresh seawater etc. is hindered, and has influenced the growth of cultured fishes.
As life in seawater, be attached to the biology of hull or marine works, very many biologies are arranged, as aquatic animals, barnacle class, ectoproctous polyzoa, セ Le Block ラ class, ascidian etc. are arranged; As plant, can list seaweeds, particularly barnacle class, seaweeds can be enumerated as representative example.
In order to prevent adhering to of these aquatic biologies that the coating that will contain tin compound or copper compound uses as ship bottom antifouling paint all the time.Yet, these tin compounds or copper compound can be from filming stripping to seawater, cause the pollution of the pollution of environment and fish, shellfish, marine alga etc., pollute and also can be extended to, thereby become the big social concern of unhealthful grade with the mankind of marine product as food.
Summary of the invention
The present invention In view of the foregoing proposes.The inventor etc. have studied the mechanism of growing nonparasitically upon another plant, grow and coming off of aquatic biology to hull bottom and netting twine etc.The effect of physiological, the physics of the aquatic biology that utilizations such as the inventor are found by above-mentioned research, and be conceived to and will can not assign to use as antifouling one-tenth by the non-stripping property organic material of stripping in seawater.The object of the present invention is to provide a kind of to environment and edible aquatic products safety and have the anti-fouling treatment method and the antifouling processing article of the novel biological antifouling composition of excellent anti-fouling effect, the antifouling paint that uses this biology antifouling composition, base material.
The inventor etc. have carried out further investigation repeatedly in order to address the above problem, found that, polymer particle is safe organic substance, be to contain the filming when being immersed in the seawater for a long time of this particle, can the material of stripping in water even come off also not with the form of particle, therefore, do not pollute the environment, even be safe to aquatic resources yet.The inventor etc. have found following phenomenon, thereby have finished the present invention: by making these particles have soil resistance and this particle being existed with high density in the film coated surface that contains this soil resistance particle, this is filmed and makes the minimizing of growing nonparasitically upon another plant of aquatic biology; In addition, the growth of the aquatic biology that adheres to by obstruction is peeled off aquatic biology as time passes from substrate surface; In addition, by the self gravitation of the aquatic biology that adheres to, and then add and the physical actions such as mobilization force of seawater aquatic biology is come off from base material.
That is, the invention provides a kind of biological antifouling composition, it is characterized in that, constitute by polymer particle with biological soil resistance group.
In the invention described above, biological soil resistance group be preferably be selected from hydrophilic radical (a), anionic property and cationic the two ionic group (following only be called sometimes " double ion group ") (b) and biology avoid in the keeping away property group (c) at least a kind, above-mentioned hydrophilic radical (a) is preferably at least a kind that is selected from anionic property group, cationic group, nonionic group, anionic/nonionic amphiprotic group, cationic/nonionic amphiprotic group and anion/cationically ampholytic group.
In addition, in the invention described above, above-mentioned double ion group (b) preferably is selected from the anionic property group, the anionic/nonionic amphiprotic group, the cationic group, the anionic property group in cationic/nonionic amphiprotic group and anion/cationically ampholytic group and the combination of cationic group, above-mentioned biology is avoided keeping away property group (c) and is preferably and is selected from aliphatic, alicyclic or aromatic amino, quaternary ammonium group, pyridine radicals, pyridine radicals, in phenol hydroxyl and the polyethylene glycol groups at least a kind, in addition, above-mentioned soil resistance particle also can be the mixture with polymer particle of different soil resistance groups.
In addition, the invention provides a kind of antifouling paint, it is characterized in that, form material and form by in the polymer particle (soil resistance particle) of the invention described above, cooperating to film.In this antifouling paint, the soil resistance particle (A) and the fit quality ratio that forms material (B) of filming are preferably A:B=95:5～5:95.
In addition, the invention provides a kind of biological anti-fouling treatment method of base material, it is characterized in that, with the biological antifouling composition of the invention described above or antifouling paint be coated with on the base material, impregnation or in base material, mix; And provide a kind of biology antifouling processing article, it is characterized in that it is the article that carried out biological antifouling processing with above-mentioned processing method.
The tin compound or the copper compound that use in the antifouling paint in the past always, their ion slowly stripping in seawater, act on aquatic biology, have and hinder of the effect of aquatic biological attachment, also make it the function that death comes off even perhaps have to adhere in hull bottom etc.Relative with it, aquatic biological antifouling composition of the present invention (soil resistance particle) is avoided the soil resistance polymer particle of keeping away function and is constituted by having biology especially.When these soil resistance particulate materials are immersed in the seawater in filming for a long time, though with the form of particle come off also not can stripping in water, therefore free from environmental pollution, be safe, in addition, also can not pollute fish or edible aquatic products such as shellfish, marine alga, be safety and sanitation.
The mechanism that has anti-fouling effect although soil resistance particle of the present invention does not have soluble heavy metal ions is not clear fully as yet.But, can think that its mechanism and aquatic biology are relevant to the physiological action and the physical action of growing nonparasitically upon another plant, grow, coming off etc. of hull bottom etc.Contain the coating of soil resistance particle and filming of forming in use, as seen following trend arranged: exist by making above-mentioned soil resistance particle be exposed to the surface of filming, make of the grow nonparasitically upon another plant minimizing of aquatic biology to filming, in addition, the cell of the aquatic biology that obstruction is adhered to is grown or is made its death, thereby the aquatic biology that adheres to is peeled off from substrate surface.Also find in addition, as its result, even other aquatic biological attachment on this ruined aquatic biology, are newly adhered to and the aquatic biology piled up also can and then add the physical action such as mobilization force of seawater and comes off from base material because of himself gravity.
Embodiment
Below enumerate the best mode that is used to carry out an invention the present invention is described in further detail.As the polymer of soil resistance particle of the present invention, can use known addition polymer, contract and polymer that polymer, heat curing copolymer etc. are all.As addition polymer, can list vinyl-based, dienes, (methyl) acrylic compounds etc.; As contracting and polymer, can enumerate ester output class, amide-type, carbamates etc.; As heat curing copolymer, can list the polymer of carbamide class, P-F class, epoxy-amine class, isocyanates-alcohols etc.
Soil resistance particle of the present invention has in its surface and is selected from hydrophilic radical (a), double ion group (b) and biology and avoids at least a kind of group in the keeping away property group (c).Formed when filming by the coating that contains this soil resistance particle, aquatic biology is difficult to be attached to the film coated surface that contains this soil resistance particle.Below illustrate to have and be selected from soil resistance particle, its synthetic method and their preparation process of mixture that above-mentioned hydrophilic radical (a), double ion group (b) or biology are avoided the group in the keeping away property group (c).
(1) surface is by the soil resistance particle of the polymer chain modification of hydrophilic radical or possess hydrophilic property group.
This soil resistance particle forms moisture film or moisture dissolved glue film or gel mould (following only be referred to as sometimes " moisture film ") on the film coated surface that is formed by the coating that contains this soil resistance particle, can stop aquatic biology adhering to its surface.
As the hydrophilic radical of above-mentioned soil resistance particle, can list at least a kind that is selected from anionic property group, cationic group, nonionic group, anionic/nonionic amphiprotic group, cationic/nonionic amphiprotic group and anion/cationically ampholytic group.
As above-mentioned anionic property group, can list sulfonic group, carboxyl, sulfate group, phosphate-based etc.As above-mentioned cationic group, can list primary, secondary, uncle is amino, quaternary ammonium group and pyridine radicals, pyridine radicals etc.As above-mentioned nonionic group, can list amide groups, polyethylene glycol groups etc.Polymer with these hydrophilic radicals is meant polymerization (copolymerization) thing that is formed by the monomer that has above-mentioned hydrophilic radical in the molecule.
Above-mentioned soil resistance particle can be synthetic with known method.The monomer that is used for synthetic soil resistance particle also can use macromonomer except common monomer.Polymerisation medium can be selected organic solvent, water-organic solvent mixed solvent or water.As the polymerization of addition polymer, be fit to the known polymerization of the form of soil resistance particle, for example polymerisation in solution, emulsion polymerization, suspension polymerisation, no soap (soap free) polymerization all can be used.Copolymer can be any one in random, block and the graft copolymer.As the soil resistance particle, also can be single particle or nuclear (core), shell (sheath) type particle.The representational synthetic method of above-mentioned soil resistance particle below is described.
(1.1) make monomer and the monomer of possess hydrophilic property group or the macromonomer copolymerization of possess hydrophilic property group as primary raw material, thus the method for giving soil resistance particle hydrophilic radical.
(1.2) make as the monomer of primary raw material and monomer or macromonomer copolymerization with the group that can be easy to change into hydrophilic radical, the group that can be easy to change into hydrophilic radical then changes the method for hydrophilic radical into.
(1.3) make as the monomer of primary raw material in advance with the monomer copolymerization with reactive group, make the method for the reactive compounds reaction of above-mentioned reactive group and possess hydrophilic property group then.
(1.4) the synthetic in advance particle that forms core, and then the monomer that will form the hydrophilic radical of sheath or have a group that can change hydrophilic radical into contains the surface that is immersed in above-mentioned particle and make its polymerization is as required with above-mentioned (1.2) method of operating equally.
As monomer, for example can list styrene sulfonic acid, vinyl sulfonic acid etc. with above-mentioned hydrophilic radical; The half ester of (methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid, these dicarboxylic acids or half amide etc.; (methyl) acrylic acid ethyl sulfuric acid ester; 2-(methyl) acryloyl ethyl acid phosphoric acid ester, (methyl) acrylic acid (dimethylaminoethyl) ester, (methyl) acrylic acid (diethyllaminoethyl) ester, trimethyl ammonium ethyl (methyl) acrylate hydrochloride, 3-trimethyl ammonium (2-hydroxyl)-propyl group (methyl) acrylate hydrochloride, vinylpyridine, vinylpyridine thiamine hydrochloride etc.
As monomer, can list methacrylic acid sulphur ethylamino ethyl ester, methacrylic acid phosphocholine ethyl ester, methacrylic acid carboxymethyl methylamino ethyl ester etc. with double ion group; Maleic acid list (dimethylaminoethyl) ester, itaconic acid list (dimethylaminoethyl) ester; (methyl) acrylic acid, maleic acid, itaconic acid etc. have hydroxyethyl ester, glyceride, macrogol ester, methoxy poly (ethylene glycol) ester of the monomer of carboxyl etc.
Having with the graft copolymer chain of macromonomer with a plurality of hydrophilic radicals or polyalkylene oxide chain (carbon number is 2～3) serves as that base comes the soil resistance particle of the polymer chain of bonding hydrophilic radical at interval, owing to can only make such hydrophilic polymer chain stripping in seawater, therefore be easy to form moisture sol layer or gel layer in film coated surface, thereby the thickness of moisture film increases, the soil resistance excellence.
The group that can change hydrophilic radical easily into as explanation in above-mentioned (1.2) can list anhydride group, low alkyl group ester group etc., as monomer, for example can list maleic anhydride, itaconic anhydride, (methyl) methyl acrylate etc.
The reactive group that reactive group or reactive monomer had as the compound of reaction of the possess hydrophilic property group of explanation in above-mentioned (1.3) for example can list anhydride group, acid halide group, low alkyl group ester group, epoxy radicals, NCO, methylol, methoxy, halogenated methyl etc.; Hydroxyl, amino, carboxyl etc.As monomer, for example can list maleic anhydride, itaconic anhydride, (methyl) acryloyl chloride, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid (glycidyl) ester, allyl glycidyl ether, (methyl) acrylic acid ethyl isocyanate, isopropenyl phenylene methyl isocyanate, methylol (methyl) acrylamide, methoxy (methyl) acrylamide, 1-chloro-4-methyl-benzene etc. with these reactive groups; Vinyl acetate (changing vinyl alcohol after the saponification into), (methyl) acrylic acid [hydroxy alkyl (C2～C6)] ester, (methyl) acrylic acid (dimethylaminoethyl) ester, (methyl) acrylic acid (diethyllaminoethyl) ester, (methyl) acrylic acid, maleic acid, itaconic acid etc.
In addition, as reactive compounds with above-mentioned hydrophilic radical, for example can list monochloro acetate, the monochloro valeric acid, glycolic acid, hydracrylic acid, the sulfo-glycolic acid, 6-caprolactone, various amino acidses, ethylene hydroxy sulfuric acid, acid sodium sulphite, sulfuric acid, sulfur trioxide, phosphoric acid, diethylamine, triethylamine, dimethylethanolamine, diethyl is for monoethanolamine, N, the N-diethyl ethylenediamine, N, N, N '-trimethyl ethylenediamine, N, N-diethyl-1, the 3-diaminopropanes, N, N-diethyl-1,3-diaminourea pentane, aniline, 4-amino-N, N-diethylaniline etc.
The preferable methods when method that makes hydrophilic monomer with above-mentioned group and known in the past hydrophobic monomer copolymerization is preparation soil resistance particle.As hydrophobic monomer, for example can list styrene, ethene, propylene, butadiene, isoprene, (methyl) acrylic acid aliphatic (C1～C30), aromatic series (C6～C15), ester ring type (hydrocarbon ester etc. of C6～C15).
In addition, as the multi-functional monomer of bringing cross-bond for the soil resistance particle, for example can list divinylbenzene, alkylidene (glycol (methyl) acrylate of C2～C4), poly-(alkylidene of C2～C30) (C2～C4) glycol (methyl) acrylate, pentaerythrite four (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, methylene bis acrylamide etc.
(2) the soil resistance particle that forms with the identical or different polymer particle of double ion base group modification.
Film by using this soil resistance particle to form, can give the film coated surface double ion, thereby stop aquatic biological attachment in filming.
The filming of soil resistance particle of containing double ion got this and filmed carry out immersion test in seawater, and the result shows aquatic biology to this trend of growing nonparasitically upon another plant and reducing of filming.In addition, the trend of finding to have the growth of the aquatic biology that adheres to be hindered and peeling off from substrate surface.It is positively charged amino that major part has this group that destroys the function of aquatic biological cell.On the other hand, aquatic biozone negative electrical charge.Therefore, assign to use as the antifouling composition one-tenth of coating by having imported amino soil resistance particle, the positively charged of filming, aquatic biology are attracted on this positively charged filming, on the other hand, by importing electronegative soil resistance particle, can obtain to make above-mentioned attraction disappearance or aquatic biology is had filming of repulsive force to filming.
In addition, contain soil resistance particle in filming with double ion group by making, can with the filming of contact with sea water in, anionic property group and cationic group are existed with very near distance.By making this double ion group approaching, both sides' ionic group is interacted, make with seawater in the bonding of soluble ions such as sodium ion, chlorion or the exchange of ionic dissociation take place continually, perhaps make film coated surface form high ion concentration environment etc., destroy the cell of the aquatic biology that adheres to by these influences, make the aquatic biological death that adheres to, thereby peel off from substrate surface.
As soil resistance particle, can list the polymer particle that sulphur ethylamino, phosphoric acid ethylamino, phosphocholine hydrochloric acid, carboxymethylamino, carboxyethyl amino, carboxymethyl pyridine radicals etc. have anionic property group and cationic group simultaneously with above-mentioned double ion group.The preparation of this soil resistance particle can be used the above-mentioned double ion monomer that has anionic property group and cationic group simultaneously.Perhaps, can be by bonding amino or bonding pyridine on the polychlorostyrene methyl styrene in the alternating polymer of poly-(maleic acid-1-chloro-4-methyl-benzene), form ionic complex by carboxylic acid, prepare water-fast soil resistance particle with adjacent maleic acid unit.
As the method for giving double ion, can list the identical method of method with above-mentioned (1) middle explanation to the soil resistance particle.And then, have the mixture of the two or more soil resistance particle of different ions by use, and by using the mixture of the soil resistance particle that has different ionic groups respectively, can make films has double ion.
(3) imported the biological soil resistance particle of avoiding keeping away property group.
Avoid keeping away property group by polymer particle is imported biology, can give the film coated surface that contains this particle the biology of aquatic biology is avoided keeping away property, thereby stop adhering to of aquatic biology.
By make have avoid keeping away property group polymer particle in filming, particularly expose in film coated surface and exist, can destroy the cell of the aquatic biology that adheres to, hindering films goes up the growth of aquatic biology, thereby the aquatic biology that adheres to is peeled off from substrate surface.
Avoid keeping away property group as the biology that is bonded on the polymer particle, can list amino, ammonium, pyridine radicals, pyridine radicals, phenylol or polyethylene glycol groups etc.
Specifically, for example can list positive decyl amino, dodecyl amino, aliphatic amino such as n-hexadecyl amino, alicyclic amino, N, N-dimethyl-n-octyl ammonium, N, N-dimethyl-positive decyl ammonium, N, N-dimethyl-dodecyl ammonium, N, N-dimethyl-n-hexadecyl ammonium etc., anilino-, aromatic series amino such as methoxybenzene amido, their ammonium, 4-octyl group anilino-, 4-nonyl benzene amido, aliphatic alkyl substituted aromatic amino such as 4-detergent alkylate amido, their ammonium, pyridine radicals, pyridine radicals, 4-octyl group pyridine radicals, 4-nonyl pyridine radicals, aliphatic alkyl substituted pyridinyls such as 4-dodecyl pyridine radicals, their pyridine radicals, phenylol, cresyl, phenol hydroxyls such as aminobenzene phenolic group and polyethylene glycol groups etc.
Have the polymer particle that these biologies are avoided keeping away property group even contain in filming, this group can not separate stripping in seawater yet, and therefore, preferred biology is avoided keeping away property group and linked by linking group and polymer particle.As giving the method that the polymer particle biology is avoided keeping away property, can list the same method of method with above-mentioned (1) middle explanation.
(4) the soil resistance particle that each functions of above-mentioned (1)～(3) is composited.
Mixture by the soil resistance particle modified with the soil resistance particle of avoiding at least 2 kinds of base group modifications in the keeping away property group (c) with above-mentioned hydrophilic radical (a), double ion group (b) and biology or with 1 functional group as antifouling become to assign to form film, can obtain to have the aquatic biological antifouling coating of compound anti-pollution function.
The average grain diameter (assay method is that dynamic light is dispersed method) of above soil resistance particle of the present invention is according to the differences of the purposes of antifouling paint or service condition and object aquatic animals etc. and difference, can not determine entirely, be generally 0.05～50 μ m, be preferably 0.1～10 μ m.If average grain diameter less than 0.05 μ m, thereby then the soil resistance particle can bury in filming and is difficult to expose to film coated surface the rough sledding that is difficult to bring into play as the characteristic of antifouling composition etc. is arranged.On the other hand, if average grain diameter surpasses 50 μ m, thus the rough sledding that has then that the physical propertys such as intensity of filming reduce, the concavo-convex increase resistance to water-flow of film coated surface increases, take place that particle comes off etc.
When the soil resistance particle of the invention described above is used as the composition of antifouling paint, be preferably by antifouling paint forms film in the soil resistance particle usually be the state that exposes to film coated surface.For example, as preferable methods, can list in antifouling paint with high concentration and add the soil resistance particle or make the relatively large method of the particle diameter of soil resistance particle etc.And then, form the film formation material of material by using to film from oneself's grinding (polishing) type of surface dissolution lentamente as coating, the soil resistance particle in filming is exposed successively to the surface.
As the above-mentioned formation material of filming, for example can list materials such as synthetic rubber resinoid, acrylic resin, vinyl-based resin, chlorinated rubber resinoid, epoxylite, polysiloxanes resinoid, fluorine-type resin etc. and their copolymer systems, mixing class.
Anti-fouling material of the present invention is by cooperating above-mentioned filming to form material (B) and form in above-mentioned soil resistance particle (A).The soil resistance particle (A) of the invention described above and the fit quality ratio that forms material (B) of filming are A:B=95:5～5:95, when making the soil resistance particle expose to film coated surface with high density, and preferred above-mentioned A:B=80:20～30:70.
By with soil resistance particle of the present invention or antifouling paint in coating on the base material, impregnation or in base material, mix (the inner interpolation), can carry out biological antifouling processing to base material, and obtain the antifouling processing article of aquatic biology.Antifouling paint of the present invention is identical with in the past antifouling paint purposes, for example can be used for marine vessel not in the covering with paint of the hull bottom face and the shipboard face of seawater, in addition, even in the plant of marine fishes, also can be used for purposes widely such as separation net.
In addition, except hull bottom and separation net etc., also use as the resin formed substance that is immersed in building in the seawater or material etc., or as fishnet or isolate synthetic fibers with net etc.For these article, use antifouling paint of the present invention the surface to be covered with paint, lacquer, colour wash, etc. or the method for impregnation, or all be excellent method to the method that soil resistance particle of the present invention is added in the inside of these synthetic resin articles or synthetic fibers goods.
When adding soil resistance particle of the present invention to the inside of base materials such as above-mentioned synthetic resin, preferably use the masterbatch of soil resistance particle.In addition, when add the inside of synthetic fibers, the preferred soil resistance dispersion of nano-particles liquid that is fit to spinning solution that uses.
As above-mentioned synthetic resin, can list known resins such as acrylic resin, polyvinyl resin, Corvic, synthetic rubber, polystyrene resin, ABS resin, nylon resin, mylar, polycarbonate resin.As synthetic fibers, can list known fibers such as polypropylene fibre, polyethylene fibre, polyacrylonitrile fibre, nylon fiber, polyester fiber.
In addition, antifouling paint of the present invention also can be used as the biological pollution at mould between the laundry of building or dwelling house etc., wash dishes, in the place of water such as pond, washing room, bathroom etc., or the antifouling paint of the blade of the air cleaner of dwelling house, hospital, communal facility etc. or packing material waits and uses.
Embodiment
Below enumerate embodiment and comparative example more specifically describes the present invention.Wherein, " part " in the literary composition or " % " expression quality criteria.
The synthetic embodiment of＜soil resistance particle 〉
[synthetic embodiment 1]
(1) prepare polymerizing reactor, its water-bath, agitator, monomer dropping device, reagent input port, counter-current cooler and nitrogen that has as heater is blown into mouth.In this polyplant, add 100 parts of entry, 342.5 parts of ethanol and, stir and make the polyacrylic acid stripping as 6 parts of the polyacrylic acid (mean molecule quantity is 250,000) of dispersion stabilizer.
Mix afterwards and add 0.75 part of 45 parts of styrene (St) and azodiisobutyronitrile (AIBN), under stream of nitrogen gas, stirred 8 hours in 70 ℃, carry out suspension polymerisation.The particle diameter of the polymer that obtains with dynamic light scattering determination, the result is about 1 μ m.
And then in this suspension polymerisation liquid, add the mixed liquor of 12.5 parts of 25 parts of 1-chloro-4-methyl-benzenes (CMS), divinylbenzene (DVB) and AIBN0.56 part, after the stirring, under stream of nitrogen gas,, obtain the surface and have the core-sheath type of reactive chloromethyl through crosslinked polymer particle in 70 ℃ of polymerizations 8 hours.Use centrifugal separator that polymer particle is filtered from polymerization reaction mixture and washs.The cross-linking polymer particle that obtains disperses (solid constituent is 21.6%) again in dimethylbenzene/n-butanol mixed solvent (75:25).Among each following synthetic embodiment, polymerisation and synthetic reaction also use device same as described above to carry out.
(2) 50% dimethylbenzene/n-butanol mixed solvent (75:25) solution of the diglycidyl ether (epoxide equivalent is 268) of adding polyethylene glycol (PEG) (average degree of polymerization is about 9) is 107.2 parts.To 41.2 parts of 50% dimethylbenzene/n-butanol mixed solvent (75:25) solution that wherein under 85～90 ℃, dripped octyl group aniline, and then under 90～115 ℃, stirred 4 hours through 3 hours.
Afterwards, 50% methyl iso-butyl ketone (MIBK) (MIBK) solution of diethylamine (DEA) was dripped through 3 hours under 50 ℃ for 15.0 parts, and then stir down at 50～55 ℃ and to make it reaction in 5 hours, carry out tertiary amineization.Acquisition is that the PEG of 3-(lignocaine) (2-hydroxyl) propyl group is arranged is the mixture solution (solid constituent is 51.8%) of the PEG derivative of main component for octyl group anilino-, another terminal bonding with an end.Confirm the carrying out of each elementary reaction with infrared spectrum.
(3) dispersion liquid of the core with chloromethyl-sheath type cross-linking polymer particle that obtains in the adding above-mentioned (1) in reaction vessel is 250 parts, add afterwards and contain 27.0 parts of dimethylbenzene/n-butanol mixed solvent (75:25) solution that the bonding that obtains has 13.5 parts in the PEG derivative of 3-(lignocaine) (2-hydroxyl) propyl group and 3-octyl group anilino-(2-hydroxyl) propyl group in above-mentioned (2), 70 ℃ of reactions 3 hours down, reacted 5 hours down at 80 ℃.
After the reaction, reactant liquor joined in 300 parts the ethanol, filter polymer particle, and use washing with alcohol.Unreacted PEG derivative is filtered, the cross-linking polymer particle pastel of being modified by octyl group aniline thereby bonding, another part between acquisition part participation polymer particle pass through the PEG chain.Below it is called " avoiding keeping away property soil resistance particle-1 ".
[synthetic embodiment 2]
(1), adds 59.6 parts of 10% dimethylbenzene of the diglycidyl ether (epoxide equivalent is 551) of PEG (its average degree of polymerization is about 22)/n-butanol mixed solvent solution according to the operation same with synthetic embodiment 1 (2).To wherein under 85～90 ℃, dripping 5 parts of octyl group aniline, and then stirred 4 hours down at 90～115 ℃ through 3 hours.Add 2.3 parts of monoxones afterwards, under 50 ℃, make it reaction.
Then, add 2.67 parts methyl chloroacetate and 50 ℃ of following reactions 8 hours, adjust pH to 8～9 with sodium hydroxide then in this reaction solution, methyl chloroacetate is removed in decompression distillation afterwards.Then 1.8 parts of DEA were dripped with 3 hours down at 50 ℃, and then stirred 5 hours down, make it reaction and carry out tertiary amineization at 50～55 ℃.Thereby obtaining with an end is that the PEG of 3-(lignocaine) (2-hydroxyl) propyl group is arranged is the PEG mixed derivative solution of main component for carboxylated octyl group anilino-, another terminal bonding.Confirm the carrying out of each elementary reaction with infrared spectrum and GPC.
(2) in reaction vessel, be added in 250 parts of the dispersion liquids of the core with chloromethyl-sheath type cross-linking polymer particle that obtains among the above-mentioned synthetic embodiment 1 (1), adding the bonding contain acquisition among above-mentioned synthetic embodiment 2 (1) afterwards has the dimethylbenzene of 13.5 parts in the PEG derivative of carboxylated octyl group anilino-and 3-(lignocaine) (2-hydroxyl) propyl group/27.0 parts of n-butanol mixed solvent solution, reacted 3 hours down at 70 ℃, reacted 5 hours down at 80 ℃.
After the reaction, reactant liquor joined in 300 parts the ethanol, filter polymer particle, use washing with alcohol.The cross-linking polymer particle pastel that obtains by the PEG chain and modify by octyl group aniline.Below it is called " avoiding keeping away property soil resistance particle-2 ".
[synthetic embodiment 3]
(1) according to the operation same with synthetic embodiment 1 (2), make 15.2 parts of 3-ethylaminos-4-methylphenol and DEA7.5 part successively with 110.2 parts of reactions of diglycidyl ether (epoxide equivalent is 551) of PEG (average degree of polymerization is about 22), obtaining with an end is that the PEG of 3-(lignocaine) (2-hydroxyl) propyl group is arranged is the PEG derivative of main component for 3-(hydroxy-methylbenzene base (ethyl) amino)-(2-hydroxyl) propyl group, another terminal bonding.
Add 0.07 part of hydroquinones afterwards, the 50%MEK solution of CMS was dripped through 1 hour under 50 ℃ for 30.6 parts, and then stirred 2 hours down, make it reaction at 50～55 ℃.With in the sodium hydrate aqueous solution and hydrochloric acid, heat up in a steamer MEK with decompression distillation then, obtaining with PEG is that base and bonding have the styrene base class monomer of 3-ethylamino-4-methylbenzene phenolic group at interval.
(2) with St80 part, what obtain in above-mentioned (1) is that at interval base and bonding have 3-ethylamino-10 parts of the styrene base class monomers of 4-methylbenzene phenolic group, DVB10 part and 2,0.2 part of mixing of 2 '-azo two (2-amidine propane) hydrochloride with PEG.In polymerizing reactor, add 400 parts of deionized waters.Import nitrogen and intensification, drip above-mentioned monomer mixed solution, under 65～70 ℃, carry out 8 hours polymerisations.Below it is called " avoiding keeping away property soil resistance particle-3 ".
[synthetic embodiment 4]
(1) in reaction unit, is added in 110.2 parts of 50% dimethylbenzene of the diglycidyl ether (epoxide equivalent is 551) of the PEG that use among the synthetic embodiment 2 (1)/n-butanol mixed solvent solution, under 50 ℃, dripped 20.4 parts of 50% dimethylbenzene of trimethyl ethylenediamine/n-butanol mixed solvent solution through 3 hours, and then under 50～55 ℃, stirred 5 hours, make it reaction, obtain the PEG solution that bonding has trimethyl ethylenediamine base.Confirm the carrying out of reaction with infrared spectrum.
(2) in reaction vessel, be added in 250 parts of the dispersion liquids of the core with chloromethyl-sheath type cross-linking polymer particle that obtains among the synthetic embodiment 1 (1), being added on the bonding that obtains in above-mentioned (1) afterwards has 27.0 parts of the MIBK solution of the PEG of trimethyl ethylenediamine base, according to making it reaction with the same operation of synthetic embodiment 1 (3).After the reaction, filter polymer particle and washing.The cross-linking polymer particle that acquisition has been carried out finishing with tertiary amine PEG chain.Below it is called " cationic soil resistance particle-1 ".
[synthetic embodiment 5～6]
(1) according to the diglycidyl ether of the PEG of synthetic embodiment 2 (1) and the reaction identical operations of DEA, use the glycidyl compound of record in the following table 1, make it respectively DEA reaction with equivalent.And then make the CMS reaction of equivalent and with the sodium hydroxide neutralization, thereby obtain to have the styrene monomer derivative of alkyl PEG chain or phenyl PEG chain by uncle's amino bonded.
(2) according to the same operation of polymerisation of synthetic embodiment 2 (2), make the bonding on two ends of PEG of record in styrene, DVB and the table 1 that the amino monomer copolymerization of styryl methyl (diethyl) be arranged, obtain the cross-linking polymer particle pastel that has carried out finishing respectively with PEG derivative chain.
Table 1
| Synthetic embodiment | Glycidyl compound with the DEA reaction | Reaction product with DEA | The title of soil resistance particle |
| 5 | Single lauryl ether-the monoglycidyl ether of PEG (n is 15) (epoxide equivalent is 971) | Bonding has the single lauryl ether (M is 1200) of the PEG of styryl (diethyl) amino methyl | Avoid keeping away property soil resistance particle-4 |
| 6 | Single phenyl ether-the monoglycidyl ether of PEG (n is 5) (epoxide equivalent is 400) | Bonding has the single phenyl ether (M is 600) of the PEG of styryl (diethyl) amino methyl | Avoid keeping away property soil resistance particle-5 |
N represents the rough average degree of polymerization of the oxirane of PEG chain.
M represents the rough mean molecule quantity of reaction product.
[synthetic embodiment 7]
(1) in reaction unit, is added in 214.4 parts of the 50% propyleneglycol monomethyl acetates solution of the PEG diglycidyl ether (epoxide equivalent is 268) that uses among the synthetic embodiment 1 (2).The 50% propyleneglycol monomethyl acetates solution of DEA was dripped through 3 hours under 50 ℃ for 58.6 parts, and then stirred 5 hours down, make it reaction, obtain the PEG solution that bonding has 3-(lignocaine) 2-(hydroxyl) propyl group at 50～55 ℃.
Confirm the carrying out of reaction with infrared spectrum.Then, the 50%MIBK solution of IPDI was dripped through 1 hour under 50 ℃ for 88.9 parts, and then stirred 2 hours down, make it and hydroxyl reaction, obtain isocyanate derivates at 50～55 ℃.
Afterwards, to contain 104.8 parts of propyleneglycol monomethyl acetates solution with lysolecithin (hydrogenating glycerine soya fatty acid monoesters-phosphatid ylcholine) of hydroxyl dripped through 2 hours under 50 ℃ for 209.5 parts, and then stirred 4 hours, make it reaction, obtain the tertiary amine that bonding has the PEG chain with phosphatid ylcholine base.
(2) in reaction vessel, be added in 250 parts in the core that obtains among the synthetic embodiment 1 (1)-sheath type cross-linking polymer particle dispersion liquid with chloromethyl, be added on the bonding that obtains in above-mentioned (1) 57.8 parts of 50% solution of the tertiary amine of the PEG chain with phosphatid ylcholine base are arranged, make it to react 8 hours the modified polymer particle surface down at 130 ℃.
After the reaction, reactant liquor is joined in 600 parts of ethanol, filter polymer particle and use washing with alcohol, obtain the cross-linking polymer particle pastel that has carried out finishing with phosphocholine.Below it is called " double ion soil resistance particle-1 ".
[synthetic embodiment 8]
Add 500 parts of deionized waters, 10 parts of 4-vinylpridines, DVB1 part and 2,0.2 part of 2 '-azo two (2-amidine propane) hydrochloride imports nitrogen and intensification.Under 65～70 ℃, carry out 8 hours polymerisations.With the particle diameter of the polymer particle in the dynamic light scattering determination polymer fluid, the result is 350nm.Below it is called " cationic soil resistance particle-2 ".
[synthetic embodiment 9]
In the 4-vinylpridine cross-linking polymer particle dispersion liquid that in synthetic embodiment 8, obtains, add 10 parts of monochloro acetate, and 25 ℃ of reactions 24 hours down, 50 ℃ of reactions 8 hours down.Filter, fully wash with deionized water, dry and pulverizing, acquisition has the copolymer particle of pyridine radicals and carboxyl.Below it is called " double ion soil resistance particle-2 ".
[synthetic embodiment 10]
Be added in 250 parts in the core that obtains among the synthetic embodiment 1 (1)-sheath type cross-linking polymer particle dispersion liquid with chloromethyl, add N, 12.3 parts of accelerines make it to react 8 hours down at 130 ℃, obtain with dimethylaniline the polymer particle of modifying have been carried out on the surface.After the reaction, reactant liquor is joined in 300 parts of ethanol, filter polymer particle and use washing with alcohol.The cross-linking polymer particle pastel that acquisition has been carried out finishing with the phenyl dimethylammonio.Below it is called " avoiding keeping away property soil resistance particle-6 ".
[synthetic embodiment 11]
According to the same operation of finishing reaction of the cross-linking polymer particle of synthetic embodiment 10, replace N for 20.3 parts with octyl group aniline, accelerine reacts.After the reaction, reactant liquor is joined in the ethanol, filter polymer particle and washing.The cross-linking polymer particle pastel of finishing has been carried out in acquisition with alkali compounds.Below it is called " avoiding keeping away property soil resistance particle-7 ".
[synthetic embodiment 12]
(styrene-content is 30% with the styrene-ethylene/butylene-styrene block copolymer of 47 parts in acrylic acid, DVB8.11 part and maleic acid modification in aggregation container, mean molecule quantity is 200,000) 5.51 parts of strippings are in 550 parts of the mixed solvents of hexahydrotoluene/MEK/ toluene (5:3:2), to the tert-butyl group-peroxide-2 ethyl hexanoic acid ester that wherein adds 0.6 part, and utilize the nonaqueous emulsion polymerization to make it to carry out radical polymerization, obtain to contain the cross-linking polymer particle of carboxyl.Below it is called " anionic property soil resistance particle-1 ".Average grain diameter with this anionic property soil resistance particle-1 of dynamic light scattering determination is about 200nm.
[synthetic embodiment 13]
In the container of belt stirrer, in 74 parts of butyl acetates, add CMS93 part, 50 parts of maleic anhydrides and AIBN3 part, stripping is to prepare to contain the monomer solution of polymerization initiator.In addition, prepare polymerizing reactor, in reaction vessel, add 100 parts of butyl acetates, import nitrogen and stirring, be warming up to 70 ℃.After wherein adding 80 parts of above-mentioned monomer solutions, making it to react 30 minutes, residual monomers solution was dripped through 2 hours, keep this state to carry out 10 hours polymerisation.
Be added in 30 parts of 50 parts of polymer solutions obtaining in above-mentioned and butyl acetates, stir also and heat up.Drip down N at 80 ℃, 15.12 parts of N '-dimethyl octylame make it to become the differential state that looses, and temperature is transferred to 120～140 ℃ and reacted 8 hours.Afterwards, drip 8.94 parts of n-butanols and carry out esterification.Carry out becoming precipitation state after the reaction in 8 hours.With reactant liquor cooling, filtration, fully wash the back drying with methyl alcohol.Acquisition has the hot ammonium of seasonization and the copolymer particle of carboxyl.Below it is called " double ion antifouling particle-3 ".
[synthetic embodiment 14]
(1) according to the operation same with synthetic embodiment 5 (1), be added in 268.0 parts of 50% MEK (MEK) solution of the diglycidyl ether of the PEG that uses among the synthetic embodiment 1 (2), the 50%MEK solution of DEA was dripped through 3 hours under 50 ℃ for 73.2 parts, and then under 50～55 ℃, stirred 5 hours, make it reaction, obtain the PEG that bonding has lignocaine.
Add 0.07 part of hydroquinones afterwards, the 50%MEK solution of CMS was dripped through 1 hour under 50 ℃ for 152.6 parts, and then stirred 2 hours down, make it reaction at 50～55 ℃.With in the sodium hydrate aqueous solution and after the hydrochloric acid, heat up in a steamer MEK with decompression distillation, obtaining has the amino monomer of N-styryl methyl (N, N-diethyl) at two terminal bondings of PEG.
(2) two the terminal bondings at PEG with St80 part, acquisition in above-mentioned (1) have 10 parts of N-styryl methyl (N, N-diethyl) amino 10 parts of monomers, DVB and 2,0.2 part of mixing of 2 '-azo two (2-amidine propane) hydrochloride.In polyplant, add 400 parts of deionized waters, to wherein dripping above-mentioned monomer mixed solution and mixing.Import nitrogen and intensification, under 65～70 ℃, carry out 8 hours polymerisations.Below it is called " cationic soil resistance particle-3 ".
[comparative example 1]
In aggregation container, add (7/3) 150 part of dimethylbenzene/n-butanol mixed solvent, be heated to 90 ℃.Monomer mixed solution with 1.5 parts of 50 parts of MMA, 35 parts of butyl methacrylates (BMA), 15 parts of HEMA and t-butyl peroxy-2 ethyl hexanoic acid ester dripped through 2 hours afterwards, reaction is 6 hours under stream of nitrogen gas, obtains the xylene solution (solid constituent is 40%) of MMA-BMA-HEMA copolymer.Below it is called " relatively using acrylic resin ".
＜be used for the Application Example of antifouling paint 〉
[Application Example 1]
Avoid keeping away property soil resistance particle-1 and the following fixing dimethylbenzene/butanol solution with acrylic resin that will obtain in synthetic embodiment 1 are 65/35 to mix with the solid constituent mass ratio, behind butyl acetate adjustment solid constituent to 25%, to avoid keeping away property soil resistance particle-1 with ultrasonic and disperse, preparation coating., with the width coating epoxies bottom-coating of about 1cm, produce and protect and the border respectively with marking the border with centre up and down around the steel plate in the test of having implemented antirust processing.Above-mentioned mixed liquor is coated with thickly and dry 10 days at normal temperatures in its latter half.Film and be roughly 110～130g/m
2The first half is coated with the relatively acrylic resin of usefulness as shown in following comparative example 2.
That uses in above-mentioned is fixing following synthetic with acrylic resin.The polyplant that use is used in synthetic embodiment 1 adds 114 parts of dimethylbenzene, 38 parts of n-butanols in aggregation container, be heated to 90 ℃.Dripped the mixed liquor of 1.5 parts of MMA35 part, 35 parts of BMA, 15 parts in acrylic acid, 15 parts of methacrylic acid (2-ethoxy) esters (HEMA) and t-butyl peroxy-2 ethyl hexanoic acid ester afterwards through 2 hours, under stream of nitrogen gas, react and made (solid constituent is 40%) in 6 hours.In addition, above-mentioned test steel plate be the two-sided sandblast of medium size of making in Test Panel company (the Japanese original text is: サ Application De プ ラ ス ト) steel plate (wide * long * thick be 70 * 150 * 1mm) to go up after drying with about 150g/m
2The bottom-coating of coating tar epoxies, make air-dry then back.
[comparative example 2]
Coating is used for the resin solution in comparative example 1 acquisition of comparison antifouling property on the first half of differentiation in Application Example 1 on each coated plate of preparation, dry 10 days at normal temperatures.The thickness of filming is roughly 110～130g/m
2In following Application Example, two parts are coated with about being divided into too, compare then.
[Application Example 2～15]
According to the prescription with solid component meter of table 2, according to the preparation method and the coating method of the coating of explanation in the Application Example 1, preparation is coated with plaque.Thickness is roughly 110～130g/m
2
Table 2-1 (expression solid constituent mass ratio.)
Table 2-2 (expression solid constituent mass ratio.)
[Application Example 16]
(1) test method and test are to carry out under the nutrient environment how in less, adjacent with the cultivation field of juvenile fish the place of the seawater stream in inland sea and owing to throw in the bait with the sea water immersion test of steel plate.Water temperature is that about 25～28 ℃, COD concentration are 4～10mg/L.It is said that COD concentration is 1～2mg/L in the cleaner place of the seawater in rapids indoor sea, as seen being green in the color of the medium water in harbour is 3～5mg/L to yellow place.
The test that will prepare in Application Example 1～15 and comparative example 2 and cover with paint, lacquer, colour wash, etc. is fixed on the framework of polyvinyl chloride system up and down and hangs with steel plate.The framework of polyvinyl chloride system is flooded to the degree of depth apart from sea 1～2m.Through 4 time-of-weeks, mention the test steel plate weekly, the attachment state of the first half of viewing test usefulness steel plate and the barnacle of the latter half is estimated the variation of state.Evaluation result is as shown in table 3 below.
(2) result of state observation and evaluation
A: have function as non-stripping property antifouling paint.
B: be non-stripping property, but insufficient slightly as the function of antifouling paint.
C: be non-stripping property, but do not have function as antifouling paint.
Table 3
[comparative example 3]
According to using the polishing type of cuprous oxide to be coated with plaque with the same operation of Application Example preparation, similarly carry out the seawater dipping, estimate soil resistance.Barnacle does not almost adhere to, and demonstrates very excellent soil resistance, and test with around the steel plate up and down, the part with the covering with paint of epoxies bottom-coating on central border equally do not have barnacle to adhere to yet.This is illustrated in and comprises that antifouling paint does not have to be subjected in the environment of adjacency of the part of covering with paint, lacquer, colour wash, etc. the influence of the stripping of cuprous oxide yet.Relative therewith, above-mentioned Application Example 1～15 to be coated with on the part that jewelry is being coated with the epoxies bottom-coating barnacle obviously more, and stiffly adhere to, show the not stripping of biological repellent of use.Thus, show that the various soil resistance particles that use in the Application Example are little to the load of environment.
By the present invention, can provide environment and edible aquatic products safety and have the anti-fouling treatment method and the antifouling processing article of the novel soil resistance particle (biological antifouling composition) of excellent anti-fouling effect, the antifouling paint that uses this particle, base material.
Claims (10)
1. a biological antifouling composition is characterized in that, is made of the polymer particle with biological soil resistance group.
2. according to the biological antifouling composition of record in the claim 1, wherein, biological soil resistance group is avoided in the keeping away property group (c) at least a kind for being selected from the two ionic group (b) and biology of hydrophilic radical (a), anionic property and cationic.
3. according to the biological antifouling composition of putting down in writing in the claim 2, wherein, described hydrophilic radical (a) is for being selected from least a kind in anionic property group, cationic group, nonionic group, anionic/nonionic amphiprotic group, cationic/nonionic amphiprotic group and anion/cationically ampholytic group.
4. according to the biological antifouling composition of putting down in writing in the claim 2, wherein, the two ionic group (b) of described anionic property and cationic is for being selected from the anionic property group in anionic property group, anionic/nonionic amphiprotic group, cationic group, cationic/nonionic amphiprotic group and anion/cationically ampholytic group and the combination of cationic group.
5. according to the biological antifouling composition of record in the claim 2, wherein, described biology is avoided keeping away property group (c) for being selected from least a kind in aliphatic, alicyclic or aromatic amino, quaternary ammonium group, pyridine radicals, pyridine radicals, phenol hydroxyl and the polyethylene glycol groups.
6. according to the biological antifouling composition of record in the claim 1, wherein, described polymer particle is the mixture with polymer particle of different soil resistance groups.
7. an antifouling paint is characterized in that, cooperates the formation material of filming to form in its polymer particle of putting down in writing in claim 1.
8. according to the antifouling paint of record in the claim 7, wherein, described polymer particle (A) and coating form the fit quality of material (B) than being A:B=95:5～5:95.
9. the biological anti-fouling treatment method of a base material is characterized in that, with the antifouling paint of record in the biological antifouling composition of record in the claim 1 or the claim 7 be coated with on the base material, impregnation or in base material, mix.
10. the antifouling processing article of biology is characterized in that, have carried out biological antifouling processing with the processing method of record in the claim 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006106766A JP4843353B2 (en) | 2006-04-07 | 2006-04-07 | Biological antifouling agent, antifouling treatment method and antifouling treatment article |
| JP106766/2006 | 2006-04-07 | ||
| PCT/JP2007/057574 WO2007116912A1 (en) | 2006-04-07 | 2007-04-04 | Anti-biofouling agent, anti-fouling coating, anti-fouling treatment method, and anti-foulingly treated material |
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| Publication Number | Publication Date |
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| CN101415330A true CN101415330A (en) | 2009-04-22 |
| CN101415330B CN101415330B (en) | 2013-09-04 |
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| Country | Link |
|---|---|
| JP (1) | JP4843353B2 (en) |
| KR (1) | KR101047642B1 (en) |
| CN (1) | CN101415330B (en) |
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| WO (1) | WO2007116912A1 (en) |
Cited By (3)
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| CN103468085A (en) * | 2013-09-13 | 2013-12-25 | 苏州蔻美新材料有限公司 | Process for preparing probe for monitoring water quality of bionic coating containing phospholipid polymers in real time |
| WO2017020147A1 (en) * | 2015-08-03 | 2017-02-09 | 天津纳微华瑞科技有限公司 | Cationic type antifouling and anti-drag composite functional paint and coating |
| CN112552769A (en) * | 2013-06-07 | 2021-03-26 | 日产化学工业株式会社 | Ion complexing material having ability to inhibit attachment of biological substance and method for producing same |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4843354B2 (en) * | 2006-04-07 | 2011-12-21 | 高知県 | Biological antifouling agent, antifouling treatment method and antifouling treatment article |
| AU2007264041B2 (en) * | 2006-06-26 | 2011-07-07 | Novartis Ag | Polymers with antimicrobial activity containing quaternary ammonium groups |
| EP2543429B1 (en) * | 2010-03-04 | 2015-12-16 | Sekisui Chemical Co., Ltd. | Macromolecular water-treatment membrane and manufacturing method therefor |
| WO2012133347A1 (en) * | 2011-03-28 | 2012-10-04 | ダイキン工業株式会社 | Sheet for preventing adhesion of aquatic organisms and coating material for preventing adhesion of aquatic organisms |
| EP2990449B1 (en) | 2013-04-23 | 2017-06-28 | Chugoku Marine Paints, Ltd. | Antifouling paint composition, antifouling paint film, antifouling substrate, and method for manufacturing antifouling substrate |
| JP2016017130A (en) * | 2014-07-08 | 2016-02-01 | 互応化学工業株式会社 | Bacterium adhesion-suppressed resin |
| JP6992757B2 (en) * | 2016-09-06 | 2022-01-13 | Ａｇｃ株式会社 | Biofouling prevention paint |
| EP3511381B1 (en) * | 2016-09-06 | 2021-10-27 | Agc Inc. | Anti-biofouling coating material |
| WO2019049854A1 (en) * | 2017-09-11 | 2019-03-14 | 日本ゼオン株式会社 | Antifouling agent and antifouling agent composition |
| CN116676011A (en) * | 2023-06-01 | 2023-09-01 | 上海船舶工艺研究所(中国船舶集团有限公司第十一研究所) | Sustained-release cellulose-cuprous oxide antifouling agent and preparation method and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0699244B2 (en) * | 1985-04-10 | 1994-12-07 | 日本ペイント株式会社 | Fine resin particles with anti-pest properties |
| JP2784652B2 (en) * | 1988-08-31 | 1998-08-06 | 日本カーバイド工業株式会社 | Aqueous dispersion type antifouling paint |
| CN1071092C (en) * | 1993-08-24 | 2001-09-19 | 詹森药业有限公司 | Antibacterial and antifouling oxathicazines and their oxides |
| JP3716375B2 (en) * | 1995-09-08 | 2005-11-16 | 日本ペイント株式会社 | Resin and paint for antifouling paint |
| JP2000302816A (en) * | 1999-04-20 | 2000-10-31 | Marine Biotechnol Inst Co Ltd | Polymer compound having stainproof activity and stainproofing material containing the same |
| JP2003073627A (en) * | 2001-06-18 | 2003-03-12 | Osaka Gas Co Ltd | Antifouling coating material |
| EP1371699A3 (en) * | 2002-06-14 | 2004-01-14 | Rohm And Haas Company | Polymeric nanoparticle and antimicrobial coating formulations |
| CN1497028A (en) * | 2002-09-30 | 2004-05-19 | 罗姆和哈斯公司 | Coating preparation containing polymer nanoparticle and biological active material |
| JP2006213861A (en) * | 2005-02-04 | 2006-08-17 | Kazuhiko Ishihara | Coating agent for fluid contact surface and material body equipped with coating agent for fluid contact surface |
-
2006
- 2006-04-07 JP JP2006106766A patent/JP4843353B2/en not_active Expired - Fee Related
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2007
- 2007-04-04 KR KR1020087024407A patent/KR101047642B1/en not_active IP Right Cessation
- 2007-04-04 CN CN2007800126065A patent/CN101415330B/en not_active Expired - Fee Related
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| CN112552769A (en) * | 2013-06-07 | 2021-03-26 | 日产化学工业株式会社 | Ion complexing material having ability to inhibit attachment of biological substance and method for producing same |
| CN112625535A (en) * | 2013-06-07 | 2021-04-09 | 日产化学工业株式会社 | Ion complexing material having ability to inhibit attachment of biological substance and method for producing same |
| CN112552769B (en) * | 2013-06-07 | 2021-12-17 | 日产化学工业株式会社 | Ion complexing material having ability to inhibit attachment of biological substance and method for producing same |
| CN103468085A (en) * | 2013-09-13 | 2013-12-25 | 苏州蔻美新材料有限公司 | Process for preparing probe for monitoring water quality of bionic coating containing phospholipid polymers in real time |
| WO2017020147A1 (en) * | 2015-08-03 | 2017-02-09 | 天津纳微华瑞科技有限公司 | Cationic type antifouling and anti-drag composite functional paint and coating |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080105148A (en) | 2008-12-03 |
| WO2007116912A1 (en) | 2007-10-18 |
| TW200806767A (en) | 2008-02-01 |
| CN101415330B (en) | 2013-09-04 |
| KR101047642B1 (en) | 2011-07-07 |
| JP4843353B2 (en) | 2011-12-21 |
| JP2007277431A (en) | 2007-10-25 |
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