CN101094899A - Water-based curing type antifouling coating composition, antifouling coating film and underwater structure - Google Patents

Water-based curing type antifouling coating composition, antifouling coating film and underwater structure Download PDF

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CN101094899A
CN101094899A CN200580045276.0A CN200580045276A CN101094899A CN 101094899 A CN101094899 A CN 101094899A CN 200580045276 A CN200580045276 A CN 200580045276A CN 101094899 A CN101094899 A CN 101094899A
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aqueous
paint compositions
antifouling paint
type antifouling
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CN101094899B (en
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枡田一明
大西勇
山盛直树
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Nippon Paint Holdings Co Ltd
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Nippon Paint Co Ltd
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Priority claimed from JP2004379674A external-priority patent/JP2006182956A/en
Priority claimed from JP2005368799A external-priority patent/JP2007169449A/en
Application filed by Nippon Paint Co Ltd filed Critical Nippon Paint Co Ltd
Priority claimed from PCT/JP2005/024116 external-priority patent/WO2006077738A1/en
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Abstract

A hydraulic stain-proof coating composition comprising an aqueous binder component having a curing property and a stain-proofing agent, which can provide a coating film applicable to the use in water. As the binder component, at least one cure system selected from a carbonyl/hydrazide system, an acetoacetoxy/amine system and an alkoxysilyl condensation system; a curing agent and an emulsion resin having a group reactive with a functional group present in the curing agent; or the like may be used. A pasty stain-proofing agent comprising a water-soluble dispersion resin having an acid value of 10 to 300 mg KOH/g and a number average molecular weight of 1000 to 20000 and a stain-proofing agent. A hydraulic stain-proof coating composition comprising an aqueous binder component having a curing property. A stain-proof coating film formed from the hydraulic stain-proof coating composition. An underwater structure having the stain-proof coating film.

Description

Aqueous solidified type antifouling paint compositions, antifouling coating and aouatic structure thing
Technical field
The present invention relates to aqueous solidified type antifouling paint compositions, antifouling coating and aouatic structure thing.
Background technology
Boats and ships, fishing net, and other aouatic structure thing on be easy to adhere to marine organisms such as barnacle, duricrust mussel, algae, therefore can hinder effectively operations such as boats and ships, have the problem that to cause waste of fuel, and fishing net etc. can produce and stop up, produce problems such as durable years shortening.In order to prevent biological attachment, form antifouling coating on the surface of aouatic structure thing in above-mentioned aouatic structure thing all the time.As forming the employed antifouling paint of this antifouling coating, the known coating composition (for example with reference to patent documentation 1～5) that the solvent based that contains non-gel-type resin is arranged.
In recent years, in most paint field, require to reduce the usage quantity of organic solvent, and carry out the exploitation use of various water-borne coatingss.But,, seldom attempt being made into waterborne compositions for antifouling paint compositions.This is caused by following reason.That is, water-borne coatings is medium with water, thereby the wetting ability of the wetting ability of the binding agent that is wherein the contained binding agent that is higher than in the solvent based coating to be contained, if directly then have the problem that is easy to be dissolved in the water used as filming.On the other hand, in order to address this problem, can be with curing of coating to guarantee its water tolerance, then stain control agent just can not stripping from the solidified film if so, thereby has produced to film and do not have the other problem of didirtresistance.Therefore, making the antifouling paint Water-borne modification is quite difficult technically.
Put down in writing the composition that contains resin, water and basic cpd in the patent documentation 6,7 with divalent metal.But this resin is non-gel-type resin, and water tolerance of filming therefrom is insufficient.
Patent documentation 1: the spy opens flat 9-52803 communique
Patent documentation 2: the spy opens flat 10-59810 communique
Patent documentation 3: the spy opens flat 11-172159 communique
Patent documentation 4: the spy opens the 2000-109729 communique
Patent documentation 5: the spy opens the 2003-277680 communique
Patent documentation 6: the spy opens the 2002-371166 communique
Patent documentation 7: the spy opens the 2003-49123 communique
Summary of the invention
In view of above-mentioned present situation, the object of the present invention is to provide a kind of aqueous solidified type antifouling paint compositions, said composition has been given play to the function as the excellence of antifouling paint; The aouatic structure thing that the antifouling coating that is obtained by said composition is provided and has this antifouling coating.
The present invention relates to a kind of aqueous solidified type antifouling paint compositions, be mixed with aqueous binders composition and stain control agent in the said composition, and be used in the purposes that water uses by resulting the filming of said composition with solidified nature.
Above-mentioned solidified nature is preferably by water or air control.
The cured article of above-mentioned aqueous binders composition preferably decomposes by water.
Above-mentioned aqueous binders composition preferably is cured by dehydrating condensation.
Above-mentioned aqueous binders composition preferably has at least a curing system in carbonyl/hydrazides class, acetoacetyl oxygen/amine and the alcoxyl silyl condensation class.
Preferred above-mentioned aqueous binders composition contains the group that emulsifying resins and solidifying agent and described emulsifying resins have the functional group reactions that can be had with described solidifying agent.
The cured article of above-mentioned aqueous binders composition can have the structure that long chain hydrocarbon groups is cross-linked to each other and forms.
Above-mentioned aqueous binders composition preferably is cured by oxypolymerization.
Preferably the group from higher unsaturated fatty acid participates in above-mentioned oxypolymerization.
Above-mentioned aqueous binders composition preferably contains emulsifying resins and the siccative that has from the group of higher unsaturated fatty acid.
Above-mentioned emulsifying resins is preferably the multipolymer that has from the ethylene linkage unsaturated monomer of the group of higher unsaturated fatty acid.
The invention still further relates to following aqueous solidified type antifouling paint compositions, the aqueous binders composition that is mixed with the stain control agent thickener in the said composition and has solidified nature, being mixed with acid number in the described stain control agent thickener is that 10～300mgKOH/g, number-average molecular weight are 1000～20000 water-soluble dispersion resin and stain control agent.
The water-soluble dispersion resin in the preferred above-mentioned stain control agent thickener and the solids component mass ratio of stain control agent are 1/99 to 50/50.
Preferably will in water, use by filming of obtaining of above-mentioned aqueous solidified type antifouling paint compositions.
Preferred above-mentioned aqueous binders composition is cured by addition reaction.
Above-mentioned aqueous binders composition preferably is cured by oxypolymerization.
Preferably the group from higher unsaturated fatty acid participates in above-mentioned oxypolymerization.
Above-mentioned aqueous binders composition preferably contains emulsifying resins and the siccative that has from the group of higher unsaturated fatty acid.
Above-mentioned emulsifying resins is preferably the multipolymer that has from the ethylene linkage unsaturated monomer of the group of higher unsaturated fatty acid.
Further be mixed with the organic polymer particle in the preferred aqueous solidified type antifouling paint compositions of the present invention.
Preferred its particle diameter of above-mentioned organic polymer particle is 0.05～100 μ m, according to the solubleness in the artificial seawater of ASTM D1141-98 defined is being below the 15g/L, is being more than the 0.01 quality % to the water regain according to the artificial seawater of ASTM D1141-98 defined in 23 ℃.
Above-mentioned organic polymer particle is preferably the polymer of natural origin.
Above-mentioned organic polymer particle preferably has the cationic group.
Preferred its particle diameter of above-mentioned organic polymer particle is 0.05～100 μ m, and for containing the organic polymer particle that is selected from least a material in the group of forming by the derivative of chitin (chitin), chitosan (chitosan), γ-PGA, spun silk crushed material and above-mentioned substance.
Above-mentioned organic polymer particle is preferably synthetic macromolecule.
Above-mentioned organic polymer particle is preferably the acrylic resin particle.
Above-mentioned organic polymer particle is preferably the composite resin particle that contains hydrophilic resin and acrylic resin, and described hydrophilic resin is for being selected from least a material in the group of being made up of starch, pulullan polysaccharide (pullulan), gum arabic, κ-carrageenan, gelatin, Mierocrystalline cellulose, chitosan and their derivative, polyvinyl alcohol, polyallylamine, polyvinylamine, poly-(methyl) acrylamide, poly-(methyl) vinylformic acid and their multipolymer.
Above-mentioned organic polymer particulate combined amount is preferably the 0.01 quality %～15 quality % of coating solids component.
The invention still further relates to antifouling coating, this antifouling coating is characterised in that it is to be obtained by above-mentioned aqueous solidified type antifouling paint compositions.
The invention still further relates to the aouatic structure thing, this aouatic structure thing is characterised in that it has above-mentioned antifouling coating.
Describe the present invention below in detail.
Aqueous solidified type antifouling paint compositions of the present invention can also form when seeking the Water-borne modification of coating has given play to filming as the desired performance of antifouling paint.
Be mixed with aqueous binders composition and stain control agent in the aqueous solidified type antifouling paint compositions of the present invention with solidified nature.
As long as the aqueous binders composition that is contained in the aqueous solidified type antifouling paint compositions of the present invention has solidified nature, be not subjected to special qualification, can by the solution that is dissolved with water soluble resin, be dispersed with water-dispersed resin emulsifying resins, utilize emulsifying agent etc. that the mandatory dispersive dispersion resin of resin is formed.From the viewpoint of various performances such as water tolerance, didirtresistance, preferred especially described aqueous binders composition contains the emulsifying resins that is dispersed with water-dispersed resin.
Above-mentioned emulsifying resins contains to be useful in water and disperses-emulsive functional group and curing functional group.Be used for disperseing-emulsive functional group as above-mentioned, be not subjected to special qualification, for example can enumerate bases such as acidic-groups such as carboxyl, sulfonic group or amino at water.Above-mentioned when being used for being acidic-group in water dispersion-emulsive functional group, be that scope below the 300mgKOH/g contains these acidic-groups preferably with the acid number of emulsifying resins, more preferably acid number is 1～20mgKOH/g.As above-mentioned acidic-group, preferred especially carboxyl.Above-mentioned when being used for being base in water dispersion-emulsive functional group, also can set equally with for acidic-group the time.In addition, also can after the addition polyoxyethylene units, in water, disperse-emulsification.
Above-mentioned when being used for being acidic-group in water dispersion-emulsive functional group, can be by in above-mentioned emulsifying resins, adding alkali; Above-mentioned when being used for being base in water dispersion-emulsive functional group, can neutralize, thereby in water, disperse-emulsification by in above-mentioned emulsifying resins, adding acid.
For the solidified nature of above-mentioned aqueous binders composition, consider the use form of coating, preferably it is cured at normal temperature.Generally be cured reaction in the forced drying by seasoning or about 80 ℃ after the coating at the composition of ambient cure, this is known for a person skilled in the art.
Among the present invention, above-mentioned ambient cure is preferably controlled by water or air.Said herein control by water or air is meant, removes moisture by drying, is cured the state of reaction thus; Perhaps contact with airborne oxygen, be cured the state of reaction etc. thus by drying.
In addition, for above-mentioned aqueous binders composition, its cured article preferably has the character of being decomposed by water.If it has this character, then will be immersed in the water and can decompose, thereby it can show self abrasive property by filming of obtaining of the coating that is mixed with above-mentioned aqueous binders composition.
Curing system as having above-mentioned character of being decomposed by water can exemplify out dehydration condensation.Also promptly, in this case, above-mentioned aqueous binders composition solidifies by dehydrating condensation.
Above-mentioned dehydration condensation is for generating the balanced reaction of water, thereby removes moisture by drying and be cured reaction.Further, if will be immersed in the water by filming of having solidified of dehydration condensation, then owing to there is a large amount of water to exist, thereby films and decompose, this is decomposed into the reversed reaction of curing reaction.
In addition, for above-mentioned aqueous binders composition, its cured article can have the structure that long chain hydrocarbon groups is cross-linked to each other and forms.In this case, had in the cured film that the aqueous binders composition of stain control agent obtains by coexistence, stain control agent is difficult for stripping, thereby preferred.It is believed that this be because, compare with the crosslinking structure that obtains by other curing system, the long chain hydrocarbon groups structure that forms that is cross-linked to each other forms latticed lentamente.In addition, the above-mentioned long chain hydrocarbon groups structure that forms that is cross-linked to each other is meant, the unsaturated link(age) of long chain hydrocarbon groups and the unsaturated link(age) of other long chain hydrocarbon groups be the structure that forms of bonding directly or indirectly.As the example of above-mentioned indirect bonding, can enumerate the bonding that is undertaken by Sauerstoffatom in the following oxidative polymerization.
The resulting curing system of structure as being cross-linked to each other by above-mentioned long chain hydrocarbon groups and forming can exemplify oxidative polymerization.
Above-mentioned oxidative polymerization is meant to be absorbed by unsaturated link(age) by oxygen and carries out polymeric reaction that this reaction is by also having the feature of rapid-drying properties excellence with siccative.In addition, if when using urethane cures system etc. not have the aqueous binders composition of above-mentioned feature, its long-term didirtresistance may variation.
When above-mentioned aqueous binders composition is cured by dehydrating condensation,, can enumerate for example carbonyl/hydrazides class, acetoacetyl oxygen/amine, alcoxyl silyl condensation class etc. as its curing system.These curing systems are known curing system, can use the combination of known resin and solidifying agent.
When above-mentioned aqueous binders composition had the curing system that utilizes carbonyl/hydrazides class, above-mentioned aqueous binders composition preferably contained resin with carbonyl and as the hydrazide compound of solidifying agent.
As above-mentioned resin with carbonyl, as long as for having the resin of at least one aldehyde radical and/or ketone group, be not particularly limited, can enumerate the modifier/mixture of acrylic resin, vibrin (comprising Synolac), urethane resin, Resins, epoxy, above-mentioned substance etc.Wherein, consider preferred acrylic resins from aspects such as water tolerance, the rerum naturas of filming.
Resin with carbonyl is when having the acrylic resin of carbonyl, and the emulsifying resins that preferably uses following monomer composition to obtain by letex polymerization, described monomer composition contain the ethylene linkage unsaturated monomer with aldehyde radical and/or ketone group.
Be not particularly limited as above-mentioned ethylene linkage unsaturated monomer, can enumerate for example propenal, diacetone-acryloamide(DAA), diacetone Methacrylamide, formyl vinylbenzene, ethenyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, acryloyloxyalkyl propionic aldehyde class, methacryloyl oxyalkyl propionic aldehyde class, diacetone acrylate, diacetone methacrylic ester, acetonyl acrylate, 2-hydroxypropyl acrylate acetylacetic ester, butanediol acrylate acetylacetic ester etc. with aldehyde radical and/or ketone group.
Above-mentioned have the ethylene linkage unsaturated monomer of aldehyde radical and/or ketone group preferably so that aldehyde radical in the resulting resin and/or ketone group are the ratio use of 0.005～20mmol/ (1g resin solid composition).If aldehyde radical and/or ketone group in the resulting resin are that then solidification reactivity is insufficient below the 0.005mmol, thereby may can not get sufficient water tolerance; And, but may bring detrimentally affect to other performance if greater than 20mmol.
The acid number that the above-mentioned acrylic resin that contains carbonyl preferably has above-mentioned scope, the monomer composition polymerization of its ethylene linkage unsaturated monomer with hydroxy-acid group by containing desired amount obtains.As above-mentioned ethylene linkage unsaturated monomer with hydroxy-acid group, be not subjected to special qualification, can enumerate for example unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid; The acid anhydrides of unsaturated carboxylic acids such as maleic anhydride; Half carboxylate of unsaturated carboxylic acids such as methylene-succinic acid, fumaric acid, toxilic acid etc.
The above-mentioned acrylic resin that contains carbonyl preferably utilizes alkali such as amine to neutralize.Its neutralization ratio is preferably below 300%, and more preferably 10%～100%.
The above-mentioned number-average molecular weight that contains the acrylic resin of carbonyl is preferably more than 3000.If above-mentioned number-average molecular weight is less than 3000, and then water tolerance may reduce, thereby not preferred.Above-mentioned number-average molecular weight is more preferably more than 10000.By using chain-transfer agent, waiting the polymerization of carrying out resin, above-mentioned number-average molecular weight can be adjusted in the scope of suitable purpose by adjustment polymerization starter amount, polymerization temperature.
The above-mentioned acrylic resin that contains carbonyl can also use other monomer except that using above-mentioned monomer.As above-mentioned other monomer, can enumerate the ethylene linkage unsaturated monomer, for example acrylate, methacrylic ester (hereinafter only representing sometimes) with (methyl) acrylate; Aromatic monomer such as vinylbenzene, Vinyl toluene; Vinyl esters such as vinyl-acetic ester, propionate, tertiary monocarboxylic acid (versatic acid) vinyl acetate; Vinyl cyanide classes such as (methyl) vinyl cyanide; Ethylene halide such as vinylchlorid, vinylidene chloride class; Divinyl etc.Further can enumerate various functional monomers, for example, (methyl) acrylamide, vinyl pyrrolidone, (methyl) vinylformic acid 2-hydroxy methacrylate, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide, methacrylic acid acid phosphorus oxygen base ethyl ester, methacrylic acid 3-chloro-2-acid phosphorus oxygen base propyl ester, the methyl propane sulfonic acid acrylamide, Vinylstyrene, (gathering) oxygen ethene list (methyl) acrylate, (gathering) propylene glycol (methyl) acrylate, (methyl) allyl acrylate, (gathering) oxygen ethene two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, γ-(methyl) acryloxy propyl trimethoxy silicane etc.
As aforesaid propylene acid esters or methacrylic ester, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) dodecylacrylate etc.
The above-mentioned resin that contains carbonyl is preferably above-mentioned emulsifying resins.As the means that are used to obtain emulsifying resins, preferably known in the past letex polymerization.Its reason is, this method is controlled the amount of the functional group that introduces easily, and the molecular weight of the resin that is obtained by this method is bigger, thereby the effect that is quantized by the polymer that curing reaction brought is bigger, also can improve its water tolerance thus and make its solids component many.As above-mentioned known in the past letex polymerization, specifically can enumerate following method for example etc.: use reactive emulsifier that above-mentioned monomer composition is carried out emulsification containing water or contain as required in the aqueous medium of organic solvent such as alcohol in advance, carry out polymerization this emulsification being carried out drip polymerization starter under the heated and stirred then.
Be not particularly limited as above-mentioned reactive emulsifier, can be any the reactive emulsifier of anionic, cationic, non-ionic type, amphoteric ion type.As above-mentioned reactive emulsifier, for example can use commercial articles such as ELEMINOL JS series (Sanyo changes into industrial society system), LATEMUL S and K series (Hua Wangshe system), Aqualon HS series (first industrial pharmacy society system), ADEKAREASOAP series (rising sun electrification society system), Antox MS-60 (Japanese emulsifying agent society system).
Be not particularly limited as above-mentioned polymerization starter, can enumerate for example Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile) azo class oiliness compound such as, 4 of anionic species, 4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two aqueous compounds such as (N-(2-carboxy ethyl)-2-methyl-prop amidine), benzoyl peroxide, chloro benzoyl peroxide, lauroyl peroxide, redox class oiliness superoxide such as t-butylperoxyl benzoate, Potassium Persulphate, water-based superoxide such as ammonium persulphate etc.
When the above-mentioned resin that contains carbonyl was emulsifying resins, for example can enumerating, median size was the emulsifying resins of 50～600nm.Above-mentioned median size is if outside above-mentioned scope, and then dispersed the reduction may have the problem such as stable insufficient of aqueous solidified type antifouling paint compositions.
When above-mentioned aqueous binders composition has the curing system of above-mentioned carbonyl/hydrazides class, contain hydrazide compound as solidifying agent.Be not particularly limited as above-mentioned hydrazide compound, can use compound with two above hydrazides groups or Urea,amino-group.
As the compound that has two above hydrazides groups in the above-mentioned molecule, can enumerate the many hydrazides of carbonic acid, carbazide, sulfo-carbazides, 4 such as dicarboxyl acid dihydrazides such as oxalic acid two hydrazides, amber acid dihydrazide, adipic dihydrazide, sebacic dihydrazide, pentanedioic acid two hydrazides, sebacic dihydrazide, Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides, carbonic acid two hydrazides, polymkeric substance hydrazides such as 4 '-oxo benzol sulfohydrazide, aliphatics, alicyclic, aromatic series diaminourea, aromatic dicarboxylic acid hydrazides, polyacrylic acid hydrazides etc.In the above-claimed cpd, preferred adipic dihydrazide.
Be not particularly limited as the compound that has two above Urea,amino-groups in the above-mentioned molecule, can enumerate 1,6-hexa-methylene two (N, N-dimethylamino urea), 1,1,1 ', 1 '-tetramethyl--4,4 '-(methylene radical-two-to phenylene) diaminourea, biuret-three amino ureas such as (hexa-methylene-N, N-dimethylamino ureas).These compounds may be used alone, used in two or more.
The mol ratio of the amount of the solidifying agent functional group of being contained in above-mentioned amount that contains the curing functional group of being contained in the resin of carbonyl and the above-mentioned solidifying agent is preferably in 1/10 to 1/0.05 scope.Above-mentioned mol ratio is if outside above-mentioned scope, and then water tolerance might reduce.From water-proof viewpoint, above-mentioned mol ratio is preferably in 1/0.6 to 1/0.1 scope.
When above-mentioned aqueous binders composition had acetoacetyl oxygen/amine curing system, above-mentioned aqueous binders composition preferably contained resin with acetoacetoxy groups and as the amine compound of solidifying agent.Be not particularly limited as the above-mentioned resin that contains acetoacetoxy groups, but the preferred and above-mentioned resin that contains carbonyl similarly is acrylic resin.Be not particularly limited as the above-mentioned acrylic resin that contains acetoacetoxy groups, for example can enumerate, contain the resin that the monomer composition of the ethylene linkage unsaturated monomer with acetoacetoxy groups obtains by letex polymerization.
Be not particularly limited as above-mentioned ethylene linkage unsaturated monomer, can enumerate the esters of acrylic acid, the methyl acrylic ester that for example have acetoacetoxy groups with acetoacetoxy groups.Specifically can enumerate acetoacetoxy groups ethyl propylene acid esters, acetoacetoxy groups ethyl-methyl acrylate etc.
The above-mentioned resin that contains acetoacetoxy groups preferably similarly is emulsifying resins with the above-mentioned resin that contains carbonyl.Be not particularly limited as polymerization process, for example can be by obtaining with the same method of the above-mentioned resin that contains carbonyl.
Be not particularly limited as above-mentioned amine compound, can enumerate for example 2-methyl pentamethylene diamine, cyclohexane diamine, hexamethylene-diamine, quadrol, 1,3-diaminopropanes, 1,4-diaminobutane, 1,6-hexanediamine, 1,12-diamino dodecane, 1,2-diamino-cyclohexane, phenylenediamine, piperazine, 2,6-diaminotoluene, diethyl toluene diamine, N, N-two (2-aminopropyl) quadrol, N, N-two (3-aminopropyl)-1,3-propylene diamine etc. has the compound of diamino or polyamino.
The mol ratio of the amount of the solidifying agent functional group of being contained in above-mentioned amount that contains the curing functional group of being contained in the resin of acetoacetoxy groups and the above-mentioned solidifying agent is preferably in 1/10 to 1/0.05 scope.Above-mentioned mol ratio is if outside above-mentioned scope, and then water tolerance may reduce.From water-proof viewpoint, above-mentioned mol ratio is more preferably in 1/0.6 to 1/0.1 scope.
When above-mentioned aqueous binders composition had the curing system that utilizes alcoxyl silyl condensation class, above-mentioned aqueous binders composition was the composition that comprises the resin with alkoxysilyl.Be not particularly limited as above-mentioned alkoxysilyl, can enumerate for example methoxy methyl silylation, (ethoxymethyl) silylation, propoxy-silyl, butoxy silyl etc.In addition, because the Si atom is the atom of 4 valencys, thereby can think that above-mentioned alkoxysilyl is for constituting the cell mesh of functional groups such as dialkyl group monoalkoxy silyl, monoalkyl dialkoxy silyl, trialkoxysilyl.In addition, the alkoxysilyl in this specification sheets be meant the Si atom and with 1 alkoxyl group of this Si atomic linkage.Therefore, for example trialkoxysilyl just has three alkoxysilyls.
Be not particularly limited as the above-mentioned resin that contains alkoxysilyl, can enumerate for example by making the monomer composition that contains ethylene linkage unsaturated monomer carry out the resin that letex polymerization obtains with alkoxysilyl.Be not particularly limited as above-mentioned ethylene linkage unsaturated monomer, can enumerate for example γ-iso-butylene acyl-oxygen base propyl trimethoxy silicane with alkoxysilyl, γ-acryloxy propyl group methyl dimethoxysilane, γ-iso-butylene acyl-oxygen base propyl group methyl dimethoxysilane, γ-acryloxy propyl-dimethyl methoxy silane, γ-iso-butylene acyl-oxygen base propyl-dimethyl methoxy silane, γ-acryloxy propyl-triethoxysilicane, γ-iso-butylene acyl-oxygen base propyl-triethoxysilicane, γ-acryloxy propyl group methyldiethoxysilane, γ-iso-butylene acyl-oxygen base propyl group methyldiethoxysilane, γ-acryloxy propyl-dimethyl Ethoxysilane, γ-iso-butylene acyl-oxygen base propyl-dimethyl Ethoxysilane, vinyltrimethoxy silane, the vinyl methyl dimethoxysilane, vinyltriethoxysilane, the vinyl methyldiethoxysilane, trimethoxysilyl vinylbenzene, dimethoxy-methyl silyl vinylbenzene, triethoxysilyl vinylbenzene, diethoxymethyl silyl vinylbenzene etc.
The above-mentioned resin that contains alkoxysilyl preferably similarly is emulsifying resins with the above-mentioned resin that contains carbonyl.Polymerization process as above-mentioned unsaturated monomer mixture is not particularly limited, for example can be by obtaining with the same method of the above-mentioned resin that contains carbonyl.
When above-mentioned aqueous binders composition had the curing system that utilizes alcoxyl silyl condensation class, above-mentioned aqueous binders composition preferably further contained acid and/or alkali.
Be not particularly limited as above-mentioned acid and alkali, can enumerate the resin of acidic groups such as for example having carboxyl, phosphate, sulfonic group, resin with bases such as amino.As above-mentioned resin, consider preferably to have phosphate or sulfonic resin from the strong aspect of catalytic activity, from being easy to introduce the resin that phosphate is considered especially preferably to have in the functional group aspect with acidic group.As above-mentioned amino, be preferably uncle's amino that bonding on the nitrogen-atoms has 2 alkyl, abovementioned alkyl can be the same or different, but preferred especially carbonatoms is 1～8 alkyl.As the concrete example of this amino, can enumerate dimethylamino, diethylamino, methylethyl amino, dibutylamino, dioctyl amino etc.Be not particularly limited as resin, for example can enumerate the resin that the polymerization of the monomer composition by containing the ethylene linkage unsaturated monomer with at least one acidic group or base obtains with above-mentioned acidic group or base.
The mol ratio of the above-mentioned amount that contains the alkoxysilyl that is contained in the resin of alkoxysilyl and above-mentioned acid and/or alkali is preferably in 1/10 to 1/0.01 scope.Above-mentioned mol ratio is if surpass 1/0.01, and then solidified nature is insufficient, and water tolerance might reduce.Above-mentioned mol ratio is if be lower than 1/10, and the amount of then unreacted acid and/or alkali can increase, and water tolerance might reduce.From water-proof viewpoint, above-mentioned mol ratio is more preferably in 1/0.6 to 1/0.1 scope.
In the above-mentioned curing system that utilizes dehydration condensation, from have the viewpoint of good self abrasive property by the reversed reaction that is cured reaction, preferred carbonyl/hydrazides class, wherein from the viewpoint of solidification reactivity excellence, the combination of preferred especially carbonyl/semicarbazide compound.
When above-mentioned aqueous binders has the curing system of the oxypolymerization of utilizing, the participation from the group of higher unsaturated fatty acid is arranged in this curing system preferably.By making, obtain structure foregoing, that long chain hydrocarbon groups is cross-linked to each other and forms from the unsaturated link(age) generation oxypolymerization in the group of higher unsaturated fatty acid.
As the above-mentioned resin that has from the group of higher unsaturated fatty acid, can enumerate for example Synolac, but the emulsifying resins of preferred acrylic type.This have from the vinylformic acid emulsifying resins of the group of higher unsaturated fatty acid and can obtain by containing the letex polymerization that has from the monomer composition of the ethylene linkage unsaturated monomer of the group of higher unsaturated fatty acid.
Be not particularly limited as the above-mentioned ethylene linkage unsaturated monomer that has from the group of higher unsaturated fatty acid, for example can enumerate, higher unsaturated fatty acid and the ethylene linkage unsaturated monomer that contains glycidyl are reacted and the monomer that obtains etc.Be not particularly limited as above-mentioned higher unsaturated fatty acid, can enumerate for example myristoleic acid, physetoleic acid, oleic acid, linolic acid (リ ノ one Le acid), linolic acid (acid of リ ノ レ イ Application), ricinolic acid etc.Further can enumerate drying oil fatty acid that Semen Lini oil lipid acid, Stigma Croci fatty acid oil, soya fatty acid, Rice pollard oil lipid acid, siritch lipid acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid, perilla herb oil fat acid, hempseed oil lipid acid, cottonseed oil fatty acid, ready denier oil acid etc. have unconjugated double bond, semi-drying oil lipid acid etc.In addition, the lipid acid that can also and have conjugated double bond with a part of tung oil lipid acid etc.
The average carbon atom number of the hydrocarbon part of above-mentioned higher unsaturated fatty acid is preferably 13～23.
Be not particularly limited as the above-mentioned ethylene linkage unsaturated monomer that contains glycidyl, can enumerate for example glycidyl acrylate, glycidyl methacrylate, vinylformic acid methyl glycidyl ester, methacrylic acid methyl glycidyl ester etc.
The above-mentioned iodine value that has from the ethylene linkage unsaturated monomer of the group of higher unsaturated fatty acid is preferably 60～180, and more preferably 70～150.
Be not particularly limited as the above-mentioned polymerization process that has from the emulsifying resins of the group of higher unsaturated fatty acid, for example can be by obtaining with the same method of the above-mentioned resin that contains carbonyl.In addition, the above-mentioned iodine value that has from the emulsifying resins of the group of higher unsaturated fatty acid is preferably 5～100.Above-mentioned iodine value is if surpass 100, and then film coated surface is dry too fast, thereby can not get effect of sufficient.
When above-mentioned aqueous binders composition had the curing system that utilizes oxidative polymerization, preferred above-mentioned aqueous binders composition further contained siccative.The performance of above-mentioned siccative is used to make the unsaturated link(age) of above-mentioned group from higher unsaturated fatty acid that crosslinked effect takes place.As above-mentioned siccative, so long as usually get final product, be not particularly limited as the material of coating with siccative, wherein can enumerate cobalt, vanadium, manganese, cerium, lead, iron, calcium, zinc, zirconium, cerium, nickel, reach the naphthenate, octylate, resinate of tin etc. etc.The combined amount of above-mentioned siccative is 0.005～5 mass parts with respect to the resin solid composition of 100 mass parts usually.
Above-mentioned aqueous binders composition also is preferably the composition of the ambient cure by addition reaction.Be not particularly limited as this curing system, for example can enumerate, urethane/urea class, Mike's that addition class, carbodiimide/carboxyl class etc.
Be not particularly limited as above-mentioned urethane/urea class, for example can enumerate, contain as the polyisocyanate compound of solidifying agent and the aqueous binders composition of resin with hydroxyl and/or amino.As above-mentioned resin with hydroxyl and/or amino, can enumerate acrylic resin, vibrin, urethane resin, polyether resin, polycarbonate resin etc., these can use respectively and well known to a person skilled in the art material.
Above-mentioned polyisocyanate compound is not particularly limited, and for example can enumerate tolylene diisocyanate (TDI), 4,4 '-diphenylmethanediisocyanate (MDI), xylylene vulcabond aromatic diisocyanate compounds such as (XDI); Hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), 2,5-or 2,6-two (isocyanato-methyl) two ring [2.2.1] heptane aliphatics or alicyclic diisocyanate compounds such as (norbornene alkyl diisocyanate NBDI); Or polyisocyanate compounds such as the dipolymer of these diisocyanate cpds, trimer and TriMethylolPropane(TMP) affixture.In order to control reactivity, part or all of above-claimed cpd also can be used active dydrogen compounds end-blocking (block).Be not particularly limited as above-mentioned end-capping reagent, for example can enumerate, fatty alcohols such as methyl alcohol, ethanol, Virahol, propyl carbinol, 2-Ethylhexyl Alcohol, ethylene glycol monobutyl ether, hexalin; Phenols such as phenol, nitrophenol, ethyl phenol; Oximes such as methyl ethyl ketone oxime; Lactams such as ε-Ji Neixianan etc.
The mol ratio of the amount of the solidifying agent functional group of being contained in above-mentioned amount that contains the curing functional group of being contained in hydroxyl and/or the amino resin and the above-mentioned polyisocyanate compound is preferably in 1/10 to 1/0.05 scope.Above-mentioned mol ratio is if surpass 1/0.05, and then solidified nature is insufficient, and water tolerance may reduce.Above-mentioned mol ratio is if be lower than 1/10, and then the amount of unreacted polyisocyanate compound increases, and water tolerance may reduce.From water-proof viewpoint, above-mentioned mol ratio is more preferably in 1/0.6 to 1/0.1 scope.
Be not particularly limited as above-mentioned carbodiimide/carboxyl class, for example can enumerate, contain have as the carboxyl that solidifies functional group contain carboxy resin and as the aqueous binders composition of the poly-carbodiimide compound of solidifying agent.
Be not particularly limited as the above-mentioned carboxy resin that contains, for example can enumerate, carboxylic acrylic resin, carboxylic vibrin, carboxylic Synolac and carboxylic urethane resin etc.Above-mentioned when containing carboxy resin and being acrylic resin, preferably adopt monomer composition to carry out the emulsifying resins that letex polymerization obtains by making acrylic or methacrylic acid etc. comprise ethylene linkage unsaturated monomer with carboxyl.
As above-mentioned poly-carbodiimide compound, can use day commercially available products such as V-02 of the clear society's system of weaving.In addition, can also use the following material that obtains: utilize the phospholene oxides that is known as the carbodiimide catalyzer to make the polyisocyanate compound carbodiimideization of above enumerating, obtain the poly-carbodiimide of isocyanic ester endization, to resulting end is that the poly-carbodiimide of isocyanic ester carries out hydrophilicity-imparting treatment, uses the material that obtains thus as described poly-carbodiimide compound.
The mol ratio of the amount of the solidifying agent functional group of being contained in the amount of the above-mentioned curing functional group that contains in the carboxy resin to be contained and the above-mentioned poly-carbodiimide compound is preferably in 1/10 to 1/0.05 scope.Above-mentioned mol ratio is if surpass 1/0.05, and then water tolerance may reduce.Above-mentioned mol ratio is if be lower than 1/10, and then water tolerance may reduce.From water-proof viewpoint, above-mentioned mol ratio is more preferably in 1/0.6 to 1/0.1 scope.
Be not particularly limited as your addition class of above-mentioned Mike, for example can enumerate, contain compound and have two above α, the aqueous binders composition of the compound of beta-unsaturated carbonyl with active methylene group and/or active methylene.
As above-mentioned compound, can enumerate for example etheric acid, propanedioic acid, cyanoacetic acid and their derivative with active methylene group and/or active methylene.Be not particularly limited as described derivative, can enumerate for example reaction product of polyvalent alcohol and above-claimed cpd.
Have two above α as above-mentioned, the compound of beta-unsaturated carbonyl is not particularly limited, for example can enumerate, has the methacrylate based and/or acrylate-based compound more than 2 in per 1 molecule, for example for having the methacrylate based and/or acrylate-based compound that between the α relevant, β carbon, has two keys more than 2 with carbonyl.Specifically, can enumerate (methyl) acrylate of polyvalent alcohol, for example can enumerate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, 1,4-cyclohexyl dimethanol two (methyl) acrylate, 4,4 '-isopropylidene, two hexalin two (methyl) acrylate, two (methylol) three ring [5.2.1.0] decane two (methyl) acrylate, 1,3,5-three (2-hydroxyethyl) cyanuric acid three (methyl) acrylate etc.; Many (methyl) acrylate resin of many (methyl) acrylate resin of acrylic polyol, many (methyl) acrylate resin of polyester polyol, polyether glycol, many (methyl) acrylate resin of epoxy polyol, many (methyl) acrylate resins of polyurethane polyol and many (methyl) acrylate resin of silicone polyvalent alcohol etc.
Above-mentioned amount with curing functional group of being contained in the compound of active methylene group and/or active methylene and above-mentionedly have two above α, the mol ratio of the unsaturated link(age) that is contained in the compound of beta-unsaturated carbonyl is preferably in 1/10 to 1/0.05 scope.Above-mentioned mol ratio is if surpass 1/0.05, and then solidified nature is insufficient, and water tolerance might reduce.Above-mentioned mol ratio is if be lower than 1/10, and then unreacted have two above α, and the amount of the compound of β one unsaturated carbonyl can increase, and water tolerance might reduce.From water-proof viewpoint, above-mentioned mol ratio is more preferably in 1/0.6 to 1/0.1 scope.
Further be mixed with stain control agent in the aqueous solidified type antifouling paint compositions of the present invention.Be not particularly limited as above-mentioned stain control agent, can use known stain control agent, can enumerate for example mineral compound, the organic compound that contains metal and metal-free organic compound etc.
Be not particularly limited as above-mentioned stain control agent, for example can enumerate, Red copper oxide, ethylenebis (dithiocarbamic acid) manganese, the dimethylamino zinc formate, 2-methyl sulfo--uncle's 4-fourth amino-6-cyclopropylamino-s-triazine, 2,4,6-tetrachloro isopropyl cyanide, N, N-dimethyl dichlorophenyl urea, ethylenebis (dithiocarbamic acid) zinc, Rhodan copper, 4,5-two chloro-2-n-octyl-3 (2H) isothiazolinone, N-(a fluorine dichloromethyl sulfo-) phthalic imidine, N, N '-dimethyl-N '-phenyl-(N-one fluorine dichloromethyl sulfo-) sulphonamide, the zinc salt and the mantoquita of 2-mercaptopyridine-1 monoxide, tetramethyl thiuram disulfide, 2,4,6-trichlorophenyl maleimide, 2,3,5,6-tetrachloro-4-(sulfonyloxy methyl) pyridine, 3-iodo-2-propyl group butyl carbamate, two iodo methyl are to three sulfones, phenyl (two pyridyl) dichloride bismuth, 2-(4-thiazolyl)-benzoglyoxaline, triphenyl pyridine boron, octadecane amine-triphenyl-boron, lauryl amine-triphenyl-boron etc.Above-mentioned substance may be used singly or two or more kinds thereof.Consider from the aspect that gives full play of its function, preferably above-mentioned substance is used in combination.
In above-mentioned aqueous solidified type antifouling paint compositions, the combined amount of preferred above-mentioned stain control agent following in the coating solids component be limited to 0.1 quality %, on be limited to 80 quality %.Its combined amount can not expect that then it has anti-fouling effect if be lower than 0.1 quality %, if surpass defectives such as 80 quality % then crack, peel off on filming.More preferably above-mentioned combined amount following be limited to 1 quality %, on be limited to 60 quality %.
Above-mentioned stain control agent can mix with the form of the stain control agent thickener that contains water-soluble dispersion resin and above-mentioned stain control agent.By above-mentioned stain control agent being made this stain control agent thickener, stain control agent is easy to discharge in water, can obtain excellent didirtresistance.When using carbamate curing system etc. not have the aqueous binders composition of above-mentioned feature, preferably use above-mentioned stain control agent thickener.
In aqueous solidified type antifouling paint compositions of the present invention, because above-mentioned stain control agent thickener together uses with the aqueous binders composition with solidified nature, resulting filming is cured film, thereby it has excellent in water resistance, and didirtresistance is also excellent.It is believed that this is that stain control agent is easy to carry out stripping by the water-soluble dispersion resin that is contained in the above-mentioned stain control agent thickener owing to use when filming in water.
Be not particularly limited as above-mentioned water-soluble dispersion resin, can use known dispersion resins such as acrylic resin, vibrin, urethane resin, the acid number of above-mentioned dispersion resin is preferably 10～300mgKOH/g, and number-average molecular weight is preferably in 1000～20000 scope.
Above-mentioned acid number is if be lower than 10mgKOH/g, and then water-soluble reduction may impair stability.On the other hand, acid number is if be higher than 300mgKOH/g, and then the wetting ability of resin is too high, and the water tolerance of filming may reduce.The upper limit of above-mentioned acid number is 100mgKOH/g more preferably.
Above-mentioned number-average molecular weight is lower than at 1000 o'clock, and molecular weight is low excessively, and stain control agent is fully disperseed.In addition, number-average molecular weight surpasses at 20000 o'clock, then can not guarantee water-solublely, and viscosity is too high, may be difficult to handle.The lower limit of above-mentioned number-average molecular weight more preferably 5000, the upper limit of above-mentioned number-average molecular weight more preferably 15000.
There is multiple material as above-mentioned water-soluble dispersion resin, can uses commercially available pigment dispersing agent.As its concrete trade(brand)name, can enumerate Solsperse 20000, Solsperse 27000, Solsperse 41090 (above-mentioned substance is the Avecia corporate system); Disperbyk 180, Disperbyk 181, Disperbyk 182, Disperbyk 183, Disperbyk 184, Disperbyk 190, Disperbyk191, Disperbyk 192 (above-mentioned substance is a BYK Japan KK system); Polymer 450, Polymer451, Polymer 452, Polymer 453, EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550 (above-mentioned substance is an EFKA Additives corporate system); Flowlen G-700, Flowlen TG-720, Flowlen 730W, Flowlen 740W, Flowlen 745W (above-mentioned substance is chemistry society of a common prosperity society system); Joncryl 678, Joncryl 679, Joncryl 62 (above-mentioned substance is a Johnson Polymer corporate system) etc.
The above-mentioned water-soluble dispersion resin in the above-mentioned stain control agent thickener and the ratio of mixture of above-mentioned stain control agent are represented preferred in 1/99 to 50/50 scope with solids component.Above-mentioned ratio of mixture is if outside above-mentioned scope, and then the dispersion viscosity of stain control agent thickener is too high, and perhaps the dispersiveness of stain control agent reduces, and stability may be insufficient.
And, except that adding mentioned component, also can add additive commonly used such as pigment described later, softening agent in the above-mentioned stain control agent thickener.
When above-mentioned stain control agent thickener contained pigment, the content of pigment was preferably below the 50 quality %.
Above-mentioned stain control agent thickener for example can obtain above-mentioned water-soluble dispersion resin and above-mentioned stain control agent blended method by utilizing colo(u)rant dispersion machines such as sand mill.
Preferred mix above-mentioned stain control agent thickener so that the combined amount of the stain control agent in the water-based antifouling paint compositions following in the coating solids component be limited to 0.1 quality %, on be limited in the scope of 80 quality %.Above-mentioned combined amount can not expect that then it has anti-fouling effect if be lower than 0.1 quality %, if surpass 80 quality %, defectives such as may cracking, peel off on then filming.More preferably above-mentioned following be limited to 1 quality %, on be limited to 60 quality %.
Preferably further be mixed with the organic polymer particle in the aqueous solidified type antifouling paint compositions of the present invention.Above-mentioned organic polymer particle can easily form the excellent properties of filming with low frictional properties by being added into as additive in the aqueous solidified type antifouling paint compositions of the present invention thereby have.
Preferred above-mentioned organic polymer particle is being below the 15g/L in 23 ℃ according to the solubleness in the artificial seawater of ASTM D1141-98 defined, to the water regain according to the artificial seawater of ASTM D1141-98 defined is more than the 0.01 quality %, and this particle grain size is 0.05～100 μ m.Also promptly, no matter high molecular chemical structure how, as long as add the organic polymer particle that satisfies above-mentioned character, just can access desired rerum natura.
In addition, employed as the benchmark of solubleness and water regain herein is the artificial seawater of defined among the ASTM D1141-98.Owing to mainly used in seawater by formed the filming of coating composition of the present invention, thereby above-mentioned solubleness and water regain need be benchmark with the seawater rather than be that benchmark is judged with the pure water.
Preferred above-mentioned organic polymer particle is being below the 15g/L in 23 ℃ according to the solubleness in the artificial seawater of ASTM D1141-98 defined.Above-mentioned solubleness then may can not brought into play sufficient low friction performance if surpass 15g/L.Above-mentioned solubleness is preferably below the 12g/L.In addition, above-mentioned solubleness is the value that following mensuration obtains: the organic polymer particle down after the drying, is carried out weighing in room temperature, decompression, and be determined at according to the solubleness in the prepared artificial seawater of ASTM D1141-98.
Preferred above-mentioned organic polymer particle is more than the 0.01 quality % to the water regain according to the artificial seawater of ASTM D1141-98 defined.Above-mentioned water regain is if be lower than 0.01 quality %, and then the affinity with seawater reduces, thereby can not get effect of sufficient, and the reduction of friction is suppressed.Swelling takes place in the organic polymer particle that uses among the present invention when contacting with water, and has the character that is not dissolved in water, thereby can give play to suitable low friction performance.Above-mentioned water regain is preferably more than the 0.1 quality %.
In addition, water regain among the present invention is the value that following mensuration obtains: accurately weighing 1g in room temperature through vacuum (decompression) exsiccant organic polymer particle, be added into 50g according to after in the artificial seawater of ASTM D1141-98 preparation, stirred 5 hours in 23 ℃, filter then, rinsing residue carries out weighing, obtains water regain.
In addition, for above-mentioned organic polymer particle, the preferred following 0.05 μ m that is limited to of its particle diameter, on be limited to 100 μ m.Above-mentioned particle diameter then can not be reduced the effect of friction fully if be lower than 0.05 μ m.Above-mentioned particle diameter then may produce the problem of the condition of surface variation of filming if surpass 100 μ m.Above-mentioned lower limit is preferably 0.1 μ m, and the above-mentioned upper limit is preferably 40 μ m.Above-mentioned particle diameter is 1～30 μ m more preferably.In addition, above-mentioned particle diameter is measured with following condition and is obtained, and refers to the mean value of the particle diameter of being exported when the distribution benchmark that the operational manual of following apparatus is put down in writing is set at volume.
Device name, manufacturers: SALD-2200, society of Shimadzu Seisakusho Ltd. system
Measure and use dispersion medium: deionized water
Above-mentioned organic polymer particle can be the polymer of natural origin, also can be synthetic macromolecule.Above-mentioned organic polymer particle has the hydrophilic functional group's of appropriateness amount, preferably has cross linked chain as required.Can enumerate hydroxyl, amino, carboxyl, amide group, polyoxyethylene groups etc. as above-mentioned hydrophilic functional group.Though can obtain high water regain by having hydrophilic group, wetting ability is too high, the solubleness in seawater is too high sometimes.When wetting ability is too high, can be by introducing hydrophobic group or carrying out the crosslinked solubleness that is adjusted in the artificial seawater.
As the polymer that can be used as organic polymer particulate natural origin of the present invention, for example can enumerate polyoses such as chitin, chitosan, gum arabic, Lalgine, carrageenin, agar, xanthan gum, gelling gum, Mierocrystalline cellulose, wood sugar, starch, pulullan polysaccharide, pectin, baked bean glue, dextran, curdlan; Keratin sulfate, collagen, spun silk, gamma-polyglutamic acid-(below be designated as protein such as γ-PGA): nucleic acid etc.In addition, as required to the polymer of these natural origins be hydrolyzed, crosslinking reaction etc. and the derivative compounds such as semi-synthetic polymer of the hydrophilization (for example hydroalkylation) that obtains, Pegylation, hydrophobization (for example alkylation), grafting, three dimensional stress be also contained in the described polymer.
The polymer of above-mentioned natural origin preferably has the cationic group.By having the cationic group, the effect of the easier reduction friction in seawater that obtains filming.Be not particularly limited as above-mentioned cationic group, can enumerate for example amino, amido, pyridyl etc.Can use the natural polymer that just has the cationic group originally, when there is not the polymer of cationic group in use, can be with this high molecular derivatives materialization to introduce the cationic group.
As above-mentioned organic polymer particle, more preferably be selected from least a organic polymer particle in the group of forming by the derivative of chitin, chitosan, γ-PGA, spun silk crushed material and these materials.
Above-mentioned chitin is a polyose, and its deacetylated thing is a chitosan.Above-mentioned deacetylated can be for deacetylated fully, also can be for partially deacetylated.Compound that also can utilize polyoxyethylene as required, contain aldehyde radical etc. is modified or is crosslinked.
Above-mentioned spun silk crushed material is that silk that silkworm is produced is that spun silk is pulverized and the granular crushed material that obtains.Among the present invention, by inference, as the principal constituent of spun silk and the polymer of the natural origin that contains is that fibroin, sericin have above-mentioned effect.
Employed spun silk crushed material can be natural spun silk directly to be pulverized and the crushed material that obtains among the present invention, also can remove impurity component as required and be hydrolyzed, make with extra care, classification etc. and the granular crushed material that obtains.
γ-PGA is the polymer shown in the following general formula (1).
Figure A20058004527600231
As similar material, mucous principal constituent that Bacillus natto produces is arranged and as polymer absorbent material, Biodegradable material, medical material, foodstuff additive, cosmetics material and prominent polymer.Use γ-PGA particle for the natural origin thing that above-mentioned mushroom produced being carried out material dry and that granulating obtains among the present invention.Above-mentioned γ-PGA particle also can be remove impurity component as required and be hydrolyzed, make with extra care, classification etc. and the granular material that obtains.
Can use synthetic macromolecule as above-mentioned organic polymer particle.Be not particularly limited as above-mentioned synthetic macromolecule, can enumerate for example acrylic resin, vibrin, amine resins, modified polyvinyl alcohol resinoid etc.Above-mentioned synthetic macromolecule be preferably have hydroxyl, the hydrophilic resin of hydrophilic radical such as amino, carboxyl, also can have partial cross-linked structure as required.Can adjust hydrophilic/hydrophobic and crosslinked ratio according to known method, obtain the organic polymer particle thus.
As above-mentioned synthetic macromolecule, the acrylic resin particle especially can suit to use.Aforesaid propylene acid resin particle for example can obtain by the monomer composition that contains acrylic monomer and cross-linkable monomer is carried out letex polymerization.
Be not particularly limited as aforesaid propylene acids monomer, for example can enumerate the alkyl ester of acrylic or methacrylic acid such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA; (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate etc. contain (methyl) acrylate of hydroxyl; Vinyl cyanide, methacrylonitrile, (methyl) vinylformic acid dimethylamino ethyl ester etc.
In the above-mentioned emulsion polymerization, can use other ethylene linkage unsaturated monomer.Be not particularly limited as above-mentioned ethylene linkage unsaturated monomer, can enumerate for example vinylbenzene, alpha-methyl styrene, Vinyl toluene, t-butyl styrene, vinyl-acetic ester, propionate etc.Aforesaid propylene acids monomer and ethylene linkage unsaturated monomer may be used alone, used in two or more.
Be not particularly limited as above-mentioned cross-linkable monomer, for example can enumerate, intramolecularly has the monomer etc. of the ethylene linkage unsaturated link(age) of plural free redical polymerization.
The monomer that has the ethylene linkage unsaturated link(age) of two above free redical polymerizations as the above-mentioned intramolecularly that can use in the manufacturing of acrylic resin particulate is not particularly limited, for example can enumerate, glycol diacrylate, ethylene glycol dimethacrylate, the triethylene glycol dimethacrylate, the TEG dimethacrylate, 1, the 3-butylene glycol dimethacrylate, Viscoat 295, trimethylolpropane trimethacrylate, 1, the 4-butylene glycol diacrylate, neopentylglycol diacrylate, 1, the 6-hexanediyl ester, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, the dimethyl allene acid glyceride, glycerol diacrylate, glycerine allyloxy dimethacrylate, 1,1,1-trimethylolethane diacrylate, 1,1,1-trimethylolethane trimethacrylate acrylate, 1,1,1-trimethylolethane dimethacrylate, 1,1,1-trimethylolethane trimethacrylate methacrylic ester, 1,1, the 1-trimethylolpropane diacrylate, 1,1, the 1-Viscoat 295,1,1-TriMethylolPropane(TMP) dimethacrylate, 1,1, the polymerizability unsaturated monocarboxylic ester of polyvalent alcohols such as 1-trimethylolpropane trimethacrylate; The unsaturated alcohol ester of polymerizability of polyprotonic acids such as triallyl cyanurate, triallyl isocyanurate, trimellitic acid triallyl, diallyl p phthalate, Phthalic acid, diallyl ester; Vinylstyrenes etc. are by aromatics of plural vinyl substituted etc.
Above-mentioned cross-linkable monomer in the above-mentioned monomer composition is preferably more than the 1 quality % of monomer composition total amount.Above-mentioned mass ratio then might can not get desired acrylic resin particle if outside above-mentioned scope.Above-mentioned mass ratio is 5～70 quality % more preferably.
Polymerization process as above-mentioned monomer composition is not particularly limited, can by letex polymerization, suspension polymerization etc. in the past known method carry out polymerization.
Above-mentioned organic polymer particle can be for comprising two or more high molecular composite resin particles.
Here saidly comprise two or more high molecular composite resin particles and be meant the material that the polymer of above-mentioned various natural origins, two or more polymers in the synthetic macromolecule is carried out granulating and obtain; concrete means as compoundization are not particularly limited, and can enumerate arbitrary method such as mixing, grafting, nucleocapsidization, IPN (structures of interpenetrating(polymer)networks) change, surface physics and chemistry.
Be not particularly limited as above-mentioned two or more polymer, can enumerate for example polymer and the above-mentioned synthetic macromolecule of above-mentioned natural origin as described above.The composite resin particle that wherein preferably contains hydrophilic resin and acrylic resin, described hydrophilic resin are selected from by starch, pulullan polysaccharide, gum arabic, κ-carrageenan, gelatin, Mierocrystalline cellulose, chitosan and their derivative; At least a material in the group that polyvinyl alcohol, polyallylamine, polyvinylamine, poly-(methyl) acrylamide, poly-(methyl) vinylformic acid and multipolymer thereof are formed.If adopt this combination, then can come by the composition of acrylic resin to change the particulate rerum natura according to expectation, also can obtain wetting ability simultaneously, be preferred therefore.The material that can not reach the object of the invention in the time of above-mentioned hydrophilic resin and acrylic resin can being used separately separately makes up and uses.As above-mentioned hydrophilic resin, more preferably use at least a resin that is selected from chitosan, chitosan derivatives, the polyvinyl alcohol.
The composite resin particle that contains above-mentioned hydrophilic resin and acrylic resin for example can be by carrying out letex polymerization to the starting monomer of acrylic resin or suspension polymerization obtains in the presence of above-mentioned hydrophilic resin.Employed emulsifying agent can use known emulsifying agent during as polymerization, but from water-proof viewpoint, preferably uses reactive emulsifier.Can enumerate above-mentioned material as above-mentioned reactive emulsifier.
The addition of above-mentioned reactive emulsifier is preferably below the 15 quality %.If surpass 15 quality %, then might reduce by the resulting water tolerance of filming of the coating that composite resin particle is mixed.
In above-mentioned composite resin particle synthetic, be preferably 40/60 to 97/3 in mass ratio (solids component) as the monomer composition of the raw material of acrylic resin and the ratio of mixture of hydrophilic resin.
In the coating composition of the present invention, above-mentioned organic polymer particulate combined amount with respect to all solids composition in the coating be in be limited to down 0.01 quality %, on be limited in the scope of 15 quality %.Above-mentioned combined amount then can not get desired effect if be lower than 0.01 quality %, thereby not preferred.Above-mentioned combined amount then might can not get reducing the effect that rubs in the water accordingly with combined amount if surpass 15 quality %.Above-mentioned lower limit is 0.1 quality % more preferably, and the above-mentioned upper limit is 12 quality % more preferably.
In addition, can mix the above-mentioned organic polymer particle of one or two or more kinds in the aqueous solidified type antifouling paint compositions of the present invention.
Have water tolerance and didirtresistance and have filming of excellent low friction performance simultaneously by mixing the surface that the aqueous solidified type antifouling paint compositions of above-mentioned organic polymer particulate is coated on applied thing, and can forming.
For example, when having above-mentioned organic polymer particulate aqueous solidified type antifouling paint compositions of the present invention to coat about 10～30 nautical miles/hour boats and ships of travel speed, can obtain good low friction performance with mixed.By the coating aforementioned coating composition, to compare with coating antifouling paint in the past, the friction impedance can reduce more than 2%～3%.Therefore, mixed have above-mentioned organic polymer particulate aforementioned coating composition of the present invention particularly can significantly give play to the effect that reduces the navigation fuel cost as ship-bottom paint the time.
Except that adding mentioned component, can also add additive commonly used such as softening agent, pigment in the aqueous solidified type antifouling paint compositions of the present invention.
For example can enumerate phthalic ester plasticizers such as dioctyl phthalate (DOP), dimethyl phthalate, dicyclohexyl phthalate as above-mentioned softening agent; Fatty diacid ester plasticizers such as hexanodioic acid isobutyl ester, Uniflex DBS; Diol-lipid softening agent such as Diethylene Glycol dibenzoate, tetramethylolmethane alkyl ester; Phosphate plasticizer such as bisphosphate trieline ester, Trichloroethyl Phosphate; Epoxy plasticiser such as epoxy soybean oil, octyl epoxy stearate; Organic tin such as dioctyltin laurate, dibutyl tin laurate softening agent; Trioctyl trimellitate, three acetylene etc.Above-mentioned substance may be used alone, used in two or more.
For example can enumerate filling pigment such as settleability barium, talcum, clay, chalk, white carbon black, white fused alumina, bentonite as above-mentioned pigment; Painted pigment such as titanium dioxide, zirconium white, alkaline lead sulfate, stannic oxide, carbon black, graphite, colcother, chrome yellow, phthalocyanine green, phthalocyanine blue, quinacridone etc.Above-mentioned substance may be used singly or two or more kinds thereof.
Except that above-mentioned substance, be not particularly limited as other additive, for example can enumerate monobasic organic acid, camphors etc. such as phthalic acid mono, mono succinate monooctyl ester; Waterbinding agent, anti-sagging agent; Anti-flooding agent; Antisettling agent; Defoamer etc.
The preparation method of aqueous solidified type antifouling paint compositions of the present invention is not particularly limited, for example, can in the aqueous binders composition, add stain control agent, organic polymer particle, softening agent, film to consume and adjust additive commonly used such as agent, pigment, utilize mixing machines such as ball mill, pebble mill, roller mill, sand mill to mix, be prepared thus.In addition; when using stain control agent with the form of stain control agent thickener; stain control agent and water-soluble dispersion resin and pigment, softening agent, other additive can be mixed with sand mill etc. in advance; then the gained mixture is mixed with aqueous binders composition and organic polymer particle, prepare aforementioned coating composition thus.
In the above-mentioned aqueous solidified type antifouling paint compositions, the amount of preferred nonvolatile component is 10～90 quality %.The amount of above-mentioned nonvolatile component then may be difficult to form thick film if be lower than 10 quality %.The amount of above-mentioned nonvolatile component is if surpass 90 quality %, the viscosity in the time of then may being difficult to adjust application.
In the above-mentioned aqueous solidified type antifouling paint compositions, preferred PWC is 50～90 quality %.Above-mentioned PWC is if be lower than 50 quality %, and then Air drying may reduce.In addition, above-mentioned PWC then may be difficult to film forming if surpass 90 quality %.
For above-mentioned aqueous solidified type antifouling paint compositions, can utilize ordinary method that it is coated the surface of coated article, moisture is removed in volatilization at normal temperatures then, forms dry coating thus.Filming of obtaining thus has the effect of the pollution that suppresses the aouatic structure thing.By being coated with the antifouling coating that above-mentioned aqueous solidified type antifouling paint compositions obtains also is one of the present invention, and the aouatic structure thing with above-mentioned antifouling coating also is one of the present invention.
Above-mentioned antifouling coating for example can by above-mentioned aqueous solidified type antifouling paint compositions is utilized pickling process, spraying method, brushing, roller coat, electrostatic applications etc. in the past known method be coated with and form.Can place carrying out drying in room temperature after the coating, or the about 80 ℃ forced dryings of carrying out about a few hours～1 day.The dry film thickness of above-mentioned antifouling coating preferably be in be limited to down 30 μ m, on be limited in the scope of 500 μ m.Above-mentioned dry film thickness is if be in the above-mentioned scope, and then the balance of water tolerance and didirtresistance is good, thereby preferred.
The resin solid composition in the above-mentioned antifouling coating and the mass ratio of stain control agent are not particularly limited, and from the viewpoint of anti-fouling effect, are preferably 1: 7 to 1: 1.In addition, when having self abrasive property by the reversed reaction that is cured reaction, from the viewpoint of water tolerance and didirtresistance, the amount of the curing functional group of being contained in the preferred above-mentioned antifouling coating with respect to the resin solid composition in the scope of 0.00015～8mmol/g.In addition, the amount of above-mentioned curing functional group can be calculated by system component.
Above-mentioned coated article can carry out pre-treatment as required.Be not particularly limited as above-mentioned coated article,, be preferably the aouatic structure thing from forming the viewpoint of filming that demonstrates excellent low friction performance.
Be not particularly limited as above-mentioned aouatic structure thing, can enumerate for example boats and ships, pipeline material, fishing net etc.
Aqueous solidified type antifouling paint compositions of the present invention can access the water tolerance excellence and have filming of good anti-fouling effect.
Can access following aqueous solidified type antifouling paint compositions according to the present invention, it is excellent and have filming of good anti-fouling effect to utilize this aqueous solidified type antifouling paint compositions can form water tolerance.Utilize the resulting antifouling coating of above-mentioned aqueous solidified type antifouling paint compositions owing to have above-mentioned effect, thereby can be widely used in the aouatic structure thing.
Embodiment
The present invention will be described in more detail to enumerate embodiment below, but the present invention is not limited in these embodiment.In addition in an embodiment, if be not particularly limited, then " part " expression " mass parts ".
Production Example 1
Contain the manufacturing of the emulsifying resins of carbonyl
To contain 10 parts of diacetone-acryloamide(DAA)s, 30 parts of methyl methacrylates, 20 parts of ethyl propenoates, 30 parts of n-butyl acrylates, 9 parts of vinylbenzene, the monomer mixture of 1 part of methacrylic acid is added to (the first industrial pharmacy society system with 60 parts of ion exchanged waters and 6 parts of Aqualon HS-10, the anionic reactive emulsifier) mixes and in the solution that obtains, carry out emulsification with stirrer then, obtain the pre-emulsion of monomer mixture.In addition 0.3 part of ammonium persulphate is dissolved in 17 parts of ion exchanged waters, obtains initiator solution.
In reaction vessel, add 70 parts of ion exchanged waters and 2 parts of Aqualon HS-10, under nitrogen atmosphere, be warming up to 80 ℃ with dropping funnel, thermometer, nitrogen ingress pipe, reflux exchanger and stirrer.Then, resulting pre-emulsion and initiator solution are utilized 3 hours time drip by different dropping funnels simultaneously.After dripping end, further continued to react two hours in this temperature.After the cooling, utilize the alkaline neutraliser aqueous solution that contains 7 parts of ion exchanged waters and 1 part of dimethylethanolamine to neutralize.Obtain containing the emulsifying resins of carbonyl thus, wherein solids component is 40 quality %, and the median size of this resin is 90nm.
Production Example 2
Contain the manufacturing of the emulsifying resins of acetoacetoxy groups
Except 10 parts diacetone-acryloamide(DAA) being changed to 10 parts acetoacetoxyethyl methacrylate, similarly obtain containing the emulsifying resins of acetoacetoxy groups with Production Example 1.The resulting solids component that contains the emulsifying resins of acetoacetoxy groups is 40 quality %, and median size is 90nm.
Production Example 3
Contain the manufacturing of the emulsifying resins of alkoxysilyl
Except 10 parts of diacetone-acryloamide(DAA)s being changed to 10 parts of KBM-503 (SHIN-ETSU HANTOTAI chemistry society system methacryloxypropyl trimethoxy silane), similarly obtain containing the emulsifying resins of alkoxysilyl with Production Example 1.The resulting solids component that contains the emulsifying resins of alkoxysilyl is 40 quality %, and median size is 90nm.
Production Example 4
Contain manufacturing from the emulsifying resins of the group of higher unsaturated fatty acid
Except 10 parts of diacetone-acryloamide(DAA)s being changed to the soya fatty acid affixture of 10 parts of glycidyl methacrylate, similarly obtain containing emulsifying resins from the group of higher unsaturated fatty acid with Production Example 1.The resulting solids component that contains from the emulsifying resins of the group of higher unsaturated fatty acid is 40 quality %, and median size is 90nm.
Production Example 5
The manufacturing of stain control agent thickener
Add 40 parts of Red copper oxide, 5 parts of pyrithione zincs, 5 parts of zinc oxide, 5 parts of colcothers, 5 parts of talcums with respect to 20 parts of deionized waters, further add 20 parts of BYK-190 (BYK Japan KK system) and as the BYK-019 (BYK Japan KK system) of defoamer as pigment dispersing agent, utilize sand mill to disperse, obtain solids component thus and be 76.5 quality %, PWC and be 92%, granularity is the stain control agent thickener of 20 μ m.
Embodiment 1
With the 100 parts of emulsifying resins that contains carbonyl, 4 parts of HardenerSC (society of Asahi Chemical Industry systems that obtain by Production Example 1, the Urea,amino-solidifying agent, solids component is 50 quality %), 200 parts of stain control agent thickener, 3 parts of PUR-2150 (Akzo Nobel society systems that obtain by Production Example 5, urethane association type tackifier, solids component is 35 quality %) disperse with dispersion machine, obtain aqueous solidified type antifouling paint compositions thus.
The PWC of this coating composition is 72%, and solids component is 64 quality %, solidifies the amount/carbonyl of functional group: 0.12mmol/g, amino urea groups: 0.047mmol/g, acid number 1.0mgKOH/g.
Further resulting coating composition is carried out the viscosity adjustment with ion exchanged water, so that its viscosity that records with the Stomer viscometer is 90KU in the time of 25 ℃.
Utilizing hairbrush to be applied to this coating composition adopts sand paper (granularity is 240) to carry out on the FRP plate (100 * 300 * 3mm handles through gluing) of hacking, so that its dry film thickness is 400 μ m.After the coating, be that 20 ℃, relative humidity are to place 1 day in 65% the atmosphere, obtain testing coated plate thus in temperature.
Embodiment 2～6
The emulsifying resins that contains acetoacetoxy groups that use is obtained by Production Example 2,3,4, the emulsifying resins that contains alkoxysilyl, contain emulsifying resins and WATERSOL 3060 (big Japanese ink chemical industry society system from the group of higher unsaturated fatty acid, aqueous alkide resin), Bayhydrol A145 (Sumika Bayer Urethane Co., Ltd. make, the aqueous polyurethane polyvalent alcohol), and change to the composition shown in the table 1, in addition, operation obtains aqueous solidified type antifouling paint compositions respectively similarly to Example 1.Further obtain testing coated plate similarly to Example 1.
Comparative example 1
Except changing to the composition shown in the table 1, the relatively non-curing antifouling paint compositions of water-based of usefulness is made in operation similarly to Example 1, obtains testing coated plate simultaneously.
For the resulting coated plate of respectively testing, adopt its water tolerance of following standard evaluation and didirtresistance.
＜water tolerance and didirtresistance 〉
At the Nippon Paint in Okayama County Yu Ye city Marine Coating Co., the Ltd. institute that borders on the sea will test coated plate and vertically be impregnated into depth of water 1m from marine buoyant raft, the condition of surface of filming of visual observation after 1 month, 6 months, 12 months.The result is as shown in table 1.
With following standard water tolerance is estimated.
Zero: no abnormal
△: only find a small amount of bubble
*: find bubble on whole surface
With following standard didirtresistance is estimated.
◎: do not have and paying biology
Zero: only be attached with the mucilage that is easy to remove
△: on the area of test board less than 10%, be attached with animals and plants
*: on the area of test board more than 10%, less than 50%, be attached with animals and plants
* *: is attached with animals and plants on the area of test board more than 50%
To resulting aqueous solidified type antifouling paint compositions, estimate self abrasive property as follows.
＜self abrasive property 〉
Utilizing coating machine to be applied to resulting aqueous solidified type antifouling paint compositions adopts sand paper (granularity is 240) to carry out on the FRP plate (handling through gluing) of hacking, so that its dry film thickness is about 240 μ m.After the coating, be that 20 ℃, relative humidity are to place 1 day in 65% the atmosphere, obtain testing coated plate thus in temperature.This test coated plate is installed on the swing roller that is arranged in the seawater, is 10 nautical miles/hour with circumferential speed and is rotated, measure per 3 months consumption thickness (μ m).It the results are shown in table 1.
[table 1]
Solids component ratio (%) Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Comparative example 1
Emulsifying resins Production Example 1 40 100 - - - - - 100
Production Example 2 40 - 100 - - - - -
Production Example 3 40 - - 100 - - - -
Production Example 4 40 - - - 100 - - -
Watersol 3060 *1 38 - - - - 105 - -
Bayhydrol A145 *2 45 - - - - - 62 -
Solidifying agent Hardener SC *3 50 4 - - - - - -
Hexamethylene-diamine 30 - 4 - - - - -
Bayhydur 3100 *4 100 - - - - - 12 -
Curing catalysts Phosphoric acid 100 - - 1 - - - -
Siccative *5 35 - - - 1 1 - -
Stain control agent thickener (Production Example 5) 76.5 200 200 200 200 200 200 200
Tackifier PUR-2150 35 3 3 3 3 3 3 3
Water tolerance 1 month ○ ○ ○ ○ ○ ○ △
6 months ○ ○ ○ ○ ○ ○ ×
12 months ○ ○ ○ ○ ○ ○ ×
Didirtresistance 1 month ◎ ◎ ◎ ◎ ○ ○ ◎
6 months ◎ ◎ ◎ ○ ○ △ -
12 months ◎ ○ ○ ○ △ × -
Self abrasive property (μ m) 3 months 34 21 15 4 3 5 Can not measure
6 months 62 44 31 5 5 5 -
9 months 105 60 48 7 5 5 -
12 months 136 83 69 7 5 5 -
* 1: big Japanese ink chemical industry society system, aqueous alkide resin
* 2: Sumika Bayer Urethane Co., Ltd. system, aqueous polyurethane polyvalent alcohol
* 3: society of Asahi Chemical Industry system, Urea,amino-solidifying agent
* 4: Sumika Bayer Urethane Co., Ltd. system, aqueous polyurethane isocyanic ester
* 5: cobalt naphthenate
Can confirm to have excellent in water resistance by table 1, have excellent didirtresistance simultaneously by resulting the filming of embodiment.But in the embodiment 6 of carbamate curing system, though the water tolerance aspect is no problem, its long-term didirtresistance is relatively poor.Relative therewith, in the comparative example 1 as non-curing system, as can be known, it is big and make the dissolved problem in seawater of filming to have water tolerance.And in an embodiment, can confirm, with used the filming of aqueous binders composition that is cured by oxypolymerization and compared, used the didirtresistance excellence of filming of the aqueous binders composition that is cured by dehydrating condensation, particularly used carbonyl/hydrazides class to have excellent didirtresistance as the embodiment 1 of curing system.In addition, it is believed that the performance didirtresistance is relevant with himself abrasive property.
Production Example 6
Contain manufacturing from the emulsifying resins of the group of higher unsaturated fatty acid
The monomer mixture that will contain the soya fatty acid affixture of 10 parts of glycidyl methacrylate, 30 parts of methyl methacrylates, 20 parts of ethyl propenoates, 30 parts of n-butyl acrylates, 9 parts of vinylbenzene, 1 part of methacrylic acid is added to (the first industrial pharmacy society system with 60 parts of ion exchanged waters and 6 parts of Aqualon HS-10, the anionic reactive emulsifier) mixes and in the solution that obtains, carry out emulsification with stirrer then, obtain the pre-emulsion of monomer mixture.In addition 0.3 part of ammonium persulphate is dissolved in 17 parts of ion exchanged waters, obtains initiator solution.
In reaction vessel, add in 70 parts of ion exchanged waters and 2 parts of Aqualon HS-10, under nitrogen atmosphere, be warming up to 80 ℃ with dropping funnel, thermometer, nitrogen ingress pipe, reflux exchanger and stirrer.Then, resulting pre-emulsion and initiator solution are utilized 3 hours time drip by different dropping funnels simultaneously.After dripping end, further continued to react two hours in this temperature.After the cooling, utilize the alkaline neutraliser aqueous solution that contains 7 parts of ion exchanged waters and 1 part of dimethylethanolamine to neutralize.Obtain containing the emulsifying resins from the group of higher unsaturated fatty acid thus, wherein solids component is 40 quality %, and the median size of this resin is 90nm.
Production Example 7
Contain the manufacturing of the emulsifying resins of carboxyl
The monomer mixture that will contain 36 parts of methyl methacrylates, 20 parts of ethyl propenoates, 30 parts of n-butyl acrylates, 10 parts of vinylbenzene, 10 parts of methacrylic acids is added to (the first industrial pharmacy society system with 60 parts of ion exchanged waters and 6 parts of Aqualon HS-10, the anionic reactive emulsifier) mixes and in the solution that obtains, carry out emulsification with stirrer then, obtain the pre-emulsion of monomer mixture.In addition 0.3 part of ammonium persulphate is dissolved in 17 parts of ion exchanged waters, obtains initiator solution.
In reaction vessel, add 70 parts of ion exchanged waters and 2 parts of Aqualon HS-10, under nitrogen atmosphere, be warming up to 80 ℃ with dropping funnel, thermometer, nitrogen ingress pipe, reflux exchanger and stirrer.Then, resulting pre-emulsion and initiator solution are utilized 3 hours time drip by different dropping funnels simultaneously.After dripping end, further continued to react two hours in this temperature.After the cooling, utilize the alkaline neutraliser aqueous solution that contains 7 parts of ion exchanged waters and 1 part of dimethylethanolamine to neutralize.
The resulting solids component that contains the emulsifying resins of carboxyl is 40 quality %, and median size is 90nm.
Embodiment 7～10
The stain control agent thickener that adds mixing element shown in the table 2 and Production Example 5 in turn obtains aqueous solidified type antifouling paint compositions.Then, resulting coating composition is carried out the viscosity adjustment with ion exchanged water, so that its viscosity that records with the Stomer viscometer is 90KU in the time of 25 ℃.
Utilizing hairbrush to be applied to this coating composition adopts sand paper (granularity is 240) to carry out on the FRP plate (100 * 300 * 3mm handles through the colloid coating) of hacking, so that its dry film thickness is 400 μ m.After the coating, be that 20 ℃, relative humidity are to place 1 day in 65% the atmosphere, obtain testing coated plate thus in temperature.Further similarly obtain testing coated plate with embodiment.
Comparative example 2～4
The stain control agent thickener that adds mixing element shown in the table 2 and stain control agent or Production Example 5 in turn obtains two kinds of relatively use curing antifouling paint compositions and the non-curing antifouling paint compositions of water-based.Further similarly obtain testing coated plate with embodiment.
For the resulting coated plate of respectively testing, be 1 month and 6 months except making dipping time, adopt with the same method of aforesaid method and estimate water tolerance and didirtresistance.The result is as shown in table 2.
[table 2]
Solids component ratio (%) Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Comparative example 2 Comparative example 3 Comparative example 4
Emulsifying resins Production Example 6 40 100 - - - 100 - -
Watersol 3060 *1 38 - 105 - - - - -
Bayhydrol A145 *2 45 - - 62 - - 62 -
Production Example 7 40 - - - 79 - - 100
Solidifying agent Bayhydur 3100 *3 100 - - 12 - - 12 -
V-02 *4 40 - - - 21 - - -
Catalyzer Siccative *5 35 1 1 - - 1 - -
Stain control agent The thickener of Production Example 5 76.5 200 200 200 200 - - 200
The ZPT water dispersion *6 50 - - - - 300 300 -
Tackifier PUR-2150 35 3 3 3 3 3 3 3
Water tolerance 1 month ○ ○ ○ ○ ○ ○ △
6 months ○ ○ ○ ○ ○ ○ ×
Didirtresistance 1 month ◎ ○ ○ ○ △ × ○
6 months ○ ○ △ △ × ×× -
* 1: big Japanese ink chemical industry society system, aqueous alkide resin
* 2: Sumika Bayer Urethane Co., Ltd. system, aqueous polyurethane polyvalent alcohol
* 3: Sumika Bayer Urethane Co., Ltd. system, aqueous polyurethane isocyanic ester
* 4: day clear society's system of weaving, carbimide solidifying agent
* 5: cobalt naphthenate
* 6: the water dispersion of pyrithione zinc
Can confirm to have excellent in water resistance by table 2, have excellent didirtresistance simultaneously by resulting the filming of embodiment.It is more excellent that the embodiment 7 of particularly oxypolymerization class curing system and the curing system of other addition polymerization are compared didirtresistance.
On the other hand, in the comparative example 2 and 3 that does not use the stain control agent thickener, though the water tolerance aspect is no problem, its didirtresistance is relatively poor; And in the comparative example 4 as non-curing system, its water tolerance aspect has problem as can be known.
Production Example 8
The manufacture method of organic polymer particle A
In four-hole boiling flask, add the 500g heptane and be heated to 80 ℃ with prolong, thermometer, stirrer, nitrogen ingress pipe.In this solution, add 30g methyl methacrylate, 20g methoxy poly (ethylene glycol) (n=9) methacrylic ester, 25g vinylformic acid N, N-dimethylamino ethyl ester, 10g ethylene glycol dimethacrylate, 7g VPE-0601 (with the pure medicine of light Co., Ltd. system), make its reaction 7 hours, obtain solid component concentration and be 18% organic polymer particle dispersion A.This dispersion liquid of centrifugation obtains organic polymer particle A.With laser diffraction granularity measure of spread device (" SALD-2200 ", trade(brand)name, society of Shimadzu Seisakusho Ltd. system) resulting organic polymer particle A is carried out particle size determination, the particle diameter that records is 1.8 μ m.
Production Example 9
The manufacture method of organic polymer particle B
Adopt jet mill to pulverize gamma-polyglutamic acid-, obtaining particle diameter is the organic polymer particle B of 4 μ m.
Production Example 10,11
The manufacture method of organic polymer particle C and D
With chitin (the society's system of refining big day, chitin P) and chitosan (the chemical society of first sun system, SK-10) pulverize with jet mill respectively, obtain respectively being the chitin formed organic polymer particle C of 7 μ m and being the formed organic polymer particle of the chitosan D of 8 μ m by particle diameter by particle diameter.
Production Example 12
The manufacture method of organic polymer particle E
7.0g chitosan (" DAICHITOSAN VL ", NV100%, the industrial society system of refining big day), 57.7g ion exchanged water, 5.3g vinylformic acid are mixed with stirrer, obtain chitosan aqueous solution.Containing this chitosan aqueous solution of 70.0g, 30.0g ER-20 (rising sun electrification society system, the non-ionic type reactive emulsifier) with in the aqueous solution of 162.6g ion exchanged water add 28.8g methyl methacrylate, 10.1g cyclohexyl methacrylate, 40.6g 2-EHA, 10.0g Ethylene glycol dimethacrylate and 4.0g PEROYL L (Japanese grease society system, the peroxide radical initiator) mixed solution, carry out emulsification with stirrer then, obtain suspension liquid (outstanding turbid particle diameter is 10 μ m).
In reaction vessel, add 0.2g quinhydrones, 9.0g ER-20 (rising sun electrification society system with dropping funnel, thermometer, nitrogen ingress pipe, reflux exchanger and stirrer, the non-ionic type reactive emulsifier), the above-mentioned chitosan aqueous solution of 70.0g and 262.2g ion exchanged water, under nitrogen atmosphere, be warming up to 70 ℃.Then, the above-mentioned suspension liquid that obtains of disposable adding 356.1g continues reaction after 4 hours in this temperature, judges that polyreaction finishes, and cools off, and obtains the dispersion liquid (solids component is 20 quality %) of organic polymer particle E.Remove the moisture in this dispersion liquid, can only obtain organic polymer particle E.The particle diameter of above-mentioned organic polymer particle E is 15 μ m.
Production Example 13
The manufacture method of organic polymer particle F
7.0g polyoxyethylene (PEO) (" PEO-1 ", NV100%, the Sumitomo society's system of refining) is mixed with stirrer with the 57.7g ion exchanged water, obtain the PEO aqueous solution.In the aqueous solution that contains the PEO aqueous solution of 64.7g gained, 30.0g ER-20 and 162.6g ion exchanged water, add 42.1g methyl methacrylate, 21.5g n-BMA, 26.4g 2-EHA, 10.0g Ethylene glycol dimethacrylate and 4.0g PEROYL L (Japanese grease society system, the peroxide radical initiator) mixed solution, carry out emulsification with stirrer then, obtain suspension liquid (outstanding turbid particle diameter is 34 μ m).
In reaction vessel, add 0.2g quinhydrones, 9.0g ER-20,64.7g and the above-mentioned same PEO aqueous solution and 262.2g ion exchanged water, under nitrogen atmosphere, be warming up to 70 ℃ with dropping funnel, thermometer, nitrogen ingress pipe, reflux exchanger and stirrer.Then, the above-mentioned suspension liquid that obtains of disposable adding 361.3g continues reaction after 4 hours in this temperature, judges that polyreaction finishes, and cools off, and obtains the dispersion liquid (solids component is 20 quality %) of organic polymer particle F.Remove the moisture in this dispersion liquid, can only obtain organic polymer particle F.The particle diameter of above-mentioned organic polymer particle F is 40 μ m.
For resulting organic polymer particle A～F, adopt solubleness and water regain in the following method mensuration artificial seawater.
(solubleness and water regain)
Accurately weighing 1g carries out the dry resulting organic polymer particle of vacuum (decompression) in room temperature, is added into 50g according in the prepared artificial seawater of ASTM D1141-98, then in 23 ℃ of stirrings 5 hours.Then filter, rinsing residue also carries out weighing, tries to achieve water regain.
Next, carry out drying under reduced pressure, carry out weighing then, try to achieve the solubleness in seawater in room temperature.The result is as shown in table 3.
Embodiment 11～19, comparative example 5
Add the stain control agent thickener and the organic polymer particle of the mixing element shown in the table 3, Production Example 5 in turn, it is disperseed with dispersion machine, obtain aqueous solidified type antifouling paint compositions.Then, resulting coating composition is carried out the viscosity adjustment with ion exchanged water, so that its viscosity that records with the Stomer viscometer is 90KU in the time of 25 ℃.In addition, the unit of combined amount all is " g " in the table 3.For organic polymer particle E and F, add each organic polymer particle dispersion.
Utilizing hairbrush to be applied to this antifouling paint compositions adopts sand paper (granularity is 240) to carry out on the FRP plate (100 * 300 * 3mm handles through gluing) of hacking, so that its dry film thickness is 400 μ m.After the coating, be that 20 ℃, relative humidity are to place 1 day in 65% the atmosphere, obtain testing coated plate thus in temperature.
For the resulting coated plate of respectively testing, be 6 months except making dipping time, adopt with the same method of aforesaid method and estimate water tolerance and didirtresistance.The result is as shown in table 3.
For resulting aqueous solidified type antifouling paint compositions, adopt following method evaluation friction impedance experiments.
(friction impedance experiments)
It is 10cm, high on the polyvinyl chloride rounding tubular cylinder of 10cm that resulting coating is applied to diameter, in seawater, be rotated (Re:2500000 and 4000000, the speed of being scaled is about 15 nautical miles/hour and about 25 nautical miles/hour), utilize torductor to measure the friction impedance.Measure as standard with the friction impedance of adopting air blowing treatment to carry out the level and smooth polyvinyl chloride rounding tubular cylinder of mirror-polishing, the increase and decrease of friction impedance separately is as shown in table 3.The friction impedance of just flooding behind the seawater and flood after 1 month is estimated.
[table 3]
Solids component ratio (%) Solubleness g/L Water regain quality % Embodiment Comparative example
11 12 13 14 15 16 17 18 19 5
Emulsifying resins Production Example 1 40 - - 100 100 100
Production Example 2 40 - - 100 100
Production Example 3 40 - - 100
Production Example 4 40 - - 100 100 100
Bayhydrol A145 *1 45 - - 62
Solidifying agent Hardener SC *2 50 - - 4 4 4
Hexamethylene-diamine 30 - - 4 4
Bayhydur 3100 *3 100 - - 12
Curing catalysts Phosphoric acid 100 - - 1
Cobalt naphthenate 35 - - 1 1 1
Stain control agent Production Example 5 76.5 - - 200 200 200 200 200 200 200 200 200 200
The organic polymer particle A 100 ＜2 0.5 7 6
B 100 ＜2 0.5 8
C 100 ＜2 6 6
D 100 ＜2 8 4 7
E 20 ＜2 1.3 20
F 20 ＜2 3.1 25 30
Tackifier *4 35 - - 3 3 3 3 3 3 3 3 3 3
Water tolerance 6 months ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Didirtresistance 6 months ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ △ ○
The friction impedance experiments Initial stage Re2500000 Be scaled speed About 15 nautical miles/hour 1.4 -1.2 1.4 0.4 2.0 -0.8 -0.9 1.8 1.5 3.9
Re4000000 About 25 nautical miles/hour 1.3 -1.1 1.5 0.5 2.1 -0.6 -0.9 2.2 1.5 3.8
After 1 month Re2500000 About 15 nautical miles/hour 1.0 -2.0 -0.1 0.3 -0.1 -2.4 -1.3 1.0 1.8 3.6
Re4000000 About 25 nautical miles/hour 1.2 -2.1 -0.2 0.3 0.2 -2.1 -1.4 0.9 1.4 4.1
* 1: Sumika Bayer Urethane Co., Ltd. system, aqueous polyurethane polyvalent alcohol
* 2: society of Asahi Chemical Industry system, Urea,amino-solidifying agent
* 3: Sumika Bayer Urethane Co., Ltd. system, aqueous polyurethane isocyanic ester
* 4: " PUR-2150 ", Akzo Nobel society system, urethane association type tackifier
As shown in Table 3, adopt filming that the coating obtained by embodiment forms to have excellent in water resistance and didirtresistance, demonstrate excellent low friction performance in addition, and its effect can access for a long time and keeps.In addition, the state of its film coated surface is also good.
Utilizability on the industry
Aqueous solidified type antifouling paint compositions of the present invention contains aqueous binders composition and the anti-fouling agent with curing property, thereby it can form also good filming of resistance to water excellence and anti-fouling effect, can be widely used in the aouatic structure thing thus.

Claims (30)

1. an aqueous solidified type antifouling paint compositions is characterized in that, is mixed with aqueous binders composition and stain control agent with solidified nature in the said composition, and is used in the purposes that water uses by filming of obtaining of said composition.
2. aqueous solidified type antifouling paint compositions as claimed in claim 1, wherein said solidified nature is by water or air-controlled.
3. aqueous solidified type antifouling paint compositions as claimed in claim 1 or 2, the cured article of wherein said aqueous binders composition decomposes by water.
4. aqueous solidified type antifouling paint compositions as claimed in claim 3, wherein said aqueous binders composition is cured by dehydrating condensation.
5. as claim 3 or 4 described aqueous solidified type antifouling paint compositions, wherein said aqueous binders composition has at least a curing system in carbonyl/hydrazides class, acetoacetyl oxygen/amine and the alcoxyl silyl condensation class.
6. as claim 3,4 or 5 described aqueous solidified type antifouling paint compositions, wherein said aqueous binders composition contains emulsifying resins and solidifying agent, and described emulsifying resins has the group of the functional group reactions that can be had with described solidifying agent.
7. aqueous solidified type antifouling paint compositions as claimed in claim 1 or 2, the cured article of wherein said aqueous binders composition has the structure that long chain hydrocarbon groups is cross-linked to each other and forms.
8. aqueous solidified type antifouling paint compositions as claimed in claim 7, wherein said aqueous binders composition is cured by oxypolymerization.
9. aqueous solidified type antifouling paint compositions as claimed in claim 8, wherein the group from higher unsaturated fatty acid participates in described oxypolymerization.
10. aqueous solidified type antifouling paint compositions as claimed in claim 9, wherein said aqueous binders composition contains emulsifying resins and the siccative that has from the group of unsaturated fatty acids.
11. aqueous solidified type antifouling paint compositions as claimed in claim 10, wherein said emulsifying resins are the multipolymer that has from the ethylene linkage unsaturated monomer of the group of higher unsaturated fatty acid.
12. aqueous solidified type antifouling paint compositions, the aqueous binders composition that is mixed with the stain control agent thickener in the said composition and has solidified nature, being mixed with acid number in the described stain control agent thickener is that 10～300mgKOH/g, number-average molecular weight are 1000～20000 water-soluble dispersion resin and stain control agent.
13. aqueous solidified type antifouling paint compositions as claimed in claim 12, the water-soluble dispersion resin in the wherein said stain control agent thickener and the solids component mass ratio of stain control agent are 1/99 to 50/50.
14., wherein in water, use by resulting the filming of said composition as claim 12 or 13 described aqueous solidified type antifouling paint compositions.
15. as claim 12,13 or 14 described aqueous solidified type antifouling paint compositions, wherein said aqueous binders composition is cured by addition reaction.
16. as claim 12,13 or 14 described aqueous solidified type antifouling paint compositions, wherein said aqueous binders composition is cured by oxypolymerization.
17. aqueous solidified type antifouling paint compositions as claimed in claim 16, wherein the group from higher unsaturated fatty acid participates in described oxypolymerization.
18. aqueous solidified type antifouling paint compositions as claimed in claim 17, wherein said aqueous binders composition contains emulsifying resins and the siccative that has from the group of unsaturated fatty acids.
19. aqueous solidified type antifouling paint compositions as claimed in claim 18, wherein said emulsifying resins are the multipolymer that has from the ethylene linkage unsaturated monomer of the group of higher unsaturated fatty acid.
20. as claim 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18 or 19 described aqueous solidified type antifouling paint compositions, it further is mixed with the organic polymer particle.
21. aqueous solidified type antifouling paint compositions as claimed in claim 20, wherein said organic polymer particle is below the 15g/L in 23 ℃ of solubleness in the artificial seawater of ASTM D1141-98 defined, water regain to the artificial seawater of ASTM D1141-98 defined is more than the 0.01 quality %, and this particle grain size is 0.05～100 μ m.
22. as claim 20 or 21 described aqueous solidified type antifouling paint compositions, wherein said organic polymer particle is the polymer of natural origin.
23. aqueous solidified type antifouling paint compositions as claimed in claim 22, wherein said organic polymer particle has the cationic group.
24. as claim 20 or 21 described aqueous solidified type antifouling paint compositions, wherein said organic polymer particle grain size is 0.05～100 μ m, and described organic polymer particle contains at least a material that is selected from the group of being made up of the derivative of chitin, chitosan, γ-PGA, spun silk crushed material and these materials.
25. as claim 20 or 21 described aqueous solidified type antifouling paint compositions, wherein said organic polymer particle is a synthetic macromolecule.
26. aqueous solidified type antifouling paint compositions as claimed in claim 25, wherein said organic polymer particle is the acrylic resin particle.
27. as claim 20 or 21 described aqueous solidified type antifouling paint compositions, wherein said organic polymer particle is the composite resin particle that contains hydrophilic resin and acrylic resin, and described hydrophilic resin is at least a material that is selected from the group of being made up of starch, pulullan polysaccharide, gum arabic, κ-carrageenan, gelatin, Mierocrystalline cellulose, chitosan and their derivative, polyvinyl alcohol, polyallylamine, polyvinylamine, poly-(methyl) acrylamide, poly-(methyl) vinylformic acid and their multipolymer.
28. as claim 20,21,22,23,24,25,26 or 27 described aqueous solidified type antifouling paint compositions, wherein said organic polymer particulate combined amount is the 0.01 quality %～15 quality % of coating solids component.
29. antifouling coating, this antifouling coating is characterised in that it is obtained by claim 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27 or 28 described aqueous solidified type antifouling paint compositions.
30. an aouatic structure thing, this aouatic structure thing are characterised in that it has the described antifouling coating of claim 29.
CN2005800452760A 2004-12-28 2005-12-28 Water-based curing type antifouling coating composition, antifouling coating film and underwater structure Expired - Fee Related CN101094899B (en)

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JP379673/2004 2004-12-28
JP379674/2004 2004-12-28
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JP2005368799A JP2007169449A (en) 2005-12-21 2005-12-21 Water-based curable antifouling coating, antifouling coating film, underwater structure, and method for reducing underwater friction
PCT/JP2005/024116 WO2006077738A1 (en) 2004-12-28 2005-12-28 Hydraulic stain-proof coating composition, stain-proof coating film and underwater structure

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