CN102702939A - Anti-fouling coating composition, anti-fouling coating film and anti-fouling method of base material - Google Patents
Anti-fouling coating composition, anti-fouling coating film and anti-fouling method of base material Download PDFInfo
- Publication number
- CN102702939A CN102702939A CN2012101972054A CN201210197205A CN102702939A CN 102702939 A CN102702939 A CN 102702939A CN 2012101972054 A CN2012101972054 A CN 2012101972054A CN 201210197205 A CN201210197205 A CN 201210197205A CN 102702939 A CN102702939 A CN 102702939A
- Authority
- CN
- China
- Prior art keywords
- antifouling paint
- paint compositions
- composition
- antifouling
- base material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a two-component hydrolytic anti-fouling coating composition, which is characterized by comprising a first component and a second component. In terms of the weight of the anti-fouling coating composition, the first component comprises 10-75 percent of polyester resin, wherein the acid value of the solid component of the polyester resin is 50-200, the hydroxyl group value of the solid component is below 100, and the viscosity at 25 DEG C is below 500 mPa.s; the second component comprises paste of 1-70 percent of zinc oxide, 2-40 percent of triphenyl borane amine salt, 2-40 percent of metal pyrithione and 2-30 percent of cuprous oxide; and based on the total amount of the first component and the second component, the content of volatile organic compound is below 400 g/L. In addition, an anti-fouling coating film is characterized by being formed by curing the two-component hydrolytic anti-fouling coating composition. In addition, an anti-fouling method of the base material is characterized in that the two-component hydrolytic anti-fouling coating composition is coated on the base material or soaked in the base material and then cured to form the anti-fouling coating film.
Description
Technical field
When the present invention relates to a kind of minimizing to the load of environment with to the influence of human body; Can give the binary liquid shape hydrolysis-type antifouling paint compositions of excellent didirtresistance and use the antifouling coat of this antifouling paint compositions and the anti-fouling method of base material the substrate surface of boats and ships, aouatic structure thing, fishing net, fishing gear etc.
Background technology
For boats and ships, aouatic structure thing, fishing net etc., on the surface that is exposed to the base material in the water for a long time, be attached with animal classes such as oyster, mussel, barnacle easily, plant classes such as marine alga, and various hydrobionts such as bacterium.When these hydrobionts when substrate surface is bred; The surfaceness of boats and ships increases; Possibly cause the decline of speed and the increase of fuel cost; In addition, the corrosion protection that is coated on substrate surface possibly cause the intensity of aouatic structure thing and the decline of function, the such destruction of remarkable shortening in life-span with being coated with membrane damage.In addition, if hydrobiont adheres to, breeds, then produce the biological caused by anoxia of fishing and hunting that the obstruction of mesh the causes serious problem of waiting indefinitely sometimes on fishing nets such as culturing net or fixed network.In addition, if hydrobiont adheres to, breeds on the water supply and sewage pipe of the seawater of firepower, nuclear plant etc., then circulation exerts an influence to the water supply and sewage of water coolant sometimes.Therefore, in order preventing hydrobiological adhering to, the various antifouling paints that are used to be coated on the substrate surface to be studied, developed always.
As antifouling paint in the past, the known antifouling paint compositions that use is arranged as the water-disintegrable vibrin of resin.Because vibrin promptly generates through esterification through the dehydrating condensation of acid and alcohol, therefore is hydrolyzed easily, be considered to not only antifouling property excellence, and get into the metabolic process of mikrobe etc. easily through hydrolysis.
For example, disclose a kind of antifouling paint that uses aliphatic polyester as the hydrolysis-type resin in the patent documentation 1, this aliphatic polyester forms the copolymerization more than a kind of glycerine, terepthaloyl moietie and 1,4 butyleneglycol in the polyester that comprises succsinic acid and 1,2 Ucar 35; Disclose a kind of antifouling paint that contains the hydrolysis-type vibrin in the patent documentation 2, this hydrolysis-type vibrin will be for being the alcohol acid of representative the and polycarboxylic acid and the polyol reaction of hydroxyl do not obtain with lactic acid; Disclose a kind of aliphatic polyester in the patent documentation 3 and used the hydrolysis-type vibrin as the antifouling paint of principal constituent with the metal-salt that contains the hydroxyl carboxylic acid; Disclose a kind of through being that 2~40 omega-dicarboxylic acids, carbonatoms are that the excellent antifouling paint of coating flexibility of the hydrolysis rate appropriateness that obtains of 2~40 glycols copolymerization is used vibrin with carbonatomss such as oxyacetic acid, lactic acid, caprolactones in the patent documentation 4.
In addition, disclosing a kind of acid number that contains in the patent documentation 5 is 20~400 resin, metallic stain control agent and the antifouling paint compositions that contains the monoprotic acid compound of carboxyl; A kind of antifouling paint compositions that has the hydrolysis-type polyester of carboxyl at two ends that contains is disclosed in the patent documentation 6; Disclosing a kind of resin, acid number that vinyl resin and the reactive metal oxide more than the divalent are formed of containing in the patent documentation 7 is 50~200 the vibrin and the antifouling paint compositions of stain control agent; Disclose a kind of antifouling anti-algae that cooperates stain control agent to form in as the polybutylene terephthalate multipolymer of copolymer composition at polytetramethylene glycol and m-phthalic acid in the patent documentation 8 and used polyester resin composition; Disclose in the patent documentation 9 and a kind ofly contained biocide and as the antifouling paint of the binder polymer of polymkeric substance that can hydrolysis in sour functionality polymkeric substance; A kind of antifouling paint that contains water-disintegrable from polishing type resin (vinyl resin or vibrin) and Red copper oxide and copper pyrithione is disclosed in the patent documentation 10.
The prior art document
Patent documentation
Patent documentation 1: No. 7166106 communiques of japanese kokai publication hei
Patent documentation 2: No. 7082513 communiques of japanese kokai publication hei
Patent documentation 3: No. 8176501 communiques of japanese kokai publication hei
Patent documentation 4: No. 753899 communiques of japanese kokai publication hei
Patent documentation 5: No. 9132736 communiques of japanese kokai publication hei
Patent documentation 6: No. 11255869 communiques of japanese kokai publication hei
Patent documentation 7: No. 2000248206 communiques of TOHKEMY
Patent documentation 8: No. 57128742 communiques of japanese kokai publication sho
Patent documentation 9: No. 2196869 communiques of japanese kokai publication hei
Patent documentation 10: No. 10298455 communiques of japanese kokai publication hei
Recently; Viewpoint from environmental problem; Field at antifouling paint; Except that having long-term durable antifouling property (long-term didirtresistance) and reducing coating and upgrade the operation, volatile organic compounds (the to call VOC:Volatile Organic Compounds in the following text) content that reduces in the coating also becomes important project.
Yet, do not do fully research for low VOCization in the above-mentioned patent documentation 1~10.
In addition; CN 102224209A discloses a kind of binary liquid shape hydrolysis-type antifouling paint compositions; It is characterized by: contain the 1st composition and the 2nd composition; The acid number that said the 1st composition contains solids component is 50 ~ 200, the OH value of solids component is below 100, the viscosity 25 ℃ the time is the vibrin below the 500mPas, and said the 2nd composition is the paste that contains zinc oxide and Red copper oxide; Total amount with the 1st composition and the 2nd composition is a benchmark, and the content of volatile organic compounds is below the 400g/L.In addition, the antifouling coat of this invention is characterized as: above-mentioned binary liquid shape hydrolysis-type antifouling paint compositions curing is formed.In addition, the anti-fouling method of the base material of this invention is characterized as: above-mentioned binary liquid shape hydrolysis-type antifouling paint compositions is coated on the base material or contained be dipped in the base material, make it be solidified to form antifouling coat then.But the said composition anti-fouling effect is not ideal enough, can not satisfy existing needs.
Summary of the invention
So the inventor studies, the result finds that the antifouling paint of use vibrin in the past has room for improvement in the following areas.
At first, in most antifouling paint in the past, the molecular weight of arbitrary resin is all high, in order to reach the viscosity that is suitable for application, needs to use a large amount of solvents.Therefore, in order to supply practicability, the VOC amount in the coating increases, and can not be called environmental friendliness coating.In addition, in order to reduce viscosity, as long as the polyester lower molecular weightization then can be reduced the organic solvent amount in the coating, but at this moment because the hydrolysis rate in seawater is excessive, can't adjust hydrolysis rate, therefore long-term didirtresistance is poor.In addition, using POLYACTIC ACID, Sodium bromoacetate homopolymer, SRU etc., also can't keep long didirtresistance because hydrolysis rate is too fast as the occasion of antifouling paint with vibrin.
In addition,, be difficult to be called hydrolysis-type coating, also be difficult to suppress the VOC value to low-level though disclose embodiment in the patent documentation 8 with the antifouling paint of vibrin and Red copper oxide and flowers of zinc cooperation.In addition, the resin that uses in the patent documentation 10 has the structure of organic acid residue owing to side chain terminal, thereby does not form the metal corsslinking body.Therefore, the application operability is impaired, reduces very difficulty of VOC value.And CN 102224209A has low VOC, but its anti-fouling effect is not ideal enough.
As stated, low VOC is these those long relations that disappear with long-term didirtresistance, still can't realize taking into account the antifouling paint of above-mentioned characteristic.
The present invention is in view of the problem that exists in the above-mentioned technology in the past; Purpose is to provide a kind of can take into account low VOC and long-term didirtresistance by high level; Can form the antifouling paint compositions of the excellent antifouling coat of physical strength, the antifouling coat of this antifouling paint compositions of use and the anti-fouling method of base material also are provided.
Solve the method for problem
In order to solve above-mentioned problem; The present invention provide a kind of binary liquid shape hydrolysis-type antifouling paint compositions (below; Sometimes abbreviate " antifouling paint compositions " according to circumstances as); It is characterized by, contain the 1st composition and the 2nd composition, according to the weight meter of said antifouling paint compositions; The acid number that said the 1st composition contains 10 ~ 75% solids components is 50~200, the OH value of solids component is below 100, the viscosity 25 ℃ the time is the vibrin below the 500mPas; Said the 2nd composition is for containing the paste of 1 ~ 70% zinc oxide, 2 ~ 40% triphenyl-boron alkanamines, 2 ~ 40% metal pyridine sulphur copper and 2 ~ 30% Red copper oxide, is benchmark with the total amount of the 1st composition and the 2nd composition, and the content of volatile organic compounds (VOC) is below the 400g/L.Here, " binary liquid shape antifouling paint " is meant the antifouling paint that before being about to application, mixes the type that two liquid use.
Antifouling paint compositions of the present invention is employed in the 1st composition and the 2nd composition and mixes the back forms water-disintegrable metal corsslinking body through the reaction of vibrin composition and zinc oxide treatment process for mixing the antifouling paint compositions of above-mentioned the 1st composition and the 2 one-tenth binary liquid shapes of assigning to use.The hydrolysis-type antifouling paint compositions that thus, can not damaged the application operability, can significantly reduce the VOC value and have the secular abrasiveness of filming through stable hydrolysis mechanism.
On the other hand, among the present invention,, can realize therefore that the flexibility that can reduce dope viscosity, film is high because the viscosity of resin self is very low, VOC is below the 400g/L, have by the coating shape of the application operability of practicality and form.In addition; The vibrin that comprises in the 1st composition is the high acid value vibrin; Through being must composition with it, can fully improve reactivity, can also improve dried coating film property, coating strength, the rerum natura of filming, water-disintegrable characteristics such as (Selfpolishing property (from polishability), didirtresistances).That is,, can keep didirtresistance chronically, can also control drying property that metal corsslinking causes, water-disintegrable through the control acid number through antifouling paint compositions of the present invention.
With regard to antifouling paint compositions of the present invention, the weight-average molecular weight of the above-mentioned vibrin through gel permeation chromatography is preferably below 5000.
Preferably, according to the weight meter of said antifouling paint compositions, the content of the zinc oxide in said the 2nd composition is 10~65%, is preferably 20 ~ 50% especially.
Preferably, said antifouling paint compositions also contains rosin and/or rosin derivative.
Preferably, said antifouling paint compositions also contains softening agent.
Preferably, said triphenyl-boron alkanamine comprises the pyridine triphenylborane.
Preferably, according to the weight meter of said antifouling paint compositions, the content of said triphenyl-boron alkanamine is 10 ~ 30%.
Preferably, according to the weight meter of said antifouling paint compositions, the content of said metal pyridine sulphur copper is 10 ~ 30%;
Preferably, according to the weight meter of said antifouling paint compositions, the content of said Red copper oxide is 10 ~ 25%.
In addition, antifouling paint compositions of the present invention preferably further contains rosin and/or rosin derivative.
In addition, antifouling paint compositions of the present invention preferably further contains stain control agent (but not being triphenyl-boron alkanamine, metal pyridine sulphur copper or Red copper oxide).
In addition, antifouling paint compositions of the present invention preferably further contains at least a kind of softening agent that is selected from clorafin, tree oil lipid, ketone resin.
In addition, antifouling paint compositions of the present invention preferably further contains pigment extender (but not being zinc oxide).
In addition, antifouling paint compositions of the present invention preferably further contains pigment dispersing agent.
In addition, antifouling paint compositions of the present invention preferably further contains tinting pigment.
In addition, the present invention provides a kind of antifouling coat, and the binary liquid shape hydrolysis-type antifouling paint compositions curing that it is characterized by the invention described above forms.
In addition, the present invention provides a kind of anti-fouling method of base material, it is characterized by, and the binary liquid shape hydrolysis-type antifouling paint compositions of the invention described above is coated on the base material or contained be dipped in the base material, makes it be solidified to form antifouling coat then.
The invention effect
According to the present invention; Can provide that a kind of can to form inhibition be low-level to the load of environment, to the influence of human body, low VOC and the various aspect of performances with antifouling coat that good application operability, drying property, long-term didirtresistance (expendable, leave standstill didirtresistance) are excellent, physical strength is excellent have been obtained the high solid type hydrolysis-type antifouling paint compositions of the low VOC of equilibrated.
In addition, according to the present invention, the antifouling coat that a kind of long-term didirtresistance is excellent, physical strength is excellent can be provided.
In addition, according to the present invention, the anti-fouling method of long-time antifouling base material such as a kind of substrate surface that can make aouatic structure thing, ship plank, fishing net, fishing gear base material etc. can be provided.
Description of drawings
Fig. 1 is the explanatory view of the metewand of the dried coating film property test (plank applied voltage test) among the expression embodiment, and among the figure, 10 is wood chip, and 20 for filming.
Embodiment
Below, with regard to explanation at length preferred embodiment of the present invention.
[antifouling paint compositions]
The related antifouling paint compositions of this embodiment is the compsn that contains the 1st composition and the 2nd composition; Weight meter according to said antifouling paint compositions; The acid number that said the 1st composition contains 10 ~ 75% solids components is 50~200, the OH value of solids component is below 100, the viscosity 25 ℃ the time is the vibrin (following be sometimes referred to as according to circumstances " vibrin (A) ") below the 500mPas; Said the 2nd composition is for containing the paste of 1 ~ 70% zinc oxide, 2 ~ 40% triphenyl-boron alkanamines, 2 ~ 40% metal pyridine sulphur copper and 2 ~ 30% Red copper oxide; Total amount with the 1st composition and the 2nd composition is a benchmark, and the content of volatile organic compounds is below the 400g/L.At first, each composition is described.
< vibrin (A) >
Sour composition as vibrin (A); Can enumerate monocarboxylic acids such as TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M., p-tert-butyl benzoic acid; Perhaps aromatic dicarboxylic acids such as terephthalic acid, m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids; Perhaps hexanodioic acid, sebacic acid, nonane diacid, Succinic Acid, nadic acid, 1; Aliphatic carboxylic acids such as 6 cyclohexane dicarboxylic acids, the polyprotonic acids more than 3 yuan such as trimellitic acid, PMA, the perhaps acid anhydrides of lower alkyl esters of above-mentioned substance (the for example alkyl ester of C1~C4) or above-mentioned substance.Diprotic acid such as monocarboxylic acid and aromatic dicarboxylic acid and saturated aliphatic dicarboxylic acids can be distinguished a kind of independent use, also can be also with more than 2 kinds.In addition, the polyprotonic acid more than 3 yuan also can use a kind separately, also can be also with more than 2 kinds.
In addition, as the pure composition of vibrin (A), can enumerate terepthaloyl moietie, Ucar 35,1; 2 Ucar 35,1,3 Ucar 35,1,3 butyleneglycol, 1; 4 butyleneglycols, NSC 6366,1,5 pentanediol, 1,6 pinakon, 3 methyl pentanediols, glycol ether, 1; 4 cyclohexanedimethanols, 3 methyl, 1,5 pentanediol, 2 methyl, 1,3 Ucar 35,2; The polyvalent alcohol that binary such as the ethylene oxide adduct of 2 diethylammonium, 1,3 Ucar 35,2 butyl, 2 ethyls, 1,3 Ucar 35, Hydrogenated Bisphenol A 99, dihydroxyphenyl propane or propylene oxide adduct, trimethylolethane, TriMethylolPropane(TMP), glycerine, tetramethylolmethane are above.Above-mentioned pure composition can use a kind separately, also can make up and use more than 2 kinds.In addition, can also alcohol acid of dimethylol propionic acid and so on and above-mentioned carboxylic acid, alcohol be used simultaneously.
From the viscosity of the related antifouling paint compositions of this embodiment and with reactive viewpoint of zinc oxide; The content from the component unit of aforementioned sour composition in the vibrin (A) (100 weight %) is preferably 5~95 weight %; Be more preferably 10~90 weight %, be preferably 20~80 weight especially.In addition, be preferably 5~95 weight %, be more preferably 10~90 weight %, be preferably 20~80 weight % especially from the content of the component unit of aforementioned pure composition.
As the method for manufacture of vibrin (A), at first, cooperate above-mentioned sour composition and pure composition; Through known method of manufacture such as scorification; The solvent methods of toluene, YLENE etc. (circumfluence method) etc. carry out esterification or transesterification reaction, thus the modulation saturated polyester resin.When the modulation vibrin, also can under the decompression in the catalyzer of Antimony Trioxide: 99.5Min, germanium oxide, tetrabutyl titanate and so on exists, under 200~300 ℃, carry out polycondensation and obtain vibrin as required through under the catalyst-free decompression.
Viscosity during 25 ℃ of vibrin (A) is below the 500mPas, to be preferably 100~500mPas, is more preferably 200~400mPas.When viscosity surpassed 500mPas, being difficult to be modulated into volatile organic compounds (VOC) content was below the 400g/L and the antifouling paint compositions that can be coated with.
The weight-average molecular weight of vibrin (A) is below 5000, is preferably below 4000, is more preferably below 3000.Because weight-average molecular weight surpasses at 5000 o'clock, resin viscosity is high, and the viscosity of final coating is too high, in order to use solvent cut to the viscosity that can be coated with, and the tendency that exists the VOC amount to increase.In addition, during less than 500, because lower molecular weight, the viscosity behind the dried coating film is residual, so preferable weight-average molecular weight is more than 500.
In addition, the value of the weight-average molecular weight of vibrin (A) for measuring, use the polystyrene standard typical curve to obtain through gel permeation chromatography (GPC) method.The GPC condition of molecular-weight determination is as follows.
< GPC condition >
Pump: Hitachi makes L6200
Chromatographic column: Hitachi changes into and makes gelpackGL420, GL430, GL440
Eluant: THF
The solids component acid number of vibrin (A) is 50~200, is preferably 80~150, is more preferably 90~110.During solids component acid number less than 50, thus since with the reaction postponement drying property variation of zinc oxide, surpass under 200 the situation, react with zinc oxide during mixing, the coating HV that becomes has through a few days and the tendency of tackify.
In addition, the solids component acid number of the vibrin in this embodiment can use Pottasium Hydroxide (KOH) to measure through titration.
The solids component OH value of vibrin (A) is below 100, is preferably below 50, is more preferably below 20, most preferably is below 10.The solids component OH value surpasses under 100 the situation and the rosin, the intermiscibility of petroleum resin, the appearance of film that use during as coating descend the poor water resistance of filming.
Here, for the solids component acid number that makes vibrin (A) in above-mentioned scope, can adopt through diprotic acid import the method for acid endways, with the method for modified by polyacid etc.More specifically, can use the alcohol of diprotic acid and binary to form sour terminal polyester, also can synthesize the polyester of main chain after, obtain through importing polyprotonic acid (trimellitic acid 1,2-anhydride etc.).The method that imports polyprotonic acid from the synthetic initial stage is also arranged, but after polyester is synthetic, minimizings such as the gelation of the method that imports through addition, tackify, reaction is control easily.In addition, polyprotonic acids such as trimellitic acid 1,2-anhydride can import separately, but because the part existenceization of carboxyl increases, polarity raises, so viscosity rises easily.Be more preferably and with monocarboxylic acid, dicarboxylicacid etc. and polyprotonic acid.
In addition, for the solids component OH value that makes vibrin (A) in (below 100), can through the synthetic initial stage to fit into professional etiquette fixed, also can in the end adjust with hydroxyl reaction through making the monocarboxylic acid reaction.
In addition, when making the polyester lower molecular weight for lowering viscousity, hydroxyl has the trend of increase, at this moment, can adjust OH value through using monocarboxylic acids such as TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. and hydroxyl reaction simultaneously.
Organic solvent during as dilution, for example can using, aromatic hydrocarbons, aliphatic hydrocarbon, ester class, ketone etc., alcohols equal solvent dilute.As its object lesson, it is aromatic hydrocarbon based to enumerate toluene, YLENE etc., aliphatic hydrocarbons such as hexane, ester classes such as ETHYLE ACETATE, butylacetate, ketones such as methyl ethyl ketone, MIBK, alcohols such as methyl alcohol, butanols, isopropylcarbinol.Above organic solvent can use separately or combination use more than 2 kinds.Because the acid number of vibrin is high, for the low VOCization that LV causes, compares with fragrant family, more preferably uses ester, ketone, pure isopolarity solvent, but use alcohol to cause alcoholysis sometimes, resin viscosity descends.The solvent of therefore preferred ester, ketone system.
< the 2nd composition >
The 2nd related composition of this embodiment is to contain zinc oxide, triphenyl-boron alkanamine, metal pyridine sulphur copper and Red copper oxide as paste that must composition (below, be called " paste (B) " according to circumstances).
The zinc oxide that contains in the paste (B) is reactive pigment, zinc oxide through and the carboxyl of vibrin (A) react and play a role as solidifying agent.
Through the reaction of vibrin (A) and zinc oxide, can form by as the COO base that has broken away from hydrionic residue from the carboxyl of vibrin (A) and as the Zn of the metals ion of zinc oxide
2+Caused metal-salt crosslinking structure (for example, COO...Zn
2+... OOC).The easy hydrolysis of this metal-salt crosslinking structure can present stable hydrolysis reaction.Thus; Owing to can bring into play the abrasiveness of filming chronically; Can obtain excellent and excellent the filming of flexibility of long-term antifouling property, and through forming two liquid response types, even set the VOC value also can obtain having practicality at 400g/L the filming of dope viscosity.
The reaction of the carboxyl of zinc oxide and vibrin (A) for example, can be confirmed from the variation of the form and aspect of the solution of the front and back of the solution of vibrin (A), mixing paste (B) sometimes.In addition, sometimes also can from mixture through the time viscosity increase confirm.
As contained zinc oxide in the paste (B), can use the material of various particle diameters.During particulate oxide zinc such as use active zinc flower; The situation of the plumbous oxide big with using particle diameter is compared; From the reaction of the carboxyl that promotes vibrin (A) and zinc oxide, smear the viewpoints such as anti-fragility that hardness improves, early stage performance is filmed in the short period of time, thereby preferably.
In the related antifouling paint compositions of this embodiment, the content of zinc oxide be preferably said antifouling paint compositions weight 1 ~ 70%, further be preferably 10~65%, be preferably 20 ~ 50% especially.The rerum natura of filming such as anti-fragility has the tendency of variation during less than 1%, surpasses the tendency that had the solidified nature variation, smears the intensity variation at 70% o'clock.
The triphenyl-boron alkanamine that in antifouling paint compositions according to the present invention, contains is the title complex that is formed by triphenylborane and amine.Said amine does not receive special restriction and for example comprises: primary amine, for example Tri N-Propyl Amine, n-Butyl Amine 99, normal hexyl Amine, NSC 9824, n-Decylamine, positive amino dodecane, positive tridecyl amine, positive tetradecy lamine, positive cetylamine, positive stearylamine, aniline, Tolylamine etc.; Secondary amine, for example Di-n-Butyl Amine, two normal hexyl Amines, two NSC 9824s, two n-Decylamines, two positive amino dodecanes, two positive tridecyl amines, two positive tetradecy lamines, two positive cetylamines, two positive stearylamines, pentanoic etc.; Tertiary amine, for example Tri-n-Propylamine, three normal hexyl Amines, tri-n-octyl amine, three n-Decylamines, three positive amino dodecanes, three positive tridecyl amines, three positive tetradecy lamines, three positive cetylamines, three positive stearylamines, triphenylamine etc.; Pyridines, for example pyridine or its nuclear substituent (for example, 2-picoline, 3-picoline, 4-picoline, 2-chloropyridine, 3-chloropyridine and 4-chloropyridine).About these triphenyl-boron alkanamines, can only use a kind ofly, maybe can at least two kinds be used together.
In above content, wherein amine is pyridine triphenylborane excellence aspect antifouling property of pyridine, and is used by preferred.
The content of triphenyl-boron alkanamine (when using multiple triphenyl-boron alkanamine, its total content) be preferably said antifouling paint compositions weight 2 ~ 40%, more preferably 10 ~ 30%.If this content less than 2%, then is tending towards being difficult to reach the anti-fouling effect of expectation.If this content surpasses 40%, then in filming, be tending towards taking place defective such as ftractureing/peeling off.
Antifouling paint compositions according to the present invention contains metal pyrithione (B1), triphenyl-boron alkanamine (B2) and the sulphonamide-based compound (B3) as stain control agent (B).Compare with using separately of common known stain control agent, significantly high long-term antifouling character can be provided according to this combination of stain control agent with making up to use.Especially, find to have obtained unexpected effect, promptly owing to this combination of stain control agent, even the charging capacity of stain control agent be reduced to be lower than before under the condition of known level, also can demonstrate the antifouling character that surmounts the level that is equal to conventional levels.Become deterioration one of the factor of the resistance to cracking in life-time service of filming although mix the stain control agent of big charging capacity usually in order to improve resulting antifouling character of filming; But the invention solves this problem, and thereby to make it possible to obtain didirtresistance of fine quality different and have an antifouling coat of excellent resistance to cracking.
The metal pyrithione that in antifouling paint compositions of the present invention, contains for example comprises the pyrithione thing, for example pyrithione sodium, pyrithione magnesium, pyrithione calcium, pyrithione barium, pyrithione aluminium, copper pyrithione, ZPT, pyrithione iron, pyrithione lead.Especially, preferred 2-mercaptopyridine-1-oxide compound zinc salt (ZPT), 2-mercaptopyridine-1-oxide compound mantoquita (copper pyrithione) etc.These can use separately, maybe can make up use.
The content of metal pyrithione (when using multiple pyrithione thing, their total content) be preferably said antifouling paint compositions weight 2 ~ 40%, more preferably 10 ~ 30%.If this content less than 2%, then is tending towards being difficult to obtain desired effects.If this content surpasses 40%, then in filming, be tending towards taking place defective such as ftractureing/peeling off.
In addition, employed paste (B) contains the necessary composition of Red copper oxide conduct as stain control agent in this embodiment.With regard to Red copper oxide, from viewpoint, can bring into play the antifouling property that keeps stable, in the effects such as didirtresistance of multiple marine site performance antifouling coat to the didirtresistance of large-scale biology.
In the related antifouling paint compositions of this embodiment, Red copper oxide be preferably said antifouling paint compositions weight 2 ~ 30%, be more preferably 10 ~ 25%.
< (C) rosin, rosin derivative >
The related antifouling paint compositions of this embodiment can further contain rosin and/or rosin derivative.As rosin, can enumerate gum resin, wood rosin, starex etc.In addition, as rosin derivative, can enumerate staybelite, polymerized rosin, maleated rosin, aldehyde modified rosin, rosin metal salt, rosin Amine D etc.Rosin and/or its verivate can use a kind or combination to use more than 2 kinds.Rosin and/or rosin derivative can contain in arbitrary composition of the 1st composition and the 2nd composition, perhaps also can after mixing the 1st composition and the 2nd composition, be added in its mixture, but preferably in the 2nd composition, contain.
The content of rosin and/or rosin derivative be preferably said antifouling paint compositions weight 0.1~70%, further be preferably 0.1~60%, most preferably be 0.1~30%.The tendency that has dope viscosity to rise during less than 0.1% surpasses at 70% o'clock and cracks etc., the tendency that has the rerum natura aspect to descend.
< (D) other stain control agent >
The related antifouling paint compositions of this embodiment can further contain stain control agent and (wherein, not comprise triphenyl-boron alkanamine, metal pyridine sulphur copper or Red copper oxide.Below be called " stain control agent (D) " according to circumstances).As stain control agent (D), can be any stain control agent of organic system, inorganic system, can use 4,5 dichloros, 2 n-octyls, 4 isothiazolines, 3 ketone, the amino s-triazine of amino 6 cyclopropyl of 2 methylthio groups, 4 tertiary butyls etc.When considering the didirtresistance under the condition of leaving standstill, preferably use 4,5 dichloros, 2 n-octyls, 4 isothiazolines, 3 ketone, the amino s-triazine of amino 6 cyclopropyl of 2 methylthio groups, 4 tertiary butyls as stain control agent (D).Stain control agent (D) preferably contains in the 2nd composition.
In the related antifouling paint compositions of this embodiment, stain control agent (D) be desirably most said antifouling paint compositions weight 1 ~ 70%, further be preferably 10 ~ 50%.
< (E) other additive >
The related antifouling paint compositions of this embodiment can contain at least a kind of additive (following general designation " additive (E) ") of from the group of being made up of softening agent (e1), pigment extender (e2), pigment dispersing agent (e3), tinting pigment (e4), anti-sagging agent (e5), anti-settling agent (e6), selecting.Additive (E) can contain in arbitrary composition of the 1st composition or the 2nd composition, perhaps also can after mixing the 1st composition and the 2nd composition, be added in its mixture, but preferably in the 2nd composition, contain.
Below softening agent (e1), pigment extender (e2) (wherein, not comprising zinc oxide), pigment dispersing agent (e3), tinting pigment (e4), anti-sagging agent (e5), anti-settling agent (e6) are detailed.
(e1) softening agent
As softening agent (e1), can enumerate clorafin, tree oil lipid, ketone resin, TCP (Tritolyl Phosphate), polyvinyl ethyl ether, bialkyl ortho phthalate etc.When the related antifouling paint compositions of this embodiment contains softening agent (e1),, be preferred therefore owing to the anti-fragility raising of film (antifouling coat) that form by this antifouling paint compositions.
Aforementioned chlorine atomize paraffin (clorafin) can be the straight chain shape, also can have branch, at room temperature can be the aqueous solid (powder) that also can be; Usually preferred its average carbon atom number of use is 8~30; Be preferably 10~26 clorafin, can preferably use its number-average molecular weight to be generally 200~1200, be preferably 300~1100; Viscosity is generally more than 1 and (moors/25 ℃); Be preferably more than 1.2 and (moor/25 ℃), its proportion is 1.05~1.80/25 ℃, is preferably 1.10~1.70/25 ℃ clorafin.When using the clorafin of such carbonatoms, use the antifouling paint compositions of gained can form break (crackle), peel off few filming.In addition, during the carbonatoms less than 8 of clorafin, the effect that suppresses crackle sometimes is not enough, and its carbonatoms surpasses at 30 o'clock, sometimes the expendable of gained film coated surface (renewal property) difference and didirtresistance is poor.In addition, the chlorination rate of above-mentioned clorafin (chlorinity) is preferably common 35~75%, preferred 35~65%.When using the clorafin of such chlorination rate, use the antifouling paint compositions of gained can form break (crackle), peel off few filming.As such clorafin, can enumerate " TOYOPARAX150 " that eastern Cao (strain) makes, " TOYOPARAXA70 " etc.In addition; As tree oil lipid, particularly, can use the hydrogenate of C5 system, C9 system, polystyrene, NSC 7352 system, above material etc.; As commercially available article, can enumerate " Quiutone1500 " that Japanese Zeon makes, " Quiutone1700 " etc.Wherein preferred chlorine atomize paraffin (clorafin), tree oil lipid, ketone resin.These softening agent can a kind of use or combination use more than 2 kinds separately.
Softening agent (e1) be desirably most said antifouling paint compositions weight 0.01~70%, be more preferably and contain 0.01~60%, most preferably contain 0.01~40%.
(e2) pigment extender
As pigment extender (e2) (wherein; Do not comprise zinc oxide); Can enumerate: talcum, silicon-dioxide, mica, clay, potassium felspar sand; Or it is white also to can be used as lime carbonate, kaolin, aluminum oxide that anti-settling agent uses, also can be used as WHITE CARBON BLACK that matting agent uses, white lake, magnesiumcarbonate, barium carbonate, permanent white etc., the pigment extender of wherein preferably from the group of being made up of talcum, silicon-dioxide, mica, clay, lime carbonate, kaolin, permanent white, potassium felspar sand, selecting.Pigment extender is that specific refractory power is little; With oil, the mixing occasion of varnish is transparent and do not cover the pigment of coated surface; When the related antifouling paint compositions of this embodiment contains pigment extender (e2), because therefore the rerum natura raisings etc. of filming such as anti-fragility are preferred.
Pigment extender (e2) be desirably most said antifouling paint compositions weight 0.01~75%, be more preferably and contain 10~50%.
(e3) pigment dispersing agent
As pigment dispersing agent (e3), can use the various dispersion agents of known in the past organic system, inorganic system.As the organic system pigment dispersing agent, can enumerate fatty amine or organic acid (" DISPERBYK101 " that " DuomeenTDO " that LION Co., Ltd. makes, BYKCHEMIE make) etc.
Pigment dispersing agent (e3) be desirably most said antifouling paint compositions weight 0.001~50%, be more preferably and contain 0.001~20%.
(e4) tinting pigment
As tinting pigment (e4), can use the various pigment of known in the past organic system, inorganic system.As organic system pigment, can enumerate carbon black, naphthol red, phthalocyanine blue etc.As inorganic series pigments, for example can enumerate red iron oxide, ground barium sulfate, titanium white, Zh 1 etc.The various tinting materials that also can contain in addition, dyeing etc.When the related antifouling paint compositions of this embodiment contains tinting pigment (e4), because therefore the form and aspect that can at random regulate the antifouling coat that is obtained by said composition are preferred.
Tinting pigment (e4) be desirably most said antifouling paint compositions weight 0.001~50%, be more preferably and contain 0.001~1%.
(e5) anti-sagging agent (being also referred to as " anti-sag agent ")
As anti-sagging agent (e5), can enumerate amide waxe, THIXCIN wax system, polyamide wax system and both mixtures, synthetic fine particle silica is desirably preferred polyamide wax, synthetic fine particle silica most.As commercially available article, can enumerate nanmu and originally change into " Supreme Being Si Balong (Disparlon) A63020XC " that (strain) make, " ASAT250F " that her rattan essential oil (strain) is made etc.When the related antifouling paint compositions of this embodiment contains anti-sagging agent (e5), because therefore the sag prevention property can adjust application time the etc. are preferred.
Anti-sagging agent (e5) be desirably most said antifouling paint compositions weight 0.01~50%, be more preferably and contain 0.01~20%.
(e6) anti-settling agent
As anti-settling agent (e6), can enumerate organic clay is the amine salt of Al, Ca, Zn, and polyethylene wax, oxidic polyethylene are wax etc., are desirably the polyethylene-based wax of preferred oxidation most.As commercially available article, can enumerate nanmu and originally change into " Supreme Being Si Balong (Disparlon) 420020X " that (strain) make etc.When the related antifouling paint compositions of this embodiment contains anti-settling agent (e6),, be preferred therefore owing to can prevent to be insoluble to deposition, the raising stirring property of material in during storage of solvent.
Anti-settling agent (e6) be desirably most said antifouling paint compositions weight 0.01~50%, be more preferably and contain 0.01~20%.
(F) solvent
The related antifouling paint compositions of this embodiment can further contain solvent (F).As solvent
(F), the solvent of the boiling point of known wide region in the past can be used, particularly, aliphatics series solvents such as terpenes can be enumerated; Aromatic series such as toluene, YLENE series solvent; Pure series solvents such as Virahol, propyl carbinol, isopropylcarbinol; Ester such as ETHYLE ACETATE, butylacetate series solvent; Ketone series solvents such as methyl ethyl ketone, MIBK, Methyl amyl ketone; The solvent of ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate system or ether-ether system etc. can be enumerated and be preferably YLENE, MIBK, propylene glycol monomethyl ether.These solvents can a kind of use or combination use more than 2 kinds separately.
The related antifouling paint compositions of this embodiment is the compsn that contains above-mentioned the 1st composition and the 2nd composition, and volatile organic compounds (VOC) content is below the 400g/L, to be preferably 100~350g/L.Through making VOC content is below the 400g/L, can reduce to the load of environment with to the influence of human body.In addition, this VOC is the value under the condition determination of in the hurdle of embodiment, explaining.
The related antifouling paint compositions of this embodiment can through synthetic aforementioned the 1st composition and aforementioned the 2nd composition are in advance stirred, mixing waits and makes.Stirring, when mixing, can suitably use known in the past mixing, whipping apptss such as high speed dispersion stirrer, sand mill, basket shredder, ball mill, three roller mixing machines, Luo Si mixing machine, planetary-type mixer, omnipotent article river stirrer.
[anti-fouling method of antifouling coat and base material]
The related antifouling coat of this embodiment forms for above-mentioned the related antifouling paint compositions of embodiment solidified.In addition, the anti-fouling method of the base material that this embodiment is related is dipped in the base material for above-mentioned the related antifouling paint compositions of embodiment coated on the base material or contained, and makes it be solidified to form antifouling coat then.
As the not special restriction of the base material of the object of anti-fouling method, be preferably any of aouatic structure thing, boats and ships, fishing net, fishing gear.For example; If with above-mentioned antifouling paint compositions on the aouatic structure things such as water supply and sewage mouth of firepower, nuclear plant, the littoral road in bay, subbottom tunnel, bay equipment, the surface of anti-mud diffusion barrier, boats and ships, fishery material various formed bodys such as (for example: rope, fishing net, fishing gear, float, buoy) like various oceans such as canal and water route civil engineering work through domestic method coating 1 time~for several times, can in long-time, slowly discharge and be coated with thick boats and ships that also have the pliability of appropriateness, an antifouling coat lining that anti-fragility is excellent or aouatic structure thing etc. even then can access didirtresistance excellence, stain control agent composition.
That is to say; The didirtresistance of the antifouling paint compositions coating curing antifouling coat that forms in the surface of various formed bodys that this embodiment is related is excellent, promptly can prevent to long-time continuous hydrobiological adhering to such as sea lettuce, barnacle, Enteromorpha, imperial cyprid, oyster, careless tongue worm.Particularly, the material of boats and ships etc. is under the situation of FRP, iron and steel, timber, duraluminum etc., also is attached to the surface of these materials well.In addition; Coat marine works surface through for example that this embodiment is related antifouling paint compositions; Can realize preventing adhering to of marine creature, can keep the function of this works for a long time, when coating fishing net; Can prevent the obstruction of the mesh of fishing net, and the possibility of environmental pollution is little.
The related antifouling paint compositions of this embodiment can directly be coated fishing net, also can coat the surface of the boats and ships that have been coated with basecoat materials such as rust-preventive agent, priming paint in advance or aouatic structure thing etc.In addition, carrying out adopting the application of antifouling paint in the past or adopting the boats and ships of the application of the related antifouling paint compositions of this embodiment, the particularly surface of FRP ship or aouatic structure thing etc. can be coated with the related antifouling paint compositions of last this embodiment of one deck and use as repairing.Being formed at not special qualification of thickness of antifouling coat on the surface of boats and ships, aouatic structure thing etc. like this, for example is 30~250 μ about m/ time.
Because the related antifouling coat of this embodiment that obtains as stated forms for the antifouling paint compositions that this embodiment is related solidifies; Therefore environmental pollution is dangerous little, for the long-term didirtresistance excellence of the settled organism of boats and ships, aouatic structure thing widely.
As stated; According to this embodiment; Can provide the load that can form few, have excellent didirtresistance, and in long-time, film and evenly consume with constant speed to environment; The even expendable of filming is excellent; Can also keep excellent antifouling property for a long time, the long-term didirtresistance of filming is kept excellent performance, is suitable for the low VOC hydrolysis-type antifouling paint compositions of binary liquid shape, antifouling coat of the antifouling coat that oceangoing vessel uses, with boats and ships, aouatic structure thing, fishing gear or the fishing net of this antifouling coat lining.
Embodiment
Below, based on embodiment and comparative example the present invention is described more specifically, but the present invention is not limited to these embodiment.In addition, among the following embodiment and comparative example, " part " and " % " is represented " weight part " and " weight % " respectively.
< manufacturing of vibrin (A) >
(make routine 1: the manufacturing of polyester resin solution (a1))
In 4 mouthfuls of flasks of 2L, cooperate 371.0 parts of m-phthalic acids, 427.1 parts of sebacic acid, 238.2 parts of NSC 6366s, 89.0 parts of terepthaloyl moietie, in the presence of nitrogen, in 5 hours (esterification) of 220 ℃ of reactions.In the reaction, removing the water of generation through reflux dewatering, carry out the mensuration of acid number and carry out the mensuration of OH value through acetylation method through the KOH volumetry, is 100 when reaching the solids component acid number, stopped reaction when the solids component OH value is 30.Behind the cooling reaction liquid; Use MIBK to dilute, obtain nonvolatile component and be 70.3%, acid number is that 70 (solids component is scaled 100), OH value are that 21 (solids component is scaled 30), viscosity are that 320mPas, weight-average molecular weight are 1800 polyester resin solution (a1).
(make routine 2: the manufacturing of polyester resin solution (a2))
Except that changing to the usage quantity of raw material the amount shown in the table 1 and embodiment 1 likewise obtains polyester resin solution (a2).
(make routine 3: the manufacturing of polyester resin solution (a3))
In 4 mouthfuls of flasks of 2L, cooperate 225.0 parts of m-phthalic acids, 366.0 parts of sebacic acid, 205.0 parts of NSC 6366s, 131.0 parts of terepthaloyl moietie, 86.0 parts of TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M.s, in the presence of nitrogen, in 6 hours (esterification) of 220 ℃ of reactions.Removing the water of generation through reflux dewatering, carry out the mensuration of acid number and carry out the mensuration of OH value through acetylation method through the KOH volumetry, is 43 when reaching the solids component acid number, stopped reaction when the solids component OH value is 115.Afterwards, be cooled to 170 ℃, add trimellitic acid 1,2-anhydride 108.0 weight parts, be incubated 2 hours, carry out addition reaction, when the solids component acid number is 90, stopped reaction when the solids component OH value is 60.Cooling back uses MIBK to dilute, and promptly obtains heating remaining composition and be 70.0%, acid number is that 63 (solids component is scaled 90), OH value are that 42 (solids component is scaled 60), viscosity are that 345mPas, weight-average molecular weight are 2060 polyester resin solution (a3).
< modulation of antifouling paint compositions >
(embodiment 1)
The 2nd composition of antifouling paint compositions is described below and modulates.
At first; In the plastic containers of 1000ml, cooperate solvent xylene (8.5 parts), PGM (2.5 parts), MIBK (1 part), DuomeenTDO (1.3 parts), rosin (7.5 parts), clorafin (2 parts), stir until uniform dissolution through the coating vibrating machine.
Then; Cooperate talcum FC1 (3 parts), zinc oxide (11 parts), potassium felspar sand (4.2 parts), NovopermRedF5RK (0.3 part), Red copper oxide (30 parts), the positive stearylamine title complex of triphenylborane (13.4 parts), copper pyrithione (2.5 parts), anti-settling agent Dis420020X (1 part); Add 200 parts of granulated glass spherees, disperseed 1 hour.
Further add anti-sagging agent Dis63020X (1.8 parts), after further disperseing 20 minutes, use 80 purpose filtering nets to filter, promptly make paste (1) as the 2nd composition.
On the other hand, as the 1st composition, former state is used through making the polyester resin solution (a1) that example 1 obtains.
To use decollator to mix equably as above-mentioned polyester resin solution (a1) 10 weight parts and above-mentioned the 2nd composition of the 1st composition, process antifouling paint compositions.
(embodiment 2~4)
Except gradation composition and the use level that changes the 2nd composition as shown in table 1ly, and the kind of the 1st composition with the amount outside and embodiment 1 likewise process antifouling paint compositions.
(Comparative Examples 1~2)
With the disclosed coating composition of CN 102224209A is Comparative Examples, and its composition is seen table 1.
Table 1
< evaluation of physical property of antifouling paint compositions >
The antifouling paint compositions of embodiment 1~4 and Comparative Examples 1~2 and the rerum natura of filming of using these formation are estimated as follows.The gained result is as shown in table 2.
(1) volatile organic compounds (VOC) weight determination
Use the value of above-mentioned coating proportion and weight NV to calculate by following formula.
VOC (g/L)=coating proportion * 1000 * (100 weight NV)/100.
(2) proportion
After the 1st composition and the 2nd composition mixed, be full of the quality of antifouling paint compositions that internal volume is the hydrometer jar of 100ml 25 ℃ of weighings immediately, thereby measure proportion (coating proportion) (g/cm3).
(3) heat remaining composition (weight NV)
After the 1st composition and the mixing of the 2nd composition; Measure antifouling paint compositions 1g immediately to the flat ware, the known wire of functional quality spreads out equably, 125 ℃ of dryings after 1 hour; Weighing residue and quality wiry are calculated heating remaining composition (weight %).
(4) viscosimetric analysis of antifouling paint compositions
Total amount by the 1st composition and the 2nd composition is that 1000g carries out weighing, is adjusted to 23 ℃, uses RION viscometer RIONCO., LTDVISCOTESTERVT04F HV usefulness, No. 1 rotor) measure mixed dope viscosity.
(5) vacuum spraying operability
Total amount by the 1st composition and the 2nd composition is that 5000g carries out weighing, confirms the application operability (sprayability, appearance of film) through vacuum spraying.In the table 2, it is good that " A " refers to the application operability, and it is poor that " B " refers to the application operability.
(6) dried coating film property test (plank applied voltage test)
The application epoxy is corrosion-proof paint (Chinese coating manufacturers's name of an article " BANNOH500 ") on the sandblasting steel plate of 150 * 70 * 3.2mm; Make dry film thickness reach 150 μ m; Room temperature (about 20 ℃) dry 1 day and form and film down; The application epoxy is adhesive coating (Chinese coating manufacturers's name of an article " BANNOH500 ") again on this surface of filming, and makes dry film thickness reach 100 μ m, forms following dry 1 day of room temperature (about 20 ℃) and films.At this external coating antifouling paint compositions of filming, make its dry film thickness reach 100 μ m, form following dry 1 day of room temperature (about 20 ℃) and film, this operation repeats 2 times, and the dry film thickness of processing antifouling coat is the test board of 200 μ m.
With above-mentioned test board 23 ℃ of room temperatures dry 1,3,5,7 day again; (central part) placed the wood chip of 30 * 30 * 10mm on filming; Vertically apply the pressure 20 minutes of 40kgf/cm2 (3.9MPa) from the top of this wood chip, observe the state (degree of deformation that mensuration is filmed) of film coated surface.Metewand is as shown in Figure 1.Among Fig. 1,10 is wood chip, and 20 for filming.Metewand 5 expression is filmed and 20 is not had distortion, is good state.20 some distortion are arranged though the expression of grading benchmark 4 can be seen filming, can't see exposing of wood chip 10, be good state.Metewand 3,2, the 1 expression state that wood chip 10 exposes owing to film 20 distortion, the degree of damage (distortion) becomes big by 3,2,1 order.
(7) the consumption degree of antifouling coat test:
On the hard vinyl chloride plate of 50 * 50 * 1.5mm, apply the antifouling paint compositions for preparing among the embodiment, make dry film thickness reach 150 μ m, it was descended dry 7 days in room temperature (about 20 ℃) indoor, process test board with spreader.This test board is installed on the side of the going barrel of the thermostatic bath that is arranged on the seawater that has added 25 ℃,, measures the consumption degree (thickness minimizing) of per 2 months antifouling coat with the SFM rotation of 15 joints.
(8) didirtresistance that leaves standstill of antifouling coat is tested:
On the sandblasting steel plate of 100 * 300 * 3.2mm, be that coating (Chinese coating manufacturers's name of an article " BANNOH500 "), epoxy are that adhesive coating (Chinese coating manufacturers's name of an article " BANNOH500 ") is with 1 day interval application after making dry film thickness reach 150 μ m, 100 μ m respectively with epoxy successively; By this epoxy be the antifouling paint compositions that the surface of filming that forms of adhesive coating prepares among the application embodiment subsequently; Make its dry film thickness reach 150 μ m; And apply with 1 day interval, process test board.
Above-mentioned test board 23 ℃ of dryings 7 days, is left standstill and impregnated in marinely, is the bond area of the settled organism at interval through visual measurement with 2 months, estimates based on following metewand:
0: no hydrobiological adhering to
0.5: hydrobiological bond area surpasses 0%, below 10%
1: hydrobiological bond area surpasses 10%, below 20%
2: hydrobiological bond area surpasses 20%, below 30%
3: hydrobiological bond area surpasses 30%, below 40%
4: hydrobiological bond area surpasses 40%, below 50%
5: hydrobiological bond area surpasses 50%.
Table 2
About the part of raw materials of using in the foregoing description and the comparative example, its details are as shown in table 3.
Table 3
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. antifouling paint compositions; Contain the 1st composition and the 2nd composition; Weight meter according to said antifouling paint compositions; The acid number that said the 1st composition contains 10 ~ 75% solids components is 50~200, the OH value of solids component is below 100, the viscosity 25 ℃ the time is the vibrin below the 500mPas; Said the 2nd composition is for containing the paste of 1 ~ 70% zinc oxide, 2 ~ 40% triphenyl-boron alkanamines, 2 ~ 40% metal pyridine sulphur copper and 2 ~ 30% Red copper oxide, is benchmark with the total amount of said the 1st composition and said the 2nd composition, and the content of volatile organic compounds is below the 400g/L.
2. antifouling paint compositions as claimed in claim 1 is characterized in that, the weight-average molecular weight of the said vibrin through gel permeation chromatography is below 5000;
Preferably, according to the weight meter of said antifouling paint compositions, the content of the zinc oxide in said the 2nd composition is 10~65%, is preferably 20 ~ 50% especially;
Preferably, said antifouling paint compositions also contains rosin and/or rosin derivative.
3. according to claim 1 or claim 2 antifouling paint compositions is characterized in that, further contain stain control agent, but said stain control agent is not triphenyl-boron alkanamine, metal pyridine sulphur copper or Red copper oxide;
Preferably, said antifouling paint compositions also contains softening agent.
4. like each described antifouling paint compositions of claim 1-3, it is characterized in that said triphenyl-boron alkanamine comprises the pyridine triphenylborane.
5. like each described antifouling paint compositions of claim 1-4, it is characterized in that according to the weight meter of said antifouling paint compositions, the content of said triphenyl-boron alkanamine is preferably 10 ~ 30%;
Preferably, according to the weight meter of said antifouling paint compositions, the content of said metal pyridine sulphur copper is 10 ~ 30%;
Preferably, according to the weight meter of said antifouling paint compositions, the content of said Red copper oxide is 10 ~ 25%.
6. like each described antifouling paint compositions of claim 1-5, it is characterized in that, further contain pigment extender, but said pigment extender is not a zinc oxide.
7. like each described antifouling paint compositions of claim 1-6, it is characterized in that, further contain pigment dispersing agent.
8. like each described antifouling paint compositions of claim 1-7, it is characterized in that, further contain tinting pigment.
9. an antifouling coat is characterized in that, the described antifouling paint compositions of each of claim 1-8 is solidified form.
10. the anti-fouling method of a base material is characterized in that, each described antifouling paint compositions of claim 1-8 is coated on the base material or contained be dipped in the base material, makes it be solidified to form antifouling coat then.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012101972054A CN102702939A (en) | 2012-06-14 | 2012-06-14 | Anti-fouling coating composition, anti-fouling coating film and anti-fouling method of base material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012101972054A CN102702939A (en) | 2012-06-14 | 2012-06-14 | Anti-fouling coating composition, anti-fouling coating film and anti-fouling method of base material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102702939A true CN102702939A (en) | 2012-10-03 |
Family
ID=46896003
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2012101972054A Pending CN102702939A (en) | 2012-06-14 | 2012-06-14 | Anti-fouling coating composition, anti-fouling coating film and anti-fouling method of base material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102702939A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105821506A (en) * | 2016-04-16 | 2016-08-03 | 巢湖市强力渔业有限责任公司 | Anti-algae fishing net thread |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002155239A (en) * | 2000-11-22 | 2002-05-28 | Kansai Paint Co Ltd | Antifouling coating composition |
CN101351514A (en) * | 2005-12-28 | 2009-01-21 | 中国涂料株式会社 | High solid antifouling coating composition, antifouling coating film, base with coating film, antifouling base, method for forming coating film on base surface, method for preventing fouling of base, |
CN101652444A (en) * | 2007-06-26 | 2010-02-17 | 中国涂料株式会社 | Triphenylboron compound-containing antifouling coating composition having improved stability, antifouling agent set used therefor, and method for suppressing/controlling decomposition of triphenylboro |
CN101755020A (en) * | 2007-07-18 | 2010-06-23 | 日本油漆船舶涂料公司 | Antifouling paint composition, antifouling coating film, and vessels and underwater structures |
CN102224209A (en) * | 2008-12-24 | 2011-10-19 | 独立行政法人海上技术安全研究所 | Antifouling coating composition, antifouling coating film, and method of preventing fouling of base |
CN102432802A (en) * | 2011-09-16 | 2012-05-02 | 海洋化工研究院 | Resin for biodegradable anti-fouling paint, synthetic method of the same, and anti-fouling paint composition containing the same |
-
2012
- 2012-06-14 CN CN2012101972054A patent/CN102702939A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002155239A (en) * | 2000-11-22 | 2002-05-28 | Kansai Paint Co Ltd | Antifouling coating composition |
CN101351514A (en) * | 2005-12-28 | 2009-01-21 | 中国涂料株式会社 | High solid antifouling coating composition, antifouling coating film, base with coating film, antifouling base, method for forming coating film on base surface, method for preventing fouling of base, |
CN101652444A (en) * | 2007-06-26 | 2010-02-17 | 中国涂料株式会社 | Triphenylboron compound-containing antifouling coating composition having improved stability, antifouling agent set used therefor, and method for suppressing/controlling decomposition of triphenylboro |
CN101755020A (en) * | 2007-07-18 | 2010-06-23 | 日本油漆船舶涂料公司 | Antifouling paint composition, antifouling coating film, and vessels and underwater structures |
CN102224209A (en) * | 2008-12-24 | 2011-10-19 | 独立行政法人海上技术安全研究所 | Antifouling coating composition, antifouling coating film, and method of preventing fouling of base |
CN102432802A (en) * | 2011-09-16 | 2012-05-02 | 海洋化工研究院 | Resin for biodegradable anti-fouling paint, synthetic method of the same, and anti-fouling paint composition containing the same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105821506A (en) * | 2016-04-16 | 2016-08-03 | 巢湖市强力渔业有限责任公司 | Anti-algae fishing net thread |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5989774B2 (en) | Polyester resin for antifouling paint, production method thereof, antifouling paint composition, antifouling coating film, antifouling substrate | |
CN102224209A (en) | Antifouling coating composition, antifouling coating film, and method of preventing fouling of base | |
JP5661766B2 (en) | Antifouling paint composition, antifouling coating film and method for antifouling substrate | |
CN101166801B (en) | Stain-proof coating composition, stain-proof coating film, substrate having coating film, stain-proof substrate, method for formation of coating film on surface of substrate, and method for stain-proofing | |
CN101796148B (en) | Antifouling coating composition, antifouling coating film, substrates with the film, fouling-resistant substrates, process for forming the film on the surfaces of substrates, and method for inhibiting substrate from fouling | |
CN102791812A (en) | Antifouling coating composition and use for same | |
CN101970529B (en) | Antifouling composition | |
JP6360909B2 (en) | Two-pack type antifouling paint composition, antifouling coating film, antifouling substrate and method for producing antifouling substrate | |
CN103608416B (en) | The manufacture method of binary liquid shape hydrolysis-type antifouling paint compositions, antifouling coat and antifouling base material | |
CN101351514A (en) | High solid antifouling coating composition, antifouling coating film, base with coating film, antifouling base, method for forming coating film on base surface, method for preventing fouling of base, | |
CN105176257A (en) | Coating composition, method for producing same, coating film and underwater structure | |
NO20210360A1 (en) | Waterborne antifouling coating material composition | |
JPWO2017022661A1 (en) | Antifouling paint composition, antifouling coating film, antifouling substrate, rosin compound for antifouling paint composition, and method for producing antifouling paint composition | |
CN102702939A (en) | Anti-fouling coating composition, anti-fouling coating film and anti-fouling method of base material | |
CN103038293B (en) | Antifouling paint | |
JP2018048247A (en) | Polyester resin for antifouling coating, antifouling coating composition, antifouling coated film, antifouling base material and method for producing antifouling base material | |
KR20140117922A (en) | Copolymeric binder for antifouling paint, method for manufacturing the same and antifouling paint composition containing the same | |
TWI385223B (en) | An antifouling paint composition, a method for producing the composition, an antifouling coating film formed using the same, a coating material having a coating film on its surface, and a antifouling treatment method for forming the coating film | |
CN103122188A (en) | Self-polished organic silicon fluorine modified acrylate antifouling paint with low surface energy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121003 |