CN1694931A - Antifouling paint composition - Google Patents
Antifouling paint composition Download PDFInfo
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- CN1694931A CN1694931A CNA2003801007440A CN200380100744A CN1694931A CN 1694931 A CN1694931 A CN 1694931A CN A2003801007440 A CNA2003801007440 A CN A2003801007440A CN 200380100744 A CN200380100744 A CN 200380100744A CN 1694931 A CN1694931 A CN 1694931A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
- C09D5/1631—Organotin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Abstract
A novel antifouling paint composition is disclosed. The antifouling paint composition comprises a resin of 5 to 20 weight %; a solvent of 3 to 30 weight %; polyhexamethyleneguanidine salt of the following chemical formula 1 of 0.05 to 20 weight %; a pigment of 1 to 50 weight %; and cuprous oxide of 22 to 75 weight % and/or zinc pyrithione of the following chemical formula 2 of 0.05 to 20 weight %. [Chemical formula 1] [Chemical formula 2] In chemical formula 1, at least one of X is an inorganic acid salt or an organic acid salt; R is an alkyl group, a phenyl group, a benzyl group, a phenethyl group, a naphthyl group or hydrogen, and n is an integer of 1 or more.
Description
Technical field
The present invention relates to a kind of antifouling paint compositions, relate more specifically to a kind of novel antifouling coating composition, it does not contain the organo-tin compound that can cause sea pollution, and comprises poly (hexamethylene) and Zinc Pyrithione and/or Red copper oxide (Cu
2O).
Background technology
Many marine organisms, for example blue freshwater mussel (blue mussel), common green turtle limpet (common turtlelimpet), liver moss, diatom, oyster, Margarita (pearl oyster), Spongia, noctilucence shellfish (turbanshell), sea lettuce (sealettuce), Ascidian (sea squirt) or the like all live in seawater, and these marine organisms damage these oceanographic equipments attached on equipment, ship, salvage waist band, port facilities, plant, fishing net or the like under the sea.If especially these marine organisms are attached to hull bottom, then the ship surface becomes coarse thereby needs maintenance continually.In addition, when the degree of roughness on ship surface reaches 0.01mm, the fuel consumption of this ship will increase 0.3%-1.0%.This can cause more serious problem to 50% the large vessel that fuel consumption accounts for running cost.
In order to prevent this class dirt of oceanographic equipment, the conventional antifouling paint compositions that is mixed with by rosin, softening agent and stain control agent and vinyl chloride resin or ethenoid resin that adopts.Yet described conventional antifouling paint compositions also comprises the sea pollution thing, because described composition comprises mercury compound or organo-tin compound as stain control agent.And other antifouling paint compositions, United States Patent (USP) the 4th, 191, No. 579 and English Patent the 1st, 457, No. 590 the automatically cleaning antifouling paint compositions is disclosed, wherein organo-tin compound (as tributyltin oxide) with unsaturated monomer (for example acrylate or methacrylate) thus combine and form ester bond (linkage) betwixt.Because this ester bond, described antifouling paint compositions be slowly hydrolysis in seawater, thereby slowly releases organo-tin compound from this antifouling paint compositions.Owing to discharging the carboxylic group formation salt that organo-tin compound produces, this makes described stain control agent become water miscible and produces and expands.Therefore, described stain control agent surfacial spalling and expose new surface.This class antifouling paint compositions is generally used for the antifouling of seawater equipment.Yet the lasting release of described organo-tin compound from described stain control agent has non-target (non-target) toxicity, and it not only causes sea pollution but also destroys the ecosystem.Therefore, need a kind of novel antifouling coating composition of exploitation, it can prevent the dirt of the seawater equipment that caused by various marine organisms and microorganism effectively, and is not having defective aspect environment and the health.
Summary of the invention
Therefore, one of purpose of the present invention just provides and a kind of human body and ocean environment is safe from harm, and the dirt that biology causes is had the antifouling paint compositions of antifouling effect preferably.
Another object of the present invention provides a kind of being applicable to such as fishing net, ship, sea oceanographic equipment antifouling of equipment etc. down, and does not contain the mercury that can cause sea pollution or the antifouling paint compositions of organo-tin compound.
In order to reach these and other purpose, the invention provides a kind of antifouling paint compositions, it comprises the resin of 5%-20% weight ratio; The solvent of 3%-30% weight ratio; The poly (hexamethylene) shown in following Chemical formula 1 of 0.05%-20% weight ratio; The pigment of 1%-50% weight ratio; And the Red copper oxide (Cu of 22%-75% weight ratio
2O) and/or the Zinc Pyrithione shown in following Chemical formula 2 of 0.05%-20% weight ratio (zinc pyrithione).
[Chemical formula 1]
[Chemical formula 2]
In Chemical formula 1, X can be identical or different, and to have an X at least be inorganic acid salt or organic acid salt; R
1Can be identical or different, and for containing straight or branched alkyl, phenyl, chlorophenyl, bromo phenyl, iodine substituted phenyl, benzyl, chloro benzyl, benzyl bromide, benzyl iodide, styroyl, naphthyl or the hydrogen of 1-20 carbon atom; And n is equal to or greater than 1 integer.Preferably, X can be identical or different, and have at least an X to be selected from HCl, HBr, HI, HNO
3, carbonic acid, sulfuric acid, phosphoric acid, acetate, phenylformic acid, dehydro-acetic acid, propionic acid, glyconic acid, Sorbic Acid, fumaric acid, toxilic acid and epoxy chloropropane.Preferably, described solvent is dimethylbenzene, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or its mixture, and described pigment is titanium oxide, zinc oxide, ferric oxide or its mixture.More preferably, described antifouling paint compositions also comprises the jelling agent that accounts for total coating composition 1%-5% weight ratio.
Detailed description of the invention
By with reference to following detailed description, can more fully understanding be arranged to the present invention and various advantage thereof.
Antifouling paint compositions of the present invention is being more satisfactory aspect environment and the health, and comprises poly (hexamethylene) and Zinc Pyrithione shown in following Chemical formula 2 and/or Red copper oxide (Cu shown in following Chemical formula 1
2O).
[Chemical formula 1]
[Chemical formula 2]
In Chemical formula 1, X can be identical or different, and to have an X at least be inorganic acid salt or organic acid salt.Preferably, having an X at least is HCl, HBr, HI, HNO
3, carbonic acid, sulfuric acid, phosphoric acid, acetate, phenylformic acid, dehydro-acetic acid, propionic acid, glyconic acid, Sorbic Acid, fumaric acid, toxilic acid or epoxy chloropropane, and more preferably to have an X at least be phosphoric acid.R
1Can be identical or different, and be straight or branched alkyl, phenyl, chlorophenyl, bromo phenyl, iodine substituted phenyl, benzyl, chloro benzyl, benzyl bromide, benzyl iodide, styroyl, naphthyl or the hydrogen that contains 1-20 carbon atom, and n is equal to or greater than 1 integer.
Consider and convenient described poly (hexamethylene) is handled (for example with other component uniform mixing of described salt and described coating composition, be easy to antifouling property time length for preparing described salt, described salt or the like), the molecular weight of described poly (hexamethylene) is preferably 500-20,000,800-10 more preferably, 000, most preferably be 900-5,000.Can prepare the poly (hexamethylene) shown in the Chemical formula 1 by known polymerization process, for example by guanidinesalt and the monomer generation polycondensation with diamine group are prepared.Stain control agent shown in the Chemical formula 1 (being poly (hexamethylene)) is soluble in water, and can be near the cytolemma of organism (it forms dirt by electrostatic adhesion power), and with phospholipids incorporate such as phosphatidyl glycerol.Then, described salt decomposes described cytolemma by upsetting membrane structure, thereby prevents that organism is attached on the oceanographic equipment.
Red copper oxide (Cu
2O) form with cupric ion or mantoquita discharges from described coating surface, and forms inner complex with amino acid or enzyme in the cell, and the protoplasma in the cell is condensed.Consequently, Red copper oxide has stoped the marine animal that adheres to or the breeding of plant, thereby has reduced the dirt that is caused by described marine animal and plant.Therefore, the preferred antifouling paint compositions of the present invention comprises that simultaneously microorganism is had the poly (hexamethylene) of better antifouling property and marine animal and plant are had the Red copper oxide of better antifouling property, so the various biologies of described dirt that cause are had extensive and effective antifouling property.The molecular weight of the stain control agent shown in the Chemical formula 2 (being Zinc Pyrithione) is 317.7, and because Zinc Pyrithione solubleness in polar solvent or non-polar solvent is minimum, therefore discharges lentamente from described coating surface.Zinc Pyrithione that is discharged and the enzyme of organism (enzyme that particularly contains metal ion) form composite salt, reduce the activity of described enzyme, and the final microbial growth that suppresses such as mucus (slime).
Antifouling paint compositions of the present invention comprises the resin of 5%-20% weight ratio; The solvent of 3%-30% weight ratio; Poly (hexamethylene) shown in the Chemical formula 1 of 0.05%-20% weight ratio; The pigment of 1%-50% weight ratio; And the Red copper oxide (Cu of 22%-75% weight ratio
2The jelling agent that O) and/or the Zinc Pyrithione shown in the Chemical formula 2 of 0.05%-20% weight ratio, also can at random comprise the 1%-5% weight ratio.When antifouling paint compositions of the present invention comprises Red copper oxide (Cu
2O) time, described coating composition preferably includes the resin of 5%-20% weight ratio, the solvent of 3%-25% weight ratio, the poly (hexamethylene) shown in the Chemical formula 1 of 1%-15% weight ratio, the Red copper oxide (Cu of 22%-75% weight ratio
2O) and the pigment of 1%-19% weight ratio.Selectively, when antifouling paint compositions of the present invention comprises Zinc Pyrithione, described coating composition preferably includes the resin of 10%-15% weight ratio, the solvent of 20%-30% weight ratio, the pigment of the weight ratio of the Zinc Pyrithione shown in poly (hexamethylene) shown in the Chemical formula 1 of 5%-20% weight ratio and the Chemical formula 2, and 40%-50% altogether.In this case, the amount of described Zinc Pyrithione be described polyhexamethyleneguasaltne saltne by weight 0.01-100 doubly.
The used resin of conventional antifouling paint compositions can be used as the resin of the present composition without restriction.Can be used for exemplary resin of the present invention comprises such as the synthetic resins of ethenoid resin (for example polyvinyl acetate resin, polyvinyl chloride (PVC) RESINS), urethane resin, chlorinated rubber resin, phthalide resin, Synolac, Resins, epoxy, phenol resins, melamine resin, acrylic resin, fluoro-resin and silicone resin and such as the natural resin of rosin.In addition, many water miscible resins or fat-soluble resin all can use with described synthetic or natural resin.The amount of preferred described resin is the 5%-20% weight ratio of total coating composition.When the amount of described resin was lower than 5% weight ratio, the adhesion of described coating composition descended.When the amount of described resin was higher than 20% weight ratio, the storage stability of described coating composition descended.
The solvent that can be used for antifouling composition of the present invention comprises variously can dissolve and disperse the solvent of every kind of component of described coating composition.Exemplary solvent comprises alkyl solvent or ketone compound, for example dimethylbenzene, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and composition thereof.The amount of preferred described solvent is the 3%-30% weight ratio of total coating composition.When the amount of described solvent was lower than 3% weight ratio, the excess stickiness of described coating composition increased.When the amount of described solvent was higher than 30% weight ratio, the adhesion of described coating composition and didirtresistance descended.
The amount of the stain control agent shown in the described Chemical formula 1 is the 0.05%-20% weight ratio of total coating composition, is preferably the 5%-20% weight ratio, 5%-15% weight ratio more preferably, and preferred Red copper oxide (Cu
2) amount be the 22%-75% weight ratio.When the amount of stain control agent shown in the described Chemical formula 1 and Red copper oxide is lower than above-mentioned preferred concentration, or when only used stain control agent shown in the described Chemical formula 1 and Red copper oxide one of them the time, the antifouling effectiveness of described composition descends.When the amount of the stain control agent of described Chemical formula 1 and Red copper oxide is higher than above-mentioned preferred concentration, the physical property of described coating composition and storage stability variation.
When the Zinc Pyrithione shown in the described Chemical formula 2 of use, the amount of the mixture of preferred described poly (hexamethylene) and Zinc Pyrithione is the 5%-20% weight ratio of total coating composition.If the amount of described mixture is lower than 5% weight ratio, then the antifouling effectiveness of described composition descends, and organism can be caused dirt attached to oceanographic equipment.If the amount of described mixture is higher than 20% weight ratio, the then physical property of described coating composition and storage stability variation.The amount of preferred described Zinc Pyrithione is the 0.05%-20% weight ratio of total coating composition, more preferably 5%-19% weight ratio, 5%-15% weight ratio most preferably, and the 0.01-100 that is preferably described polyhexamethyleneguasaltne saltne by weight is doubly, more preferably 0.05-50 doubly most preferably is 0.1-10 doubly.When the amount of described Zinc Pyrithione is not in above-mentioned scope, can not obtain required antifouling effectiveness.
Conventional pigment can be used as the pigment of antifouling paint compositions of the present invention without restriction.Exemplary pigment comprises metal oxide pigment, pigment dyestuff and composition thereof.Described metal oxide pigment comprises titanium oxide, zinc oxide and ferric oxide.The amount of preferred described pigment is the 1%-50% weight ratio of total coating composition.When the amount of described pigment is lower than 1% weight ratio, the color variation of described coating composition.When the amount of described pigment is higher than 50% weight ratio, the weathering resistance variation of described coating composition.
Antifouling paint compositions of the present invention can comprise various conventional additives.An example of this class additive is the jelling agent such as polyamide wax, wilkinite, polyethylene wax or the like.The amount of preferred described jelling agent is the 1%-5% weight ratio of total coating composition.When the amount of described jelling agent was lower than 1% weight ratio, the coating of described coating composition operation can not be carried out effectively.When the amount of described jelling agent was higher than 5% weight ratio, the excess stickiness of described coating composition increased.
That antifouling paint compositions of the present invention itself has is abundant and antimicrobial widely, anti-mildew and anti-algae characteristic.Yet antifouling paint compositions of the present invention can comprise conventional antimicrobial, anti-mildew or anti-algae reagent arbitrarily.Exemplary is conventional antimicrobial; anti-mildew or anti-algae reagent comprise 3-iodo-2-propynyl butyl carbamate; diiodomethyl is to toluene sulfone (diiodomethyl-p-tolysulfone); 1; the 2-benzisothiazole-3-ketone; 2-methylthio group-4-tertiary butyl amino-6-cyclopropyl amino-s-triazine; 2-(4-thiocyanomethylthio) benzothiazole; 2; 3; 5; 6-tetrachloro-4-(methylsulfonyl) pyridine; 3-(3; the 4-dichlorophenyl)-1; the 1-dimethyl urea; 2-n-octyl-4-isothiazoline-3-ketone; the different phthalonitrile of tetrachloro; N-(fluorine dichloromethane sulfenyl) phthalic imidine; N-dichloro fluorine methylthio group-N '; N '-dimethyl-N-para toluene sulfonamide; α-[2-(4-chloro-phenyl-) ethyl]-α-(1; the 1-dimethyl ethyl)-1H-1; 2; 4-triazole-1-ethanol; N, N-dimethyl-N '-phenyl-(fluorine dichloromethane sulfenyl)-sulphamide (sulphamide); (2-sulfo-pyridine-1-oxygen) zinc (zinc (2-pyridylthio-1-oxide)); (2-sulfo-pyridine-1-oxygen) copper (copper (2-pyridylthio-1-oxide)); silver compound and composition thereof.
Antifouling paint compositions of the present invention can be by conventional preparation method for coating preparation.For example, with dimethylbenzene and a spot of ketone compounds resin is dissolved fully.Subsequently to wherein adding pigment, and disperse with sand mill.Then described stain control agent and additive are added in the dispersed mixture of gained, and stir with high speed dispersor.After described mixture stirring, also stir to wherein adding remaining solvent, thereby obtain antifouling paint compositions of the present invention.
In order to understand the present invention better, below will describe the preferred embodiments of the present invention.Yet the following example is for the present invention is described, but the present invention should not be limited to following examples.
[embodiment 1]
The rosin of the ethenoid resin of 12% weight ratio and 2% weight ratio is dissolved in fully in the mixed solvent of methyl iso-butyl ketone (MIBK) of the dimethylbenzene that comprises 3% weight ratio and 3% weight ratio.Disperse twice subsequently to the zinc oxide that wherein adds 13% weight ratio, and with sand mill.Stain control agent (poly (hexamethylene), the wherein X=H shown in the Chemical formula 1 of adding 7% weight ratio in the dispersed mixture of gained
3PO
4, R
1=H, n=3 and MW=1020), the Red copper oxide of 50% weight ratio and the polyamide wax as jelling agent of 3% weight ratio, and stirred 30 minutes at 1500rpm with high speed dispersor.At last, to methyl iso-butyl ketone (MIBK) that wherein adds remaining 7% weight ratio and stirring, obtain the antifouling paint compositions shown in the table 1.
＜table 1 〉
| Coating composition | Weight ratio % |
| Ethenoid resin (Union Carbide Corp., ProductName: " VINYLITE VYHH ") | ????12 |
| Rosin (ROM Rosin) | ????2 |
| Dimethylbenzene | ????3 |
| Zinc oxide | ????13 |
| Red copper oxide | ????50 |
| Poly (hexamethylene) | ????7 |
| Jelling agent (polyamide wax) | ????3 |
| Methyl iso-butyl ketone (MIBK) | ????10 |
| Total amount | ????100 |
[embodiment 2]
Except that the Red copper oxide of poly (hexamethylene) that uses 14% weight ratio and 43% weight ratio, prepare described antifouling paint compositions according to the method described in the embodiment 1.
[comparative example 1]
Except that the Red copper oxide that uses 57% weight ratio and do not use the poly (hexamethylene), prepare described antifouling paint compositions according to the method described in the embodiment 1.
[comparative example 2]
Except that the Red copper oxide of poly (hexamethylene) that uses 36% weight ratio and 21% weight ratio, prepare described antifouling paint compositions according to the method described in the embodiment 1.
[comparative example 3]
Except that not using poly (hexamethylene) and Red copper oxide, prepare described antifouling paint compositions according to the method described in the embodiment 1.
[comparative example 4]
The mixture of the dimethylbenzene of the Diisopropyl azodicarboxylate of 0.5 weight part and 10 weight parts is added in the mixture that the dimethylbenzene by the methyl methacrylate of the tributyl tin methylacrylate of 15 weight parts, 35 weight parts and 40 weight parts constitutes, and obtained polymkeric substance in 3 hours 80 ℃ of reactions.Then, add the talcum of 10 weight parts, the barium sulfate of 5 weight parts, the Red copper oxide of fluoridizing tributyl tin, 20 weight parts of 10 weight parts and the dimethylbenzene of 40 weight parts, obtain the polymkeric substance of 100 weight parts.The gained mixture was disperseed 2 hours at 2500rpm with high speed dispersor, obtain antifouling paint compositions.
[embodiment 3]
Ethenoid resin and rosin are dissolved in the mixed solvent that comprises dimethylbenzene and methyl iso-butyl ketone (MIBK) fully.Disperse twice subsequently to wherein adding zinc oxide and ferric oxide, and with sand mill.In the dispersed mixture of gained, add by stain control agent (poly (hexamethylene), the wherein X=H shown in the Chemical formula 1 of 7.5% weight ratio
3PO
4, R
1=H, n=3 and MW=1020) and the Chemical formula 2 of 7.5% weight ratio shown in stain control agent (poly (hexamethylene): Zinc Pyrithione=5: 5) the stain control agent mixture and the jelling agent of Gou Chenging, and stirred 30 minutes at 1500rpm with high speed dispersor.At last, to wherein adding remaining ketone compound solvent and stirring, obtain the antifouling paint compositions shown in the table 2.
＜table 2 〉
| Coating composition | Weight ratio % |
| Ethenoid resin (Union Carbide Corp., ProductName: " VINYLITE VYHH ") | ????5 |
| Rosin (ROM Rosin) | ????8 |
| Dimethylbenzene | ????10 |
| Zinc oxide | ????27 |
| Ferric oxide | ????17 |
| The poly (hexamethylene) of Chemical formula 1 | ????7.5 |
| The Zinc Pyrithione of Chemical formula 2 | ????7.5 |
| Jelling agent (polyamide wax) | ????3 |
| Methyl iso-butyl ketone (MIBK) | ????15 |
| Total amount | ????100 |
[embodiment 4]
Except using by (the poly (hexamethylene): Zinc Pyrithione=3: 7) the stain control agent mixture of Gou Chenging, prepare described antifouling paint compositions of the stain control agent shown in the Chemical formula 2 of stain control agent shown in the Chemical formula 1 of 4.5% weight ratio and 10.5% weight ratio according to the method described in the embodiment 3.
[embodiment 5]
Except using by (the poly (hexamethylene): Zinc Pyrithione=7: 3) the stain control agent mixture of Gou Chenging, prepare described antifouling paint compositions of the stain control agent shown in the Chemical formula 2 of stain control agent shown in the Chemical formula 1 of 10.5% weight ratio and 4.5% weight ratio according to the method described in the embodiment 3.
[comparative example 5]
Except the stain control agent shown in the Chemical formula 1 that uses 15% weight ratio and do not use the stain control agent shown in the Chemical formula 2, prepare described antifouling paint compositions according to the method described in the embodiment 3.
[comparative example 6]
Except the stain control agent shown in the Chemical formula 2 that uses 15% weight ratio and do not use the stain control agent shown in the Chemical formula 1, prepare described antifouling paint compositions according to the method described in the embodiment 3.
[comparative example 7]
The polyvinyl chloride resin of 12 weight parts, red iron oxide, 10 parts by weight of titanium oxide, the zinc oxide of 10 weight parts and the Red copper oxide of 40 weight parts of 5 weight parts were disperseed 1 hour at 2500rpm with high speed dispersor, and is ground to particle size less than 40 μ m with sand mill.The dispersed mixture of gained is added in the container of Tritolyl Phosphate (tricresyl phosphate) of the rosin of methyl iso-butyl ketone (MIBK), 8 weight parts of the dimethylbenzene that contains 40 weight parts, 30 weight parts and 5 weight parts, and stirred 30 minutes at 1500rpm with high speed dispersor, obtain described antifouling paint compositions.
[experimental example]
By following method the antifouling property of embodiment and comparative example's antifouling paint compositions is measured., and get rusty coated with preventing to carrying out sandblasting (sand blast) according to the method for KSM 5569 with the tar ethenoid resin according to the Koream Industrial Standard KSD 3501 rolling steel thin slices that are of a size of 300 * 300 * 3.2mm (width * length * thickness).Antifouling paint compositions with embodiment and comparative example sprays twice on described steel thin slice then, makes the build of coating reach 150 μ m.To three testing plate of every kind of antifouling paint compositions preparation.Under the temperature of the relative humidity 75% and 25 ℃ described testing plate after the dry week, is placed described testing plate next meter depths, sea, the place ahead, Goeje island of Korea S Tongyoung-Si.After 12 months, detect described antifouling property.Calculate three parts 52,000mm
2The arithmetical av of the dirt area in the useful area, the result is shown in table 3 and table 4, and wherein said useful area limits (define) by following lines: apart from the line of described testing plate top margin 70mm, apart from the line of described testing plate base 30mm and respectively apart from the line of every side 20mm of described testing plate.
＜table 3 〉
| Antifouling property | Embodiment 1 | Embodiment 2 | The comparative example 1 | The comparative example 2 | The comparative example 3 | The comparative example 4 | |
| The dirt area | Mucus | ????5 | ????5 | ????50 | ????10 | ????100 | ????40 |
| Algae | ????0 | ????0 | ????5 | ????30 | ????40 | ????0 | |
| Barnacle | ????0 | ????0 | ????0 | ????5 | ????50 | ????0 | |
＜table 4 〉
| Antifouling property | Embodiment 3 | Embodiment 4 | Embodiment 5 | The comparative example 5 | The comparative example 6 | The comparative example 7 | |
| The dirt area | Mucus | ????5 | ????15 | ????10 | ????20 | ????25 | ????40 |
| Algae | ????0 | ????0 | ????5 | ????0 | ????0 | ????0 | |
| Barnacle | ????0 | ????0 | ????0 | ????0 | ????0 | ????0 | |
As shown in table 3, embodiment 1 compares with comparative example 4 the antifouling paint compositions that comprises mercury or organo-tin compound (conventional automatically cleaning antifouling paint compositions) with 2 the antifouling paint compositions that comprises poly (hexamethylene) shown in the Chemical formula 1 and Red copper oxide has better antifouling property.In addition, the coating composition that a kind of stain control agent or Red copper oxide is lower than 22% weight ratio that includes only among the comparative example 1 and 2 has inadequate antifouling property.As shown in table 4, the antifouling paint compositions that comprises poly (hexamethylene) shown in the Chemical formula 1 and the Zinc Pyrithione shown in the Chemical formula 2 with include only poly (hexamethylene) and one of Zinc Pyrithione or comprise that the antifouling paint compositions of Red copper oxide, mercury or organo-tin compound compares, have similar or better antifouling property.In addition, the Zinc Pyrithione shown in poly (hexamethylene) shown in the Chemical formula 1 and the Chemical formula 2 is harmless to human body and ocean environment, and is suitable as the mercury that can cause Marine Environmental Pollution or the substitute of organo-tin compound.Therefore, antifouling paint compositions of the present invention can be used for preventing such as fishing net, ship, the extra large dirt of equipment or the like down.
Claims (10)
1. antifouling paint compositions comprises:
The resin of 5%-20% weight ratio;
The solvent of 3%-30% weight ratio;
The poly (hexamethylene) shown in following Chemical formula 1 of 0.05%-20% weight ratio;
The pigment of 1%-50% weight ratio; And
The Zinc Pyrithione shown in following Chemical formula 2 of the Red copper oxide of 22%-75% weight ratio and/or 0.05%-20% weight ratio,
[Chemical formula 1]
[Chemical formula 2]
In Chemical formula 1, X can be identical or different, and to have an X at least be inorganic acid salt or organic acid salt; R
1Can be identical or different, and for containing straight or branched alkyl, phenyl, chlorophenyl, bromo phenyl, iodine substituted phenyl, benzyl, chloro benzyl, benzyl bromide, benzyl iodide, styroyl, naphthyl or the hydrogen of 1-20 carbon atom; And n is equal to or greater than 1 integer.
2. antifouling paint compositions as claimed in claim 1, wherein said coating composition comprises the resin of 5%-20% weight ratio, the solvent of 3%-25% weight ratio, poly (hexamethylene) shown in the Chemical formula 1 of 1%-15% weight ratio, the pigment of the Red copper oxide of 22%-75% weight ratio and 1%-19% weight ratio.
3. antifouling paint compositions as claimed in claim 1, wherein said coating composition comprises the resin of 10%-15% weight ratio, the solvent of 20%-30% weight ratio, account for poly (hexamethylene) shown in the Chemical formula 1 of 5%-20% weight ratio and the Zinc Pyrithione shown in the Chemical formula 2 altogether, with the pigment of 40%-50% weight ratio, and the amount of described Zinc Pyrithione is 0.01-100 times of described polyhexamethyleneguasaltne saltne by weight.
4. antifouling paint compositions as claimed in claim 1, wherein X can be identical or different, and have at least an X to be selected from HCl, HBr, HI, HNO
3, carbonic acid, sulfuric acid, phosphoric acid, acetate, phenylformic acid, dehydro-acetic acid, propionic acid, glyconic acid, Sorbic Acid, fumaric acid, toxilic acid and epoxy chloropropane.
5. antifouling paint compositions as claimed in claim 1, the molecular weight of wherein said poly (hexamethylene) are 500-20,000.
6. antifouling paint compositions as claimed in claim 1, wherein said solvent is selected from dimethylbenzene, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and composition thereof.
7. antifouling paint compositions as claimed in claim 1, wherein said pigment is selected from titanium oxide, zinc oxide, ferric oxide and composition thereof.
8. antifouling paint compositions as claimed in claim 1 also comprises the jelling agent based on the 1%-5% weight ratio of total coating composition.
9. antifouling paint compositions as claimed in claim 1, wherein said resin is selected from ethenoid resin, urethane resin, chlorinated rubber resin, phthalide resin, Synolac, Resins, epoxy, phenol resins, melamine resin, acrylic resin, fluoro-resin, silicone resin, rosin and composition thereof.
10. antifouling paint compositions as claimed in claim 1; also comprise the compound that is selected from following material: 3-iodo-2-propynyl butyl carbamate; diiodomethyl is to the toluene sulfone; 1; the 2-benzisothiazole-3-ketone; 2-methylthio group-4-tertiary butyl amino-6-cyclopropyl amino-s-triazine; 2-(4-thiocyanomethylthio) benzothiazole; 2; 3; 5; 6-tetrachloro-4-(methylsulfonyl) pyridine; 3-(3; the 4-dichlorophenyl)-1; the 1-dimethyl urea; 2-n-octyl-4-isothiazoline-3-ketone; the different phthalonitrile of tetrachloro; N-(fluorine dichloromethane sulfenyl) phthalic imidine; N-dichloro fluorine methylthio group-N '; N '-dimethyl-N-para toluene sulfonamide; α-[2-(4-chloro-phenyl-) ethyl]-α-(1; the 1-dimethyl ethyl)-1H-1; 2; 4-triazole-1-ethanol; N, N-dimethyl-N '-phenyl-(fluorine dichloromethane sulfenyl)-sulphamide; (2-sulfo-pyridine-1-oxygen) zinc; (2-sulfo-pyridine-1-oxygen) copper; silver compound and composition thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020020065270 | 2002-10-24 | ||
| KR1020020065270A KR100904174B1 (en) | 2002-10-24 | 2002-10-24 | Antifouling Paint Composition Comprising Zinc pyrithione |
| KR1020020067191 | 2002-10-31 |
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| Publication Number | Publication Date |
|---|---|
| CN1694931A true CN1694931A (en) | 2005-11-09 |
| CN1304496C CN1304496C (en) | 2007-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2003801007440A Expired - Fee Related CN1304496C (en) | 2002-10-24 | 2003-10-23 | Antifouling paint composition |
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| KR (1) | KR100904174B1 (en) |
| CN (1) | CN1304496C (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100904174B1 (en) | 2009-06-22 |
| KR20040036305A (en) | 2004-04-30 |
| CN1304496C (en) | 2007-03-14 |
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