KR101732542B1 - Antifouling paint composition comprising organic polysiloxane copolymer - Google Patents
Antifouling paint composition comprising organic polysiloxane copolymer Download PDFInfo
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- KR101732542B1 KR101732542B1 KR1020150065893A KR20150065893A KR101732542B1 KR 101732542 B1 KR101732542 B1 KR 101732542B1 KR 1020150065893 A KR1020150065893 A KR 1020150065893A KR 20150065893 A KR20150065893 A KR 20150065893A KR 101732542 B1 KR101732542 B1 KR 101732542B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09D7/1233—
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Abstract
The present invention relates to an antifouling paint composition comprising an organopolysiloxane copolymer. The antifouling paint composition of the present invention exhibits antifouling performance through self-abrasion performance, surface characteristics and self-antifouling effect without adding an antifouling agent.
Description
The present invention relates to an antifouling paint composition comprising an organopolysiloxane copolymer.
The coating composition to which the antifouling resin is applied is intended to prevent or control adhesion and growth of marine organisms causing surface contamination of the seawater-deposited coating film. When various marine organisms are attached to the surface of the film, the frictional force between the surface of the film and the sea water during the operation of the ship increases, which may increase the fuel cost, which is a large part of the operating expenses. The antifouling paint is a paint for removing such adherence to reduce the coefficient of friction between water and ship during operation.
The antifouling paints are of the insoluble type using a binder which is insoluble in water and the water-soluble type using a binder which is soluble in water. The insoluble type is an antifouling paint prepared by adding a large amount of an antifouling agent such as copper oxyhydroxide to an old-fashion antifouling paint using water-insoluble vinyl, a chlorinated rubber resin or the like. In the state that the resin- Antifouling agents such as ash acid are gradually diffused into seawater to exhibit antifouling performance. The water-soluble type is a paint used together with an antifouling agent by mixing insoluble resin and water-soluble resin such as rosin. The antifouling agent contained in the coating film while the resin is dissolved in water exhibits the antifouling performance as seawater. The water-soluble type has a longer antifouling performance than the insoluble type, but the time period during which the coating film does not melt uniformly and the antifouling performance is exhibited is within three years.
The antifouling paint widely used at present is a method in which an insoluble resin is mixed with seawater to hydrolyze and gradually dissolves into water-soluble and dissolves the antifouling agent such as copper oxide to release the antifouling performance. Since the rate of dissolution in seawater is controlled uniformly compared to existing water-soluble types, long-term antifouling performance can be achieved.
Antifouling paints can be classified into tin type and non-tin type depending on whether there is tin or not. Non-tin type can be divided into metal type and silyl type. The tin type is a structure in which tributyl tin oxide is chemically bonded to the acrylic main chain. The alkali is hydrolyzed at a pH of 8 or higher to become a copolymer of acrylic acid, which gradually dissolves in weakly alkaline sea water. Especially hydrolyzed tributyltin has its own antifouling property, so it has the merit of magnetic wear characteristics and self - repellant. However, due to tributyltin poisoning, negative factors such as fish malformation and female males became more important.
The non-ferrous metal type has a similar structure to the tin type. Acrylic acid or acid compound with Zn or Cu, which is dissolved in seawater due to hydrolysis. Since non-ferrous metal type has no self-antifouling property, it merely controls the self-abrasion through hydrolysis and adds oil / inorganic antifouling agent to give flame proof. In addition, the silyl type, which has recently been attracting attention, has a high chemical stability and can be used in various antifouling agents, and has a more stable wear rate than the non-sapphire metal type. The silyl type acrylic monomers are high in cost, and the total raw material cost is high, which is a disadvantage. Since the abrasion rate at the time of anchoring is low, the antifouling property may not be sufficient.
In recent years, the ability to prevent or control the attachment and growth of marine organisms that cause pollution has been extended to include long-term use, reduction of frictional resistance with seawater, reduction of fuel costs, and the inclusion of volatile organic compounds (VOC) And additional functions such as the ability to reduce the amount of data are added.
JP-A-1990-196869 discloses a hydrolyzable copolymer composed of trimethylsilyl (meth) acrylate and an unsaturated monomer. Trimethylsilyl (meth) acrylate has been reported to have a degree of hydrolysis of about 70% as compared to conventional tin-based binders. This is because the metal ester structure is relatively covalent to silicon in comparison with tin, It seems to be because of Therefore, the content of hydrolyzed trimethylsilyl (meth) acrylate must be higher than that of other antifouling coating compositions. However, the trimethylsilyl (meth) acrylate monomer is relatively expensive in terms of cost and has a problem that the crack resistance of the binder becomes poor when the content is higher than necessary. Further, when a material having a small number of carbon atoms of an alkyl group bonded to silicon is applied to improve the hydrolysis property, there is a problem that the long term storage property is poor.
Korean Patent Laid-Open Publication No. 1997-7004840 discloses a method of mixing a plastic (meth) acrylate copolymer to solve the problem of a copolymer composed of a trimethylsilyl (meth) acrylate monomer. However, in this case, there is a problem that as the nonhydrolyzable binder remains after long-term wear in seawater, the wear rate gradually decreases.
Korean Patent Laid-Open Publication No. 2013-0093840 discloses a process for producing an organic acid containing a carboxylic acid group and an amine group by a radical reaction of a monomer containing a divalent metal and a double bond and a carboxylic acid group and a double bond and an alkyl group A resin for an antifouling paint prepared by a condensation reaction with an acrylic resin, and an antifouling paint composition containing the same. In this case, application of an organic acid containing a carboxylic acid group and an amine group has physical properties improved in discoloration resistance and crack resistance, but it is insufficient to exhibit low viscosity and high specific gravity.
An object of the present invention is to provide an antifouling coating composition which exhibits antifouling performance of existing antifouling paints through self-abrasion performance, surface characteristics, and self-antifouling effect without adding antifouling agents to be applied in the prior art.
The antifouling paint composition of the present invention comprises a copolymer comprising as a polymerized unit an organopolysiloxane, a hydrophilic monomer having no carboxylic acid group, a monomer having a double bond and a carboxylic acid group, and a polymerizable monomer having a non-reactive alkyl group.
The antifouling paint composition according to the present invention is characterized in that an antifouling agent is obtained by applying a copolymer comprising an organopolysiloxane as a polymerization unit, a hydrophilic monomer having no carboxylic acid group, a monomer having a double bond and a carboxylic acid group and a polymerizable monomer containing a non- It has the effect of imparting hydrophobicity to the surface of the coating film and hydrolyzing the coating film due to the reaction with seawater, thereby reducing occurrence and adherence of marine pollutants.
Hereinafter, the present invention will be described in more detail.
As used herein, the term " (meth) acrylic " is a concept that includes both acrylic and methacrylic.
The copolymer contained in the antifouling paint composition of the present invention includes an organopolysiloxane as a polymerization unit. The organopolysiloxane has hydrophobicity imparted to the surface of the antifouling coating film to reduce the occurrence of contamination by marine organisms and the like, and may have a structure represented by the following formula (1).
[Chemical Formula 1]
In Formula 1, R1 is a (meth) acrylic acid, C 1 -C 5 alkyl (meth) acrylate groups, C 2 -C 10 alkenyl group, C 1 -C 10 An alkoxy group, an OH group, an epoxy group, a COOH group or hydrogen, and m is an integer of 0 to 60.
The organopolysiloxane may have a number average molecular weight (Mn) of 1,000 to 10,000. If the number average molecular weight of the organopolysiloxane is too low, there may be a problem that the component having hydrophobicity is reduced and the propensity to prevent contaminants is lowered. On the other hand, when the number is too high, compatibility with the hydrophobic component increases, There may be a problem.
The amount of the organopolysiloxane contained in 100 wt% of the copolymer contained in the antifouling paint composition of the present invention may be, for example, 10 to 40 wt%. If the content of the organopolysiloxane in the copolymer is too low, there may be a problem that the hydrophobic property of the surface of the coating film is lowered. On the other hand, if the content is too high, the coating film is too hydrophobic.
The copolymer contained in the antifouling paint composition of the present invention also contains a hydrophilic monomer having no carboxylic acid group as a polymerization unit. The carboxylic acid group-free hydrophilic monomer is used in an antifouling resin to impart hydrophilicity to promote magnetic abrasion performance to increase the abrasion rate and to improve the antifouling property, and includes hydroxyalkyl (meth) acrylate and the following formulas One or more monomers selected from the group consisting of monomers to be represented.
(2)
In the above formula (2), R4, R5 and R6 are independently hydrogen or a methyl group, and n and o are independently an integer of 0 to 12.
(3)
Wherein R 7 and R 8 are independently hydrogen or a methyl group, R 9 is hydrogen or an alkyl group having 1 to 5 carbon atoms, and p is an integer of 1 to 12.
[Chemical Formula 4]
delete
Wherein R 10 is hydrogen or a methyl group, R 11 is an alkylene group having 1 to 10 carbon atoms, R 12 is an alkylene group having 2 to 12 carbon atoms, R 13 is hydrogen or an alkyl group having 1 to 20 carbon atoms, Lt; / RTI >
The hydroxyalkyl (meth) acrylate is not particularly limited as far as it does not adversely affect, but it is possible to use those having an alkyl group having 1 to 20 carbon atoms. Illustratively, at least one selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate can be used.
The amount of the carboxylic acid group-containing hydrophilic monomer contained in 100 wt% of the copolymer contained in the antifouling paint composition of the present invention may be, for example, 5 to 30 wt%. If the content of the hydrophilic monomer having no carboxylic acid group in the copolymer is too low, the abrasion rate may be lowered. On the other hand, if the content is too high, the discoloration resistance may be deteriorated.
The copolymer contained in the antifouling paint composition of the present invention also includes a monomer containing a double bond and a carboxylic acid group as a polymerization unit. Examples of the monomer containing a double bond and a carboxylic acid group include (meth) acrylic acid, or a monomer prepared by a ring-opening reaction of a monomer containing a double bond and an alcohol group and an acid anhydride monomer. Examples of the monomer having a double bond and an alcohol group include a C 2 -C 12 hydroxyalkyl (meth) acrylate (e.g., 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) At least one selected from the group consisting of hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxybutyl (meth) acrylate, have. As the acid anhydride monomer, at least one selected from the group consisting of an aliphatic acid anhydride having 1 to 24 carbon atoms, an alicyclic acid anhydride having 3 to 24 carbon atoms, and an aromatic acid anhydride having 6 to 24 carbon atoms can be used. (PMDA), pyromellitic dianhydride (PMDA), pyromellitic dianhydride (PMDA), pyromellitic acid dianhydride (PMDA), and the like. 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroantimonate, (Meth) acrylic acid dianhydride, and (meth) acrylic acid anhydride, and at least one member selected from the group consisting of (meth) acrylic acid diisocyanate It can be used.
The amount of the monomer containing a double bond and a carboxylic acid group contained as a polymerization unit in 100 wt% of the copolymer contained in the antifouling paint composition of the present invention may be, for example, 10 to 45 wt%. If the amount of the monomer containing a double bond and a carboxylic acid group is less than the above range, there may be a problem that the discoloration resistance and abrasion rate are lowered, and if it is more than this range, there is a problem that crack resistance is poor.
The copolymer contained in the antifouling paint composition of the present invention also includes a non-reactive alkyl group-containing polymerizable monomer as a polymerization unit. The non-reactive alkyl group-containing polymerizable monomer is not particularly limited as long as it does not adversely affect the group of the alkyl (meth) acrylate, the cycloalkyl (meth) acrylate and the bicycloalkyl (meth) At least one selected can be used. Illustrative examples include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (Meth) acrylate, n-octyl (meth) acrylate and isobonyl (meth) acrylate.
The amount of the non-reactive alkyl group-containing polymerizable monomer contained in 100 wt% of the copolymer contained in the antifouling paint composition of the present invention may be, for example, 25 to 70 wt%. If the amount of the non-reactive alkyl group-containing polymerizable monomer is less than the above range, there may be a problem that the physical properties of the binder are lowered, and if the amount is more than that, the physical properties may become excessively high.
The copolymer contained in the antifouling paint composition of the present invention can be produced by radical reaction of the above-mentioned organopolysiloxane, a hydrophilic monomer having no carboxylic acid group, a monomer having a double bond and a carboxylic acid group, and a non-reactive alkyl group-containing polymerizable monomer , There is no particular limitation on the method, and conventional radical polymerization methods can be used.
The antifouling paint composition of the present invention may further contain an organic acid. The organic acid may be a low molecular weight organic acid including monofunctional, bifunctional, trifunctional or higher polyfunctional carboxylic acid groups, and the number average molecular weight thereof may be 1,000 or less. Examples of the organic acid include an aliphatic organic acid having 1 to 24 carbon atoms, an alicyclic organic acid having 3 to 24 carbon atoms, an aromatic organic acid having 6 to 24 carbon atoms, and a half ester derived from the reaction of an acid anhydride with an alcohol Or more can be used.
Examples of the aliphatic, alicyclic and aromatic organic acids include aliphatic acids such as acetic acid, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, succinic acid, malonic acid, oxalic acid, glutaric acid, adipic acid At least one selected from the group consisting of azelaic acid, sebacic acid, fumaric acid, glycolic acid, citric acid, phthalic acid, isophthalic acid, terephthalic acid and naphthenic acid.
As the acid anhydride for producing the half ester, at least one selected from the above-mentioned ones can be used.
Examples of the alcohols for producing the half ester include aliphatic alcohols having 1 to 12 carbon atoms, alicyclic alcohols having 3 to 24 carbon atoms, and aliphatic alcohols having 6 to 24 carbon atoms such as monofunctional, bifunctional, 24 aromatic alcohols may be used. Specific examples of the solvent include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, 2-methoxypropanol, ethylene glycol, propylene glycol, trimethylol propane, trimethylolethane, , Triethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, ditrimethylolpropane, triethylolpropane, glycerin, pentaerythritol, 2- (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, and caprolactone (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Rate can be used.
The antifouling paint composition of the present invention may further contain a divalent metal ion. The divalent metal ions, serves to produce a bond which enables be hydrolyzed in sea water abrasion coating film and, for example, Zn 2 +, Cu 2 +, one selected from the group consisting of Mn 2+ and Co + 2 or more But is not limited thereto.
For example, a copolymer is first prepared by radical reaction of the organopolysiloxane, a carboxylic acid group-free hydrophilic monomer, a double bond and a carboxylic acid group-containing monomer, and a non-reactive alkyl group-containing polymerizable monomer, Is reacted with a source of a metal ion (for example, an oxide of a divalent metal) in a secondary reaction, whereby a binder component for the antifouling paint composition of the present invention can be produced.
As the amount of each component used in the production of the binder component, for example, 60 to 80 parts by weight of the organic acid and 15 to 25 parts by weight of the source of the divalent metal ion may be used based on 100 parts by weight of the copolymer , But it is not limited thereto.
The solvent used in the production of the binder component is not particularly limited so long as it does not adversely affect the reaction, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, methyl ethyl ketone, methylpropyl ketone, methyl butyl ketone, Ketone solvents such as methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and methyl aryl ketone; ketone solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, Acetate, and carbitol acetate, or alcohol solvents such as n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol. When an acid anhydride is used in the reaction, the use of an alcohol group other than the alcohol group used for the reaction purpose should be restricted since the alcoholic solvent may cause a side reaction with the acid anhydride.
For example, the solid content of the binder component may be 30 to 70 wt%, and the acid value (based on solid content) may be 50 to 225 mg KOH / g. If the solid content of the binder component is too low, the abrasion rate and discoloration resistance may be deteriorated. On the other hand, if the content of the binder component is too high, the reaction temperature may not be controlled. If the acid value of the binder component is too low, the abrasion rate, the antifouling property and the discoloration resistance may be lowered. On the contrary, if the acid value is too high, the crack resistance may be lowered and the abrasion rate may be higher than necessary.
In the antifouling paint composition of the present invention, the binder component may be contained in an amount of, for example, 20 to 60% by weight based on 100% by weight of the total composition. If the content of the binder component in the composition is too low, the mechanical properties and the wear rate may be lowered. On the other hand, if the content is too high, the workability and crack resistance may be deteriorated and the wear rate may be increased more than necessary.
The antifouling paint composition of the present invention may further comprise a pigment. The pigment plays an role of improving the film strength, controlling the wear rate and coloring, and for example, extender pigments or color pigments can be used. Specifically, at least one selected from titanium white, red iron oxide, black iron oxide, zinc oxide and talc may be used, but is not limited thereto.
In the antifouling paint composition of the present invention, the pigment may be contained in an amount of, for example, 20 to 40% by weight based on 100% by weight of the total composition. If the content of the pigment in the composition is too low, there may be a problem that the strength or coloring effect of the coating film is lowered. On the other hand, if the pigment content is excessively high, the flexibility is lowered and the workability and viscosity of the coating material may be difficult to control.
The antifouling paint composition of the present invention may further contain a solvent. The solvent is not particularly limited so long as it does not adversely affect the reaction. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, methyl isobutyl ketone , Ketone solvents such as methylaryl ketone, esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate Based solvent, or an alcohol-based solvent such as n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol. More specifically, toluene or xylene can be used.
In the antifouling paint composition of the present invention, the solvent may be contained in an amount of, for example, 10 to 30% by weight based on 100% by weight of the total composition. If the content of the solvent in the composition is excessively low, the viscosity may increase and the workability may deteriorate. On the other hand, if the content is too high, the solids content and SVR (solid volume ratio) have.
The antifouling paint composition of the present invention may further comprise at least one additive selected from a plasticizer, an anti-flow agent, an anti-settling agent and a defoaming agent. Examples of such additives include plasticizers such as paraffin chloride, anti-flow agents such as amide wax, which contribute to improving the crack resistance of the antifouling coating film, and may be selected from those conventionally used in the art , And is not particularly limited. The amount of such an additive to be used may be determined from the viewpoint of the antifouling performance and the water resistance of the coating film. For example, the amount of each additive may be appropriately controlled within a range of 5 to 20% by weight based on 100% .
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.
[ Example ]
Synthetic example 1: Binder (A)
180 g of xylene and 180 g of butyl alcohol were fed into a four-necked flask for synthesis equipped with a stirrer, a thermometer and a stirrer, and the temperature was gradually raised to the reflux temperature (about 120 ° C). After warming, the mixture was heated to reflux, to which 92 g of methacrylic acid, 120 g of methyl methacrylate, 68 g of butyl acrylate, 80 g of methacrylate-terminated organopolysiloxane (Mn: 2,000), polyethylene glycol monomethyl ether methacrylate Methyl, R5 = R6 = H) and Mn: 468), 60 g of tertiary amyl peroxyhexanoate as an initiator and 120 g of xylene were simultaneously charged into the flask for 4 hours at the same time, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to 60 DEG C, 102 g of the half ester produced by the reaction of methyltetrahydrophthalic anhydride and 2-methoxypropanol, 174 g of naphthenic acid, 87 g of zinc oxide, 20 g of ionized water and 40 g of xylene were charged, After raising the temperature to 100 占 폚, refluxing was maintained for 8 hours to obtain a resin binder (A) having a solid content of 55.0% and a viscosity Z1.
Synthetic example 2: binder (B)
180 g of xylene and 180 g of butyl alcohol were fed into a four-necked flask for synthesis equipped with a stirrer, a thermometer and a stirrer, and the temperature was gradually raised to the reflux temperature (about 120 ° C). (R7 = R8 = 0) was added under the reflux maintained at a temperature elevated temperature, 92 g of methacrylic acid, 120 g of methyl methacrylate, 68 g of butyl acrylate, 80 g of methacrylate end organopolysiloxane (Mn: 2,000), 80 g of polyethylene glycol monomethacrylate H, R9 = methyl), Mn: 406), 60 g of tertiary amyl peroxyhexanoate as an initiator, and 120 g of xylene were simultaneously charged simultaneously for 4 hours, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to 60 DEG C, 102 g of the half ester produced by the reaction of methyltetrahydrophthalic anhydride and 2-methoxypropanol, 174 g of naphthenic acid, 87 g of zinc oxide, 20 g of ionized water and 40 g of xylene were charged, After raising the temperature to 100 占 폚, refluxing was maintained for 8 hours to obtain a resin binder (B) having a solid content of 55.0% and a viscosity Z. [
Synthetic example 3: Binder (C)
180 g of xylene and 180 g of butyl alcohol were fed into a four-necked flask for synthesis equipped with a stirrer, a thermometer and a stirrer, and the temperature was gradually raised to the reflux temperature (about 120 ° C). (R 10 = methyl, R 11 = C 2 H 4 , and R 10 = methyl) were added under the reflux maintained at the temperature elevated temperature, 92 g of methacrylic acid, 120 g of methyl methacrylate, 48 g of butyl acrylate, 120 g of methacrylate one end organopolysiloxane R12 = C 5 h 10, R13 = h) (Mn: 344) was a 20g and the initiator tertiary amyl peroxy-hexanoate uniformly added while 60g, xylene for 4 hours a mixture of alkylene 120g at the same time, reflux for 2 hours Respectively. Thereafter, the reaction mixture was cooled to 60 DEG C, 102 g of the half ester produced by the reaction of hexahydrophthalic anhydride and propanol, 174 g of naphthenic acid, 87 g of zinc oxide, 20 g of ionic water and 40 g of xylene were charged and heated to 100 DEG C Thereafter, the mixture was refluxed for 8 hours to obtain a resin binder (C) having a solid content of 55.0% and a viscosity of Z2.
Synthetic example 4: Binder (D)
180 g of xylene and 180 g of butyl alcohol were added to a synthetic four-necked flask equipped with a stirrer, a thermometer and a stirrer, and the temperature was gradually raised to the reflux temperature (about 120 ° C.). After warming up, 92 g of methacrylic acid, 120 g of methyl methacrylate, 88 g of butyl acrylate, 40 g of methacrylate-terminated organopolysiloxane (Mn: 3,000), polypropylene glycol monomethacrylate (compound of formula 2 = R6 = methyl), Mn: 376), 60 g of tertiary amyl peroxyhexanoate as an initiator, and 120 g of xylene were simultaneously charged simultaneously for 4 hours, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to 60 DEG C, 102 g of the half ester produced by the reaction of methyltetrahydrophthalic anhydride and 2-methoxypropanol, 174 g of naphthenic acid, 87 g of zinc oxide, 20 g of ionized water and 40 g of xylene were charged, After raising the temperature to 100 占 폚, refluxing was maintained for 8 hours to obtain a resin binder (D) having a solid content of 55.0% and a viscosity Z1.
Synthetic example 5: Binder (E) ( Comparative Example )
180 g of xylene and 180 g of butyl alcohol were added to a synthetic four-necked flask equipped with a stirrer, a thermometer and a stirrer, and the temperature was gradually raised to the reflux temperature (about 120 ° C.). After warming up, 92 g of methacrylic acid, 120 g of methyl methacrylate, 108 g of butyl acrylate, 80 g of methacrylate one end organopolysiloxane (Mn: 2,000), 60 g of tertiary amyl peroxyhexanoate as initiator, 120 g of xylene Were homogeneously charged simultaneously for 4 hours, and then refluxed for 2 hours. Thereafter, the reaction mixture was cooled to 60 DEG C, 102 g of the half ester produced by the reaction of hexahydrophthalic anhydride and propanol, 174 g of naphthenic acid, 87 g of zinc oxide, 20 g of ionic water and 40 g of xylene were charged and heated to a reflux temperature of 100 Thereafter, the mixture was refluxed for 8 hours to obtain a resin binder (E) having a solid content of 55.0% and a viscosity Z as a comparative example.
Synthetic example 6: Binder (F) ( Comparative Example )
104 g of xylene and 104 g of butyl alcohol were placed in a synthetic four-necked flask equipped with a stirrer, a thermometer and a stirrer, and the temperature was gradually raised to the reflux temperature (about 120 ° C.). After the temperature rise, a mixture of 60 g of methacrylic acid, 104 g of methyl methacrylate, 130 g of butyl acrylate, 52 g of triisopropylsilyl acrylate, 48 g of tertiary amyl peroxyhexanoate as an initiator and 125 g of xylene was simultaneously stirred for 4 hours , And the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to 60 DEG C and 54 g of the half ester produced by the reaction of hexahydrophthalic anhydride and propanol, 108 g of naphthenic acid, 57 g of zinc oxide, 16 g of ionized water and 35 g of xylene were charged and heated to 100 DEG C Thereafter, the mixture was refluxed for 8 hours to obtain a resin binder (F) having a solid content of 55.0% and a viscosity of Z1 as a comparative example.
Preparation of coating composition: Example 1 to 4 and Comparative Example 1-2
The antifouling paint compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were respectively prepared according to the compositions of Table 1 using the binders prepared in Synthesis Examples 1 to 6, and their physical properties were evaluated and shown in Table 2.
Paint Property Evaluation
Paint solid
1) Test conditions: about 3.0 g of the prepared coating, sampling at 150 ° C for 24 hours
2) Solid (%): weight after heating / weight before heating × 100
Paint viscosity
Test conditions: Measurement at 25 ° C, Kreb's Unit
Press exam
1) Specimen: 100 × 300 × 3 (mm) Steel plate
2) Specimen treatment: Sand blasting → Epoxy system paint 150 ㎛ → Epoxy binder paint 100 ㎛ (After drying each painting and drying at room temperature (20 ℃) for 1 day)
3) Antifouling paint: 300 ㎛ After painting 1 week Dry at room temperature (20 ℃)
4) Test conditions: 20 × 20 × 20 (mm) Stress after 50 kgf / ㎤ pressure for 40 minutes
5) Strain (%): 100- (film thickness after application of pressure / film thickness before applying pressure)
6) Evaluation Criteria
5: Less than 3%
4: 3% or more, less than 5%
3: 5% or more, less than 7%
2: 7% or more, less than 10%
1: 10% or more
Crack resistance exam
1) Specimen: 100 x 300 x 1.5 (mm)
2) Specimen treatment: Sand blasting → Epoxy system paint 150 ㎛ → Epoxy binder paint 100 ㎛ (After drying each painting and drying at room temperature (20 ℃) for 1 day)
3) Antifouling paint: 600 ㎛ After painting 1 week Dry at room temperature (20 ℃)
4) Test conditions: 23 ℃ sea water 24 hours immersion → 24 hours outdoor drying - 30 times repeated
5) Evaluation Criteria
5: No cracks or visible defects
4: Less than 5% of the total area of test specimen cracked.
3: Cracking occurs at 5% or more and less than 20% of the total area of the test specimen.
2: More than 20% and less than 50% of the total area of the test specimen cracked.
1: Cracks occur in more than 50% and less than 70% of the total area of test specimen.
0: Crack occurs at 70% or more of the total area of test specimen
Antifouling performance exam
1) Specimen: 550 × 150 × 2 (mm) Steel plate
2) Specimen treatment: Sandblasting → Epoxy system paint 200 ㎛ → Epoxy binder paint 100 ㎛ (After drying each painting and drying at room temperature (20 ℃) for 1 day)
3) Antifouling paint: 300 ㎛ After painting 1 week Dry at room temperature (20 ℃)
4) Test conditions: 1 m below the sea level in a raft type test equipment installed on the coast of Ulsan (east coast) and Geoje Island (south coast)
5) Evaluation Criteria
5: In the absence of marine organisms (non-polluted)
4: A state in which a thin slime layer is observed
3: A thick slime layer is observed, or the vegetation contaminated area is less than 20% of the effective area of the specimen
2: The condition that the vegetable contamination area exceeds 20% and 50% or less of the effective area of the specimen
1: The condition that the vegetable contamination area exceeds 50% and less than 100% of the effective area of the specimen
X: Animal contamination occurred
My discoloration property Measure
1) Specimen: 150 x 70 x 3 (mm) Glass Specimen
2) Sample preparation: XL washing (dirt and debris removal) and drying
3) Antifouling paint: 250 ㎛ After painting 1 week Dry at room temperature (20 ℃)
4) Test conditions: After immersing in fresh water container, after removing a certain amount of fresh water at intervals of 1 day, observed discoloration degree, visual judgment - 14 days observation
5) Evaluation criteria: 5 (good) → 1 (bad)
Evaluation of wear rate (㎛ / month)
1) Specimen: 150 × 70 × 1 (mm) Stainless steel plate
2) Specimen treatment: Sandblasting Epoxy system → epoxy system paint 50㎛ → sealer coat 50㎛
3) Antifouling paint: 100 ㎛ is coated at intervals of one day and then dried for one week at room temperature (20 ℃)
4) Test conditions: It was installed on the outside of a rotating drum having a diameter of 600 (mm) and a height of 300 (mm), then rapidly rotated at a rate of 25 (knot) under a constant temperature condition of 25 ° C, Evaluation of wear rate by measuring change
Claims (9)
Wherein the hydrophilic monomer having no carboxylic acid group is a monomer represented by the following formula (4):
[Chemical Formula 4]
Wherein R 10 is hydrogen or a methyl group, R 11 is an alkylene group having 1 to 10 carbon atoms, R 12 is an alkylene group having 2 to 12 carbon atoms, R 13 is hydrogen or an alkyl group having 1 to 20 carbon atoms, Lt; / RTI >
[Chemical Formula 1]
In Formula 1, R1 is a (meth) acrylic acid, C 1 -C 5 alkyl (meth) acrylate groups, C 2 -C 10 alkenyl group, C 1 -C 10 An alkoxy group, an OH group, an epoxy group, a COOH group or hydrogen, and m is an integer of 0 to 60.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020150065893A KR101732542B1 (en) | 2015-05-12 | 2015-05-12 | Antifouling paint composition comprising organic polysiloxane copolymer |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020150065893A KR101732542B1 (en) | 2015-05-12 | 2015-05-12 | Antifouling paint composition comprising organic polysiloxane copolymer |
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| KR101732542B1 true KR101732542B1 (en) | 2017-05-08 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5144389B2 (en) * | 2008-06-20 | 2013-02-13 | 三菱レイヨン株式会社 | Resin composition for water-based antifouling paint |
| JP5466347B2 (en) * | 2004-09-08 | 2014-04-09 | 中国塗料株式会社 | Antifouling paint composition, coating film thereof, ship or underwater structure coated with the coating film, and antifouling method |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5466347B2 (en) * | 2004-09-08 | 2014-04-09 | 中国塗料株式会社 | Antifouling paint composition, coating film thereof, ship or underwater structure coated with the coating film, and antifouling method |
| JP5144389B2 (en) * | 2008-06-20 | 2013-02-13 | 三菱レイヨン株式会社 | Resin composition for water-based antifouling paint |
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| KR20160133592A (en) | 2016-11-23 |
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