KR101786293B1 - Resin for antifouling paint and antifouling paint composition comprising thereof - Google Patents
Resin for antifouling paint and antifouling paint composition comprising thereof Download PDFInfo
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- KR101786293B1 KR101786293B1 KR1020160004382A KR20160004382A KR101786293B1 KR 101786293 B1 KR101786293 B1 KR 101786293B1 KR 1020160004382 A KR1020160004382 A KR 1020160004382A KR 20160004382 A KR20160004382 A KR 20160004382A KR 101786293 B1 KR101786293 B1 KR 101786293B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- 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
- C09D5/1668—Vinyl-type polymers
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Abstract
The present invention relates to an antifouling paint capable of producing a high SVR type antifouling paint which is coated on a ship's hull and an underwater structure in order to prevent the attachment and growth of marine life, thereby improving the discoloration resistance and crack resistance of the coating film, And to an antifouling coating composition containing the same.
Description
The present invention relates to a resin for an antifouling paint and an antifouling paint composition containing the same.
Japanese Patent Application No. 2010-506059 describes a two-part curing antifouling coating composition of a polyester type capable of hydrolysis as one of high-grade differentiation techniques. Due to the nature of the two-part curing type, relatively high solid content However, it has a disadvantage that the workability is inferior to that of the conventional one-pack type antifouling paint.
International Patent Application No. PCT-DK2011-050385 describes a self-leveling antifouling coating composition containing a pre-polymer having both an alkoxysilyl functional group and a hydroxyl functional group, wherein the alkoxy group and the hydroxyl group are water- And it may cause appearance problems such as causing discoloration of the coating film. As the recurring unit or alkyl group of the alkoxysilyl functional group described is increased, the viscosity of the resin composition may increase during the synthesis of the resin composition, and there may be a certain limit on the high-
Japanese Patent Application No. 2010-150355 discloses an acrylic resin composition which is a hydrolytic element and which is applied to acrylic acid alone, acrylic acid and methacrylic acid mixture, acrylic acid and triisopropylacrylate mixture, and triisopropylacrylate alone, However, there may still be a problem to be supplemented with the high-grade differentiation technique of the antifouling paint.
The present invention relates to an antifouling paint of high SVR (Solid Volume ratio) type which is coated on the ship's hull and underwater structure to prevent the attachment and growth of marine life, thereby improving the discoloration resistance and crack resistance of the coating film, The present invention also provides an antifouling paint composition comprising the same.
The copolymer resin of the present invention is an alkylamine adduct of a copolymer, wherein the copolymer contains, as polymerized units, (1) an anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer; (2) a monomer containing a double bond and a silyl group; (3) a monomer containing a double bond and a carboxylic acid group; And (4) a monomer comprising a double bond and an alkyl group, said alkylamine being represented by the formula (1)
[Chemical Formula 1]
Wherein R 1 to R 3 are independently H or an alkyl group having 1 to 8 carbon atoms, and m and n are independently an integer of 0 to 18.
The antifouling paint composition of the present invention comprises the resin for the antifouling paint.
According to the present invention, it is possible to produce a resin for an antifouling paint, which comprises polyalkylene glycol mono (meth) acrylate and is capable of high-grade differentiation by simultaneously modifying a specific alkylamine and a metal ester functional group, It is possible to produce a high SVR type antifouling paint having a low content, and by applying this, the physical properties of the final coating film in which the discoloration resistance and the crack resistance are simultaneously improved can be obtained. Such antifouling paints can prevent adhesion and growth of marine life as an image of a coating film applied to a ship hull and an underwater structure.
Hereinafter, the present invention will be described in more detail.
The copolymer resin of the present invention is an alkylamine adduct of a copolymer, wherein the copolymer contains, as polymerized units, (1) an anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer; (2) a monomer containing a double bond and a silyl group; (3) a monomer containing a double bond and a carboxylic acid group; And (4) a monomer containing a double bond and an alkyl group, and the alkylamine is represented by the formula (1).
The copolymer of the present invention comprises an anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer as polymerized units.
The anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer may be obtained by reacting polyalkylene glycol mono (meth) acrylate with an acid anhydride. The preferred polyalkylene glycol mono (meth) acrylate is at least one poly (C 2 -C 4 ) alkylene glycol mono (meth) acrylate, more preferably represented by the following formula 2 or 3 May be used.
(2)
(3)
Wherein R4 to R8 are independently H or an alkyl group having 1 to 8 carbon atoms, and p, q and r are independently an integer of 1 to 22.)
The acid anhydrides which react with the polyalkylene glycol mono (meth) acrylate are preferably C 2 to C 24 aliphatic acid anhydrides, C 4 to C 24 alicyclic oxalic anhydrides, and C 7 to C 24 aromatic acid anhydrides , And more preferably at least one selected from the group consisting of succinic anhydride, maleic anhydride, dodecylsuccinic anhydride, octylsuccinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, pyromellitic dianhydride (PMDA), 3,3 ', 4,4-oxydiphthalic dianhydride (ODPA), 3,3', 4,4'-benzophenonetetracarboxylic acid Dianhydride (6FDA), benzoquinonetetracarboxylic acid dianhydride, ethylene tetracarboxylic acid dianhydride, and (meth) acrylate dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride ) It can be used at least one selected from the group consisting of acrylic anhydride.
There is no particular limitation on the amount of the acid anhydride used in the reaction with the polyalkylene glycol mono (meth) acrylate, and for example, 1 mole of the acid anhydride per mole of the polyalkylene glycol mono (meth) acrylate can be used. Specifically, if the amount of the acid anhydride to be used is too small, the carboxyl group group is relatively reduced, which may cause a problem that the coupling ratio with the metal oxide is changed during the second reaction. On the contrary, if the amount of the acid anhydride is excessively large, the acidic acid remaining after bonding is formed, so that the metal oxide reacts with the low molecular weight anhydride during the second reaction, and the physical properties of the coating may be lowered.
The reaction of the polyalkylene glycol mono (meth) acrylate and the acid anhydride can be carried out under generally known conditions and can be carried out under elevated temperature conditions, for example 70 to 110 DEG C, in the presence of a suitable catalyst such as butylated hydroxytoluene, ), But is not limited thereto.
The obtained anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer preferably has a number average molecular weight of 400 to 1000, an acid value (based on solids) of 50 to 200 mg KOH / g, and a Gardner viscosity of U or T 25 < 0 > C).
The amount of the anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer contained as a polymerization unit in 100 parts by weight of the copolymer of the present invention may be preferably 5 to 30 parts by weight. When the amount of the anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer is less than the above range, there is a problem that the abrasion rate of the coating film is lowered, and if it is more than this amount, the crack resistance of the coating film is lowered, There may be a problem of speeding up.
In addition, the copolymer of the present invention includes, as a polymerization unit, a monomer containing a double bond and a silyl group which is hydrolyzable. The monomer containing the double bond and the silyl group is preferably at least one mono-, di- or tri (C 1 -C 6 ) alkylsilyl (meth) acrylate, more preferably trimethylsilyl acrylate, trimethyl At least one selected from the group consisting of silyl methacrylate, triisopropylsilyl acrylate, triisopropylsilyl methacrylate, tributylsilyl acrylate and tributylsilyl methacrylate can be used.
The amount of the monomer containing a double bond and a silyl group contained as a polymerization unit in 100 parts by weight of the copolymer of the present invention may be preferably 10 to 40 parts by weight. If the amount of the monomer containing a double bond and a silyl group is less than the above range, there is a problem that the antifouling property is poor, and if it exceeds this amount, the abrasion rate is lowered and the cost may be increased.
In addition, the copolymer of the present invention includes a monomer containing a double bond and a carboxylic acid group as a polymerization unit. As the monomer containing a double bond and a carboxylic acid group, there may be used (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 containing the double bond and the alcohol group include C 2 -C 12 hydroxyalkyl (meth) acrylates, preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) , At least one selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, have. As the acid anhydride, those described above can be used.
The amount of the monomer containing a double bond and a carboxylic acid group contained as a polymerization unit in 100 parts by weight of the copolymer of the present invention may be preferably 10 to 40 parts by weight. 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 to heat and the wear rate are lowered, and if it is more than this range, there is a problem that the crack resistance is poor.
Further, the copolymer of the present invention comprises a monomer containing a double bond and an alkyl group as polymerized units. As the monomer containing a double bond and an alkyl group, at least one selected from the group consisting of alkyl (meth) acrylate, cycloalkyl (meth) acrylate and bicycloalkyl (meth) acrylate can be used. preferably consisting of (C 1 -C 12) alkyl (meth) acrylate, (C 3 -C 12) cycloalkyl (meth) acrylate, (C 7 -C 12)) bicyclo (meth) acrylate (Meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate and isobonyl (meth) acrylate.
The amount of the double bond and the alkyl group-containing monomer contained as a polymerization unit in 100 parts by weight of the copolymer of the present invention may be preferably 30 to 60 parts by weight. When the amount of the monomer containing a double bond and an alkyl group is less than the above range, it is difficult to control the Tg, which is not preferable. The copolymer of the present invention can be produced by polymerizing the above-mentioned monomer components by a conventional radical polymerization method. The solvent which can be used in the radical polymerization reaction is not particularly limited so long as it does not adversely affect the reaction, but aromatic solvents such as toluene and xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, Methyl acetate, isopropyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, Acetate, and carbitol acetate; alcoholic solvents such as n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol may be used. The radical polymerization reaction can be carried out in this solvent under reflux.
The present invention relates to a method for directly reacting a monomer represented by the general formula (1) with an acrylic main binder resin for high-grade differentiation of a copolymer resin for an antifouling paint to reduce interaction between a metal and an organic substance of a metal ester serving as a hydrolyzing agent, The present invention is applied to produce high solids type acrylic binder resin having low viscosity.
(1) an anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer; (2) a monomer containing a double bond and a silyl group; (3) a monomer containing a double bond and a carboxylic acid group; And (4) a monomer containing a double bond and an alkyl group, the alkylamine to be additionally reacted has a structure of the formula (1), for example, 2-ethylenehexylamine, butylamine, di- -Ethylhexylamine), dibutylamine, diethylamine anhydrous, dihexylamine, dimethylamine anhydrous, dimethylethylamine, dimethylpropylamine, dipropylamine, ditridecylamine, hexylamine, isopropylamine N-dimethylaminopropylamine, N-ethyl-N-propylamine azetrope, N-octylamine, ter-butylamine, laurylamine, tridecylamine, tetradecylamine and combinations thereof May be used.
[Chemical Formula 1]
Wherein R 1 to R 3 are independently H or an alkyl group having 1 to 8 carbon atoms, and m and n are independently an integer of 0 to 18.
If the amount of the alkylamine represented by the formula (1) is 1 to 10 parts by weight based on 100 parts by weight of the copolymer, if the amount of the alkylamine is less than 1 part by weight, the high solids content becomes difficult due to the repulsive action between the metal ions, , The secondary reaction of the metal ester (that is, the condensation reaction of the copolymer resin of the present invention with the divalent metal and the low-molecular organic acid containing a carboxylic acid) is significantly slowed by the influence of the alkylamine added, There may be a problem.
(1) an anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer; (2) a monomer containing a double bond and a silyl group; (3) a monomer containing a double bond and a carboxylic acid group; And (4) a monomer containing a double bond and an alkyl group, and more specifically an alkylamine adduct of an alkylamine adduct of the formula (1) has a solid content of 40% or more and less than 80% , And an acid value (based on solid content) of 130 to 180 mgKOH / g. If the solid content of the copolymer resin is too low, the abrasion rate and discoloration resistance of the coating film may be lowered. On the other hand, if the solid content is too large, the reaction temperature control may not be controlled well. If the acid value of the copolymer resin is less than 130 mgKOH / g, the abrasion rate, antifouling property and discoloration resistance of the coating film may be lowered. If the acid value exceeds 180 mgKOH / g, the crack resistance of the coating film is lowered, There may be a problem.
According to another aspect of the present invention, there is provided an antifouling paint composition comprising the reaction product of the copolymer resin of the present invention, a divalent metal cation, and an organic carboxylic acid having a molecular weight of 1000 or less. The reaction of the copolymer resin, the divalent metal cation, and the organic carboxylic acid having a molecular weight of 1000 or less is a condensation reaction.
The divalent metal cation has a role of generating a bond that enables the coating film to be abraded by hydrolysis in seawater. Preferably, the divalent metal cation is one selected from the group consisting of Zn 2 + , Cu 2 + , Mn 2 +, and Co 2 + But is not limited thereto.
As the organic carboxylic acid having a molecular weight of 1000 or less, at least one selected from the group consisting of aliphatic acids, alicyclic acids and aromatic acids containing at least one carboxylic acid group (for example, 1 to 4) Preferably at least one selected from the group consisting of C 2 to C 24 aliphatic acids, C 4 to C 24 alicyclic acids and C 7 to C 24 aromatic acids can be used. Examples of the organic acid include acetic acid, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, naphthenic acid, succinic acid, malonic acid, oxalic acid, glutaric acid, adipic acid, At least one selected from the group consisting of lauric acid, glycolic acid, citric acid, phthalic acid, isophthalic acid and terephthalic acid can be used. Alternatively, a half ester resulting from the reaction of an acid anhydride with an alcohol may be used. As the acid anhydride, those described above can be used. The alcohol may be selected from the group consisting of C 1 to C 12 aliphatic alcohols containing one or more (for example, 1 to 4) hydroxyl groups, C 3 to C 12 alicyclic alcohols and C 6 to C 12 aromatic alcohols Can be used. Examples of the solvent include ethylene glycol, propylene glycol, trimethylol propane, trimethylol ethane, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-butylene glycol, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyisopropyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, butanediol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate and caprolactone (meth) acrylate.
The condensation reaction of the copolymer resin, the divalent metal cation and the organic carboxylic acid having a molecular weight of 1000 or less can be carried out under a generally known condition and can be carried out in a suitable solvent as described above under reflux However, the present invention is not limited thereto.
The antifouling paint composition of the present invention may further contain at least one additive component that can be commonly used in an antifouling paint, in addition to the reaction product of the copolymer resin, the divalent metal salt and the organic carboxylic acid having a molecular weight of 1000 or less. Examples of such additives include antifouling agents in the form of organic or inorganic compounds, organic or inorganic pigment components (for example, titanium white, red iron oxide, organic red pigment, talc, etc.), anti-sagging agents, , Various resins such as plasticizers, acrylic resins and polyalkyl vinyl ethers (vinyl ether (co) polymers), defoaming agents, and the like, but are not limited thereto.
In addition, the antifouling paint composition of the present invention may further comprise an elution regulator component that serves to control the elution rate of the antifouling agent together with the controlled abrasion behavior of the coating film in seawater. As the elution regulator component, at least one selected from the group consisting of rosin, rosin derivatives, monocarboxylic acids and salts thereof can be used. Examples of the rosin include rosin, rosin and tall oil rosin. Examples of the rosin derivative include (low melting point) disintegrating rosin, hydrogenated rosin, polymerized rosin, rosin and rosin derivative metal salts Salts, zinc salts or magnesium salts) and rosin amines. The rosin and rosin derivatives may be used singly or in combination of two or more. Examples of the monocarboxylic acid include a fatty acid having 5 to 30 carbon atoms or naphthenic acid. It is preferable that the elution regulator is contained in an amount of 0.1 to 25% by weight (in terms of solid content) based on the total weight of the antifouling paint composition, and the compounding ratio thereof can be determined from the viewpoints of the antifouling performance and the water resistance performance of the coating film.
In one embodiment of the present invention, 15 to 40% by weight of the copolymer resin for the antifouling paint, 20 to 40% by weight of the antifouling agent and 0.1 to 25% by weight of the antifouling agent elution controlling agent are added to 100% 1 to 10% by weight of a pigment, 10 to 30% by weight of an extender pigment and 5 to 20% by weight of a solvent.
Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
[Example]
1. Preparation of anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer
Oligomer 1
A thermometer and a condenser was charged with 820 g of polyethylene glycol monomethacrylate, 1.0 g of butylated hydroxytoluene and 345 g of hexahydrophthalic anhydride in a nitrogen atmosphere, and the mixture was heated to 90 DEG C and held for 6 hours. An acid value of 108 mg KOH / g, a Gardner viscosity (25 캜) U, and a light brown transparent oligomer.
Oligomer 2
Necked flask equipped with a thermometer and a condenser was charged with 770 g of polyethylene glycol monoacrylate, 1.0 g of butylated hydroxytoluene and 345 g of hexahydrophthalic anhydride in a nitrogen atmosphere, and the mixture was heated to 90 DEG C and maintained for 6 hours. An acid value of 115 mg KOH / g, a Gardner viscosity (25 DEG C) U, and a light brown transparent oligomer.
Oligomer 3
Neck flask equipped with a thermometer and a condenser was charged with 1270 g of polyethylene glycol monoacrylate, 1.0 g of butylated hydroxytoluene and 345 g of hexahydrophthalic anhydride in a nitrogen atmosphere, and the mixture was heated to 90 DEG C and maintained for 6 hours. An acid value of 78 mg KOH / g, a Gardner viscosity (25 DEG C) T, a light brown transparent oligomer.
2. Manufacture of resin for antifouling paints
Comparative Example Resin 1
A thermometer and a condenser, 300 g of butanol and 300 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. A mixed solution obtained by mixing 175 g of methacrylic acid, 340 g of ethyl acrylate, 335 g of butyl acrylate, 150 g of triisopropylsilyl acrylate, 150 g of tertiary amyl peroxyhexanoate as an initiator and 350 g of xylene was mixed for 4 hours The mixture was refluxed for 2 hours and then cooled to 60 ° C. Then, 446 g of naphthenic acid, 164 g of zinc oxide, 300 g of xylene and 36 g of ionized water were charged and the temperature was raised to 100 ° C. at the reflux temperature. The mixture was refluxed at 100 ° C for 5 hours to obtain a transparent resin having a solid content of 55.3%, a Gardner viscosity (25 ° C) Y, and a brown color.
Comparative Example Resin 2
A thermometer and a condenser, 300 g of butanol and 300 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. 150 g of oligomer 1, 140 g of methacrylic acid, 240 g of methyl methacrylate, 290 g of butyl acrylate, 145 g of triisopropylsilyl acrylate, 150 g of tertiary amyl peroxyhexanoate as initiator and 350 g of xylene were mixed The mixed solution was uniformly added dropwise over 4 hours, refluxed for 2 hours, cooled to 60 ° C, and then 435 g of naphthenic acid, 160 g of zinc oxide, 150 g of xylene and 45 g of ionized water were charged and the temperature was raised to 100 ° C. at the reflux temperature. The mixture was refluxed at 100 DEG C for 5 hours to obtain a solid resin having a solid content of 55.3%, a Gardner viscosity (25 DEG C) Z, and a brown transparent resin
Example Resin 1.
A thermometer and a condenser was charged with 250 g of butanol and 250 g of xylene in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. 150 g of oligomer 1, 157 g of methacrylic acid, 240 g of methyl methacrylate, 290 g of butyl acrylate, 145 g of triisopropylsilyl acrylate, 150 g of tertiary amyl peroxyhexanoate as initiator and 250 g of xylene were mixed The mixed solution was added dropwise uniformly for 4 hours, refluxed for 2 hours, cooled to 60 ° C, and 26 g of N-octylamine was added thereto and maintained at 60 ° C. for 1 hour. Then, 435 g of naphthenic acid, 160 g of zinc oxide, And 45 g of ionized water were charged, and the temperature was raised to a reflux temperature of 100 占 폚. The mixture was refluxed at 100 DEG C for 5 hours to obtain a high-solid-content brown transparent resin having a solid content of 64.9% and a Gardner viscosity (25 DEG C) of Z1.
Example Resin 2.
A thermometer and a condenser was charged with 250 g of butanol and 250 g of xylene in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. 150 g of oligomer 2, 157 g of methacrylic acid, 250 g of methyl methacrylate, 300 g of butyl acrylate, 145 g of triisopropylsilyl acrylate, 150 g of tertiary amyl peroxyhexanoate as initiator and 250 g of xylene were mixed After the mixture was homogeneously added dropwise for 4 hours, the mixture was refluxed for 2 hours, cooled to 60 DEG C, and 26 g of 2-ethylhexylamine was added thereto. The mixture was maintained at 60 DEG C for 1 hour. Then, 435 g of naphthenic acid, 160 g of zinc oxide, And 45 g of ionized water were charged, and the temperature was raised to a reflux temperature of 100 占 폚. And the mixture was refluxed at 100 ° C for 5 hours to obtain a high solid dispersion type brown transparent resin having a solid content of 65.1% and a Gardner viscosity (25 ° C) of Z1.
Example Resin 3.
A thermometer and a condenser was charged with 250 g of butanol and 250 g of xylene in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. 215 g of oligomer 3, 157 g of methacrylic acid, 245 g of methyl methacrylate, 225 g of butyl acrylate, 145 g of triisopropylsilyl acrylate, 150 g of tertiary amyl peroxyhexanoate as initiator and 200 g of xylene were mixed The mixed solution was homogeneously added dropwise for 4 hours, refluxed for 2 hours, cooled to 60 ° C, and 37 g of laurylamine was added thereto. The mixture was kept at 60 ° C. for 1 hour. Then, 435 g of naphthenic acid, 160 g of zinc oxide, 45 g of ionized water was added and the temperature was raised to a reflux temperature of 100 캜. The mixture was refluxed at 100 DEG C for 5 hours to obtain a transparent resin having a solid content of 65.3%, a Gardner viscosity (25 DEG C) Z, and a brown color.
3. Preparation of antifouling paint composition
An antifouling paint composition containing the above-prepared Comparative Resins 1 and 2 and Examples 1, 2 and 3 as a binder component was prepared as shown in Table 1 below, and physical properties were measured.
week)
1. Plasticizer: Paraffin plastoil 152 [Handy chemical corporation]
2. Pigment: Geolor Red 108 [Woo shin pigment co ,. Ltd.]
3. Extension Pigment: NA-400 [Young woo chemical co, .Ltd.]
4. Copper salt pyrithione: Copper Omadine [Lonza] antifoaming agent
5. Aliphatic amide wax: X9120 [KCC]
6. Asan East: LoLo tint LM [American Chemet] antifouling agent
7. Xylene: Xylene [SK corporation]
4. Antifouling paint Basic properties and main properties
The physical properties of the antifouling paint composition are evaluated as follows.
Paint SVR
Test conditions: ASTM D2652
Paint viscosity
Test conditions: Measurement at 25 ° C, Kreb's Unit
Crack resistance test
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 condition: immersion for 24 hours in 40 ℃ sea water → outdoor drying for 24 hours →
-5 ℃ Low temperature 24 hours - 10 times repeated
5) Evaluation Criteria
5: No cracks or visible defects
4: Less than 5% of the total area of test specimen.
3: 5 ~ 20% cracks of the total area of test specimen
2: 20 ~ 50% of the total area of test specimen cracked.
1: 50 ~ 70% of the total area of test specimen is cracked
0: More than 70% of the total area of the specimen is cracked.
Antifouling performance test
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 condition: Observation of the upper and lower level of immersion / non-infiltration on the sea surface in a raft-type test device installed on the coast of Ulsan (east coast) and off the coast of 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 vegetable contamination area is less than 20% of the effective area of the specimen
2: The condition that the vegetable contamination area is 20 to 50% of the effective area of the specimen
1: The condition that the vegetable contamination area is 50 ~ 100% of the effective area of the specimen
X: Animal contamination occurred
Measuring discoloration resistance
1) Specimen: 150 x 70 x 3 (mm) Glass Specimen
2) Sample preparation: XL washing and drying
3) Antifouling paint: 250 ㎛ After painting 1 week Dry at room temperature (20 ℃)
4) Test conditions: After 3 days from fresh water immersion, the discoloration (ΔE) of the non-immersion area and the immersion area was confirmed
5) Evaluation criteria: ΔE (the lower the better)
As can be seen from Table 2, it can be seen that Examples 1 to 3 coating compositions of the present invention are highly SVR-type antifouling paints having a low solvent content and excellent in discoloration resistance, crack resistance and antifouling performance And it was found. On the other hand, Comparative Examples 1 and 2 showed low SVR values, and especially discoloration resistance was poor compared with the paint of the present invention.
Claims (6)
Wherein the alkylamine is represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
Wherein R 1 to R 3 are independently H or an alkyl group having 1 to 8 carbon atoms, and m and n are independently an integer of 0 to 18.
Wherein the anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer is obtained by the reaction of a polyalkylene glycol mono (meth) acrylate and an acid anhydride,
Wherein the polyalkylene glycol mono (meth) acrylate is at least one compound represented by the following formula (2)
Wherein said acid anhydride is at least one member selected from the group consisting of C 2 to C 24 aliphatic acid anhydrides, C 4 to C 24 alicyclic oxalic anhydrides, and C 7 to C 24 aromatic acid anhydrides,
Copolymer resin:
(2)
(Wherein R4 and R5 are independently H or an alkyl group having 1 to 8 carbon atoms, and p is independently an integer of 1 to 22.)
Wherein the anhydride-modified polyalkylene glycol mono (meth) acrylate oligomer is obtained by the reaction of a polyalkylene glycol mono (meth) acrylate and an acid anhydride,
Wherein the polyalkylene glycol mono (meth) acrylate is at least one member represented by the following general formula (3)
Wherein said acid anhydride is at least one member selected from the group consisting of C 2 to C 24 aliphatic acid anhydrides, C 4 to C 24 alicyclic oxalic anhydrides, and C 7 to C 24 aromatic acid anhydrides,
Copolymer resin:
(3)
Wherein R 6 to R 8 are independently H or an alkyl group having 1 to 8 carbon atoms, and q and r are independently an integer of 1 to 22.
Monomer is one or more mono-containing group and the double bond silyl, di-or tri-and (C 1 -C 6) alkylsilyl (meth) acrylate,
Wherein the monomer containing a double bond and a carboxylic acid group is a monomer prepared by a ring-opening reaction of a (meth) acrylic acid or a monomer containing a double bond and an alcohol group and an acid anhydride monomer,
Wherein the monomer containing the double bond and the alkyl group is selected from the group consisting of (C 1 -C 12 ) alkyl (meth) acrylate, (C 3 -C 12 ) cycloalkyl (meth) acrylate and (C 7 -C 12 ) bicycloalkyl (Meth) acrylate, and at least one selected from the group consisting of
Copolymer resin.
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| KR1020160004382A KR101786293B1 (en) | 2016-01-13 | 2016-01-13 | Resin for antifouling paint and antifouling paint composition comprising thereof |
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| KR1020160004382A KR101786293B1 (en) | 2016-01-13 | 2016-01-13 | Resin for antifouling paint and antifouling paint composition comprising thereof |
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| KR101786293B1 true KR101786293B1 (en) | 2017-10-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190057650A (en) | 2017-11-20 | 2019-05-29 | 주식회사 에코웨이브 | Polymer for antifouling coating |
| KR20190068281A (en) * | 2017-12-08 | 2019-06-18 | 주식회사 케이씨씨 | Additive composition, manufacturing mehtod thereof, and antifouling paint composition comprising the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014743A1 (en) | 1990-03-21 | 1991-10-03 | Courtaulds Coatings (Holdings) Limited | Antifouling coating compositions |
| KR100556016B1 (en) | 1998-01-27 | 2006-03-03 | 인터내셔널 페인트 리미티드 | Antifouling coatings |
| JP2006182955A (en) | 2004-12-28 | 2006-07-13 | Nippon Paint Co Ltd | Water-based curing type antifouling coating composition, antifouling coating film and underwater structure |
-
2016
- 2016-01-13 KR KR1020160004382A patent/KR101786293B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014743A1 (en) | 1990-03-21 | 1991-10-03 | Courtaulds Coatings (Holdings) Limited | Antifouling coating compositions |
| KR100556016B1 (en) | 1998-01-27 | 2006-03-03 | 인터내셔널 페인트 리미티드 | Antifouling coatings |
| JP2006182955A (en) | 2004-12-28 | 2006-07-13 | Nippon Paint Co Ltd | Water-based curing type antifouling coating composition, antifouling coating film and underwater structure |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190057650A (en) | 2017-11-20 | 2019-05-29 | 주식회사 에코웨이브 | Polymer for antifouling coating |
| KR20190068281A (en) * | 2017-12-08 | 2019-06-18 | 주식회사 케이씨씨 | Additive composition, manufacturing mehtod thereof, and antifouling paint composition comprising the same |
| KR102114057B1 (en) * | 2017-12-08 | 2020-05-25 | 주식회사 케이씨씨 | Additive composition, manufacturing mehtod thereof, and antifouling paint composition comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170085181A (en) | 2017-07-24 |
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