KR940003192B1 - Antifouling coat composition - Google Patents

Abstract

copolymerizing the unsatd. monomer contg. one or more acid anhydride gp. of formula (1) with one or more of the radical polymerizing unsatd. monomers of formula (11); then esterification-additioning reacting one or more cpds. contg. one hydroxy gp. in aromatic or hetero ring of formula (4) with the resultant; and esterifying the resultant with the cpd. contg. one hydroxy gp. of formula, R'-OH, to lower than 150 of the acid value. In formulas, R1 and R2 is H, halogen, halogen-substd. phenyl; C1-20 alkyl or phenyl; X1-X8 are C1-4 alkyl, C1-4 alkoxy, halogen, H, nitro, mercapto, cyan, thiocyan, phenyl or halogen-substd. phenyl; Y and Z are each halogen or H.

Description

Manufacturing method of marine biological pollution prevention copolymer and antifouling coating composition containing same

The present invention relates to a method for preparing a novel marine biological pollution prevention copolymer having self-polishing properties and an antifouling coating composition containing the same. More specifically, the present invention relates to an aromatic or heterocyclic monomer in an unsaturated monomer containing one acid anhydride group in one step. Homopolymerization of a compound containing one hydroxyl group on a ring followed by a radical polymerization of a modified unsaturated monomer esterified to a acid value of 150 or less with a compound containing one hydroxyl group in two steps. In one step, an esterified addition of a compound containing one hydroxyl group on an aromatic or heterocyclic ring is carried out to an unsaturated monomer containing one acid anhydride group, and then a compound containing one hydroxyl crab in two steps. A copolymer prepared by copolymerizing at least one radically polymerizable unsaturated monomer with a modified unsaturated unsaturated monomer esterified to The esterification addition reaction is carried out in an intermediate polymer obtained by polymerizing a single radical of an unsaturated monomer containing one copolymer 1-2 and one acid anhydride group in one step using at least one compound containing one hydroxyl group on an aromatic or hetero ring. And copolymerizing at least one radical polymerizable unsaturated monomer with a homopolymer 2-1 and an unsaturated monomer containing one acid anhydride group prepared by esterifying a compound containing one hydroxyl group in two steps to an acid value of 150 or less. Esterification addition reaction using at least one compound containing one hydroxyl group on an aromatic or heterocyclic ring in one step of the intermediate polymer, followed by esterification to a acid value of 150 or less with a compound containing one hydroxyl group in two steps For the prevention of marine biological pollution, characterized in that the copolymer 2-2, prepared alone or in combination, is used as a colorant component. Method for producing a polymer, and relates to an antifouling coating composition containing the same.

Underwater, many sea creatures such as reefs, shellfish, moss diatoms, oysters, pearls, sponges, seashells, beatings, green shellfish, and sea urchins are found. Parasitic attachment to nets can cause damage to deposits.

In particular, when marine life is attached to the hull, the speed of fuel consumption increases due to the decrease in the ship speed due to the increase in frictional force on the water during operation.

Therefore, in order to prevent marine biological contamination of the underwater building, there has been conventionally used an antifouling coating composition obtained by mixing an antifouling agent such as rosin, plasticizer and copper dioxide with vinyl chloride resin or vinyl resin. Not only does it require an excessive amount of antifouling agent, but also the selective elution of soluble components such as rosin causes microchannels to be formed in the coating composition, and the microchannels thus formed contain the secretions of organisms or the debris of dead organisms. By interfering with the release of antifouling agent in the site, only antifouling performance could be expected for a short time.

In addition, US Pat. No. 4,191,579 and UK Pat. No. 1,457,590 disclose self-polishing antifouling coating compositions which are capable of hydrolyzing in seawater by coupling organic tin components such as tributyl tin oxide in the form of esters to unsaturated monomers such as acrylic acid or methacrylic acid. An antifouling system using a has been described.

The antifouling coating composition described in the patent is characterized in that the organic tin component is gradually hydrolyzed at the site of contact with seawater, and the carboxyl group at the site of release leaves a salt, so that the polymer is solubilized or swelled and released from the surface, thereby protruding a new surface layer. As a system, the surface wear rate is controlled to 2 ~ 10㎛ / month to show long term antifouling for 3 ~ 5 years, but it is the most used antifouling system, but it causes marine pollution by continuously dissolving toxic organic tin components. The impact on the ecosystem is quite serious.

Therefore, there is a demand for the development of new antifouling coatings that are excellent in pollution prevention for marine organisms and microorganisms and have no environmental hygiene problems.

The antifouling coating composition prepared according to the above object was used to produce a half ester compound by adding a phenol derivative to an acid anhydride, and then reacting a radical polymerizable unsaturated monomer containing an epoxy group or a hydroxyl group with the other carboxyl group. Although the method is described in Korean Patent Application Publication No. 89-14700, such an antifouling coating composition is not only complicated in the manufacturing process but also insufficient in water solubility after the phenol derivative is hydrolyzed, and thus has a disadvantage in that slime is easily caught. Could not provide excellent antifouling performance.

In addition, WO 86/02660 describes an antifouling coating composition prepared by simply copolymerizing a carboxyl group-containing unsaturated monomer such as acrylic acid with methyl methacrylate, butyl methacrylate, and the like, which contains too much carboxyl group, Water resistance is sharply reduced and wear rate is nonuniform.

Accordingly, an object of the present invention is to provide a method for preparing a marine biological pollution prevention copolymer which exhibits antifouling performance for a long time and has no environmental hygiene problems.

That is, the present invention provides an antifouling antifouling coating composition containing a homopolymer or a copolymer as a colorant component and a marine biological antifouling method comprising coating the antifouling coating composition on a surface thereof.

The present invention is described in more detail as follows.

One or more compounds (hereinafter referred to as "component b") containing one hydroxyl group on an aromatic or hetero ring in an unsaturated monomer containing one acid anhydride group (hereinafter referred to as "component a") in one step. A compound containing one hydroxyl group on another aromatic or heterocyclic ring so as to add an equivalent ratio of the group / hydroxyl group to 1 / 0.5 to 1 and an acid value of 150 or less in two steps (hereinafter referred to as "component b") Homopolymer (hereinafter referred to as "monopolymer 1-1") which is a radical polymer of a modified unsaturated unsaturated monomer (hereinafter referred to as "component c") obtained by esterification with a component, containing a hydroxyl group on an aromatic or heterocyclic ring in component a Modified unsaturated monomer obtained by adding at least one component b to an acid anhydride group / hydroxyl group in an equivalent ratio of 1 / 0.5 to 1, and then esterifying it with component b 'so as to have an acid value of 550 or less in two steps. c)) Copolymers prepared by copolymerizing one or more radically polymerizable unsaturated monomers (hereinafter referred to as "component d") to be 150 or less (hereinafter referred to as "copolymer 1-2"), an intermediate polymer obtained by homopolymerizing component a first (Hereinafter, referred to as "component e") by adding one or more components b in one step with an acid anhydride group / hydroxy group molar ratio of 1 / 0.5 to 1, and then adding the component b 'so that the acid value is 150 or less in two steps. At least one homopolymer (hereinafter referred to as "monopolymer 2-1") and an interpolymer (hereinafter referred to as "component f") copolymerized with at least one component d to component a A copolymer prepared by addition reaction with an acid anhydride group / hydroxyl group equivalent ratio of 1 / 0.5 to 1, and then esterified with component b 'so as to have an acid value of 150 or less in two steps (hereinafter referred to as "copolymer 2-2") To prevent marine organisms adhesion as a colorant Opicoat composition was prepared.

In this invention, the preferable example of the component a which is an unsaturated monomer containing one intramolecular acid anhydride group is a compound represented by following General formula (1), (2) and (3).

General formula (1)

It is a C1-C20 alkyl group or a phenyl group.

General formula (2)

It is 1-8 alkyl groups.

General formula (3)

1-8 alkyl groups, R ₇ is methylene, ethylene or dichloromethylene.

Preferred examples of the compound represented by the general formula (1) include maleic anhydride, thichloromaleic anhydride, and the like, and preferable examples of the compound represented by the general formula (2) are cis-4-cyclohexene-1,2-di Carboxylic anhydride, trans-4-cyclohexene-1,2-dicarboxylic anhydride, cis-3,3 ', 6,6'-tetrachloro-4-cyclohexene-1,2- Dicarboxylic anhydride and the like, and preferred examples of the compound represented by the general formula (3) include 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic Anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride and the like.

Still other preferred examples of component a include itaconic anhydride, dodecyl rosinic anhydride, and the like, but these examples do not limit the scope of the present invention.

Preferred examples of component b containing one hydroxyl group on an aromatic or hetero ring are compounds represented by the following general formulas (4), (5), (6), (7), (8) and (9).

General formula (4) General formula (5)

General formula (6) General formula (7)

Formula (8) Formula (9)

Here, each of X ₁ to X ₈ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen element, a hydrogen element, a nitro group, a mercapto group, a cyan group thiocyanate group, a phenyl group or a halogen-substituted phenyl group , Y and Z are halogen or hydrogen.

Preferred examples of the compound represented by formula (4) include phenol, 2-methyl phenol, 3-methyl phenol, 4-methylphenol, 2-methoxy phenol, 3-methoxy phenol, 4-methoxy phenol, 2- Chloro phenol, 3-chloro phenol, 4-chloro phenol, 2-bromo phenol, 3-bromo phenol, 4-bromo phenol, 2-fluoro phenol, 3-fluoro phenol, 4-fluoro phenol, 2 -Nitrophenol, 3-nitro phenol, 4-nitro phenol, 2-mercapto phenol, 3-mercapto phenol, 4-mercapto phenol, 2-cyano phenol, 3-cyano phenol, 4-cyano phenol, 2-thiocyano phenol, 3-thiocyano phenol, 4-thiocyano phenol, 4-phenyl phenol, 4- (2chloro phenyl) phenyl, 4- (3nitrophenyl) phenol, 2,4-dimethyl phenol , 2,4-dichloro phenol, 2,4-dibromo phenol, 2-4dinitro phenol, 2,4-dithiocyano phenol, 2,6-dimethyl phenol, 2,6-dimethoxy phenol, 2 , 6-dichloro phenol, 2,6-dinitro phenol, 2-6-dimercapto phenol, 2,6-dicyano phenol, 2,6-dithiosi Nophenol, 3,5-dimethyl phenol, 3,5-dimethoxy phenol, 3,5-diethoxy phenol, 3,5-dichloro phenol, 3,5-difluoro phenol, 3,5-dinitro phenol, 3,5-dicyano phenol, 3,5-dithiocyano phenol, 2,3,4,5,6-pentachloro phenol, 2,3,4,5,6-pentabromo phenol, 2,4 6-trichloro phenol, 2,4,6-trinitro phenol, 2 chloro-4 bromo phenol, 2 bromo-4 chloro phenol, 2 bromo-4 chloro-6 nitro phenol, 3 chloro-5 methyl phenol, 3 methyl-5 cyano phenol, 3 nitro-6 chloro phenol, 2 methyl-4 bromo phenol, and the like, and preferable examples of the compound represented by the general formula (5) are 4-lysineimido 2-chloro phenol, 4 -Lysine imido 2-bromo phenol, 4- lysine amido, 3,5-dichloro phenol, 4- lysine imido 3,5-dimethyl phenol, 4- lysine imido 3-nitro phenol, 3-lysine imido 5 methyl phenol and the like, and a preferable example of the compound represented by the general formula (6) is N- (4-hydroxy 2chlorophene ) Footimide, N- (4-hydroxy phenyl) footimide, N- (3-hydroxy phenyl) footimide, N- (4-hydroxy 2nitro 3 bromo phenyl) footimide, etc. Preferred examples of the compound represented by the general formula (7) include 4-hydroxy pyridine, 3-hydroxy pyridine, 4-hydroxy 2,6 dimethyl pyridine, 4-hydroxy 2,6 dibromo pyridine, 4 -Hydroxy 2-nitro pyridine, 4-hydroxy 2-cyano pyridine, 4-hydroxy 2-cyano pyridine, 6-chloro pyridine, and the like, and preferred examples of the compound represented by the general formula (8) include 1 -Hydroxy pyrimidine, 2-hydroxy pyrimidine, 1-hydroxy 2chloro pyrimidine, 1-hydroxy 2-methyl pyrimidine, 1-hydroxy-5-methyl pyrimidine, and the like. Preferred examples of the compound represented by) include 4-hydroxy indole and 5-hydroxy indole.

Another preferred example of component b is 2-hydroxy dibenzofuran, hydroxy phenyl benzo oxide, 4-hydroxy 9furorenone, 5-hydroxy isoquinoline, 8-hydroxy junolidine, 2-hydroxy Naphthalene and the like, and these examples do not limit the scope of the present invention.

As component b, the said compound can be used individually or in mixture of 2 or more types.

Using component a and component b, it is preferable to make the hydroxyl equivalent ratio 1 / 0.5 to 1 of the acid anhydride / component b of the esterification addition reaction component a in one step.When the hydroxyl group is 0.5 equivalent or less, the wear rate is uneven and antifouling performance is achieved. When the amount of hydroxyl groups is 1 equivalent or more, crystals are generated during storage, and the surface roughness is degraded when the seawater is deposited by the antifouling coating composition.

In the esterification addition reaction of component a and component b, the temperature is suitably 100 to 200 ° C, and an organic solvent may be used if necessary.

Useful organic solvents include acetone, tetrahydrofuran, cellosolve, cellosolve acetate, xylene, toluene, dioxane, methylethylketone, methylisobutylketone, N, N-dimethyl formamide, N-methyl pyrrolidone, and the like. .

If necessary, the reaction may be accelerated by using a tertiary amine, tertiary amine salt, triphenyl phosphine, or the like as a reaction catalyst.

In addition, the preferable example of component b 'is a compound represented by following General formula (10).

General formula (10) R'-OH Here, R 'is a C1-C20 alkyl group, a benzyl group, or a C1-C20 halogen substituted alkyl group.

Preferred examples of the compound represented by the general formula (10) include methanol, ethanol, N-propanol, isopropanol, n-butanol, n-octanol, benzyl alcohol, and the like, but these examples do not limit the scope of the present invention.

The esterification reaction temperature with the two-step reaction (component b ') is suitably 120-200 캜, and the content of (component b') needs to be adjusted so that the final reaction acid value is 150 or less.

If the acid value is too high, such as 150 or more, water resistance is difficult to provide long-term antifouling performance and uniform wear rate.

Component d is used to provide a suitable glass transition temperature (Tg), flexibility, auxiliary antifouling property, hydrolyzability, etc. of the polymer, and a preferable example is a compound represented by the following general formulas (11) to (18).

General Formula (11) General Formula (12)

Formula (13) Formula (14)

General Formula (15) General Formula (16)

General Formula (17) General Formula (18)

R ₁ , R ₂ and R ₃ are each an alkyl group having 1 to 4 carbon atoms, a halogen element, a hydrogen element, a phenyl group or a halogen substituted phenyl group, and each of X ₁ to X ₅ is an alkyl group having 1 to 4 carbon atoms or 1 to 2 carbon atoms. An alkoxy group, a hydrogen element, a halogen element, a nitro group, a cyano group, a cyano group, a mercapto group, a phenyl group or a halogen-substituted phenyl group, A is ethylene or propylene, Q is an alkyl group having 1 to 4 carbon atoms, a hydrogen atom or a halogen a substituted alkyl group having 1 to 20 carbon atoms, n is an integer of 0 ~ 4, m is an integer of 1 ~ 70, R ₄ is a C 1 -C 20 alkyl group or a C 1 -C 20 halogen substituted alkyl group.

Preferred examples of the compound represented by the general formula (11) include methyl acrylate, ethyl acrylate, propofyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, methyl cinnamate, ethyl cinnamate, methyl 2- Chloro cinnamate, 2-chloro methyl acrylate, 2-bromo methyl acrylate, 2-chloro ethyl acrylate, 2-chloro lauryl acrylate, ethyl crotonate, and the like, represented by the general formula (12) Preferred examples of the compound are styrene, vinyl 4-chloro benzene, vinyl 3-chloro benzene, vinyl 3,5-dichlorobenzene, vinyl 2,4,6-trichloro benzene, vinyl 2-cyano benzene, vinyl 4-cyano Benzene, vinyl 2-nitrobenzene, vinyl biphenyl and the like, and preferred examples of the compound represented by the general formula (13) are ethoxy acrylate acrylate, polypropylene glycol acrylate (m = 20), poly methacrylate Propylene glycol (m = 10), ethylene glycol acrylate (m = 10), acrylate polypropylene glycol (m = 20), and the like. Preferred examples of the compound represented by the general formula (14) include 4-vinyl pyridine, 2-vinyl pyridine, 2-nitro pyridine, 2-chloro pyridine, 2-vinyl-6-methyl pyridine, 2-vinyl-5-ethyl pyridine, and the like, and preferable examples of the compound represented by the general formula (15) are N -Methyl maleimide, N-ethyl maleimide, N-propofyl maleimide, N-butyl maleimide, N-hexyl maleimide, and the like, and preferred examples of the compound represented by the general formula (16) are N-phenyl maleim Mid, N- (nitrophenyl phenyl) maleimide, N- (2,6-dichloro phenyl) maleimide, N- (2,6-dimethyl phenyl) maleimide, N- (4-chloro phenyl) maleimide, N -(4-bromo phenyl) maleimide, N- (4-thiocyano phenyl) maleimide, N- (2-nitro-4-nitro phenyl) maleimide, and the like. Preferred examples of the compound to be represented are methacrylic acid polydimethylsiloxane furophyll (m = 70), methacrylic acid polydimethylsiloxane ethyl (m = 10), methacrylic acid polydimethylsiloxane furophyll (m = 30), acrylic acid poly Dimethyl siloxane furophyll (m = 30), acrylic polydimethylsiloxane furophyll (m = 70), etc., Preferred examples of the compound represented by the general formula (18) are 4-vinyl benzene sulfonyl butyrate, 4-vinyl benzene Sulfonyl caprate, 4-vinyl benzene octoate, and the like.

Still other preferred examples of component d include acrylonitrile butadiene, propylene, vinyl imidazole, chloroprene, vinyl acetate, acrylamide, N, Ndimethyl acrylamide, and the like, but these examples do not limit the scope of the present invention.

The polymerization method of homopolymer 1-1 and co-conjugate 1-2 using the component c and the component c 'may be a known radical polymerization method, and there are bulk polymerization, emulsion polymerization and solution polymerization. Most preferred.

Preferred examples of the solution polymerization method are as follows.

The organic solvent was placed in a circular flask equipped with a stirrer and a cooler and stirred under a nitrogen atmosphere to adjust the temperature of the contents to 50 ° C. to 150 ° C., and then the initiator was well dissolved in the component c or a mixture of component c ′ and component d. The solution can be added dropwise for 2 to 5 hours.

In order to minimize the amount of unreacted monomer, it is preferable to dropwise add a mixture of an organic solvent and an initiator.

Residual unreacted monomer is possible by analysis by GPC (gel chromatography) and measurement of non volatile matter.

Preferred examples of useful organic solvents include acetone, tetrahydrofuran, cellosolve, cellosolve acetate, xylene, toluene, benzene, dioxane, N, N-dimethyl chloroaldehyde, methyl ethyl ketone, methyl isobutyl ketone and the like. It can also be used in combination to control. In addition, it is preferable to use a low boiling point solvent to improve room temperature drying as possible.

It is preferable to use 80-120 weight part of organic solvents with respect to 100 weight part of component c or the mixture of component c 'and d. At 80 parts by weight or less, the viscosity is high at the end of the reaction, the stirring is not good, and more than 120 parts by weight has a disadvantage that the solvent selection is not free when preparing the antifouling coating composition.

Suitable initiators are peroxides such as azobis isobutyronitrile (AIBN), benzoyl peroxide (BPO), differential butyl peroxide and the like. It is preferable to control the reaction temperature and the amount of the polymerization initiator during the polymerization so that the number average molecular weight of the produced polymer is in the range of 1,000 to 200,000. If the molecular weight is less than 1,000, the film is weak and the durability is lowered. If the molecular weight is 200,000 or more, the viscosity is high, and the drying is slow due to the use of solvents more than necessary, and the film becomes thin in one operation.

The reaction temperature during polymerization is preferably in the range of 50 ° C to 150 ° C, and the amount of initiator is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the solid content.

If the polymerization temperature is too high, the half-life of the initiator is too short while the molecular weight is reduced, and if the polymerization temperature is too low, there is a problem that the reaction time takes a long time.

In addition, if the amount of the initiator is too large, the molecular weight is small, if the amount of the initiator is too small there is a problem that the polymerization is not good.

In the preparation of homopolymer 2-1 and copolymer 2-2 according to method 2, the polymerization method of component e or component f and the esterification method of component b and component b 'may be according to method 1.

Method 2 is preferably applied when the difference in reactivity ratio between component c and component d is large and when the boiling point of component a is low to make component c difficult to prepare.

The ester groups introduced in the above-mentioned homopolymer 1-1 and copolymer 1-2, homopolymer 2-1 and copolymer 2-2 have a moderate hydrolysis rate of 5 to 10 times that of ordinary alkyl ester bonds. It is possible to provide an antifouling coating composition that is suitable to exhibit the desired self-polishing property as well as having no environmental hygiene problems.

The content of component a in the polymers is preferably 10 parts by weight or more based on 100 parts by weight of polymer, and 10 parts by weight or less of the antifouling performance and bad wear rate occurs.

In addition, the polymer component may be used alone or mixed, and the polymer itself may provide an antifouling coating having excellent antifouling performance. However, it is preferable to prepare and use the antifouling coating composition A by mixing an auxiliary antifouling agent and an additive. . Useful auxiliary antifouling agents include copper compounds such as copper dioxide, copper powder and copper thiocyanate; Carbamates such as zinc dimethyl dithio carbamate and 2, 3-dihydro-2,2-dimethyl-n-benzofuraryl-methyl carbamate; Anilides such as 2-chloro-2,6-diethyl-n (butoxy methyl) acetanilide and 2-chloro-2,6-diethyl-n- (methoxy methyl) acetanilide; Ethyl-p-nitro phenyl thiono benzene phosphate and O-ethyl-S, S-diphenyl dithio phosphate; O-ethyl-S, S-difurofilphospho dithiazole, St-butylthio methyl-O, O-diethyl phosphor dithiazole, benzo thiazole, 4,5-dichloro-2-n-octyl Toothbrushes such as -3-isothiazol; Imides such as N- (trichloromethyl thi) phthalimide, N-phenyl maleide, N-butyl maleide, N-3,5-dichloro maleimide; Imidazoles such as methyl imidazole and 2-ethyl-4-methyl imidazole; Triazines such as 2-methylthio-4-t-butyl amino-6-cycloamino-S-triazine and the like.

It is preferable to use 5-50 weight part of auxiliary antifouling agents with respect to 100 weight part of antifouling coating compositions. In 5 parts by weight or less, the antifouling performance is lowered, and more than 50 parts by weight of not only free formulation, but also has a disadvantage of poor shelf life and the composition is increased in price.

The additives may contain known additives such as coloring pigments, coloring pigments, pigments for controlling the wear rate, pigment dispersants, plasticizers, resins, thickeners, antisettling agents and the like.

The antifouling skin composition A mixed as described above according to the present invention prepares an antifouling coating composition having high stability to the human body as well as being suitable for long-term prevention from contamination of marine life.

The antifouling coating composition A according to the present invention is preferably used after being coated on a medium or rust preventive coating composition of a rubber chloride type, a vinyl resin type, an epoxy resin type or the like.

Coating methods include brush coating, spray coating, roller coating, and the like, and the coating thickness is appropriately 50 to 500 µm.

If the coating thickness is too thin, it is difficult to use for a long time due to the self-polishing property. If the coating thickness is too thick, drying is slow and internal pores remain.

The antifouling coating composition A according to the present invention facilitates the elution of component b by hydrolysis of the ester bond sites introduced into the polymer backbone when immersed in seawater.

The component b forms mineral components, especially sodium ions and carboxylates, in the seawater at the eluted site and is located at a short distance from the main chain to help the main chain's solubility.

Usually, the rate of hydrolysis by seawater at the ester linkage site is shown in the order of lauryl <butyl < ethyl <methyl <benzyl <phenyl < chloro methyl < bromo methyl.

In the case of ester bond sites such as lauryl and butyl, the hydrolysis rate is too slow to provide a proper wear rate, and in the case of chloromethyl and bromomethyl, the hydrolysis rate is too fast and the wear rate is too large for practical use. There is no

In addition, in the case of benzyl group, there is a disadvantage in that the pollution prevention property is poor after hydrolysis.

The present invention has been made in view of this fact, and as a result of various studies, it is possible to provide self-polishing properties by limiting the hydrolysis rate by using component b as well as limiting the hydrophilic carboxyl group to a range not deteriorating the water resistance. By being prepared, it is possible to provide an antifouling coating composition having excellent marine biofouling resistance.

The following Preparation Examples, Examples and Comparative Examples will be described in more detail the coating composition for preventing marine biological contamination of the present invention and its effects, but are not intended to limit the scope of the present invention.

[Production Example 1-1]

1 mole of maleic anhydride and 1 mole of p-bromo phenol were placed in a 1 L flask equipped with a cooler, a heater, and a stirrer, and heated to 120 ° C. while injecting nitrogen. Let's do it.

When the acid anhydride group disappeared through IR analysis, 0.7 mol of benzyl alcohol was added thereto, and the temperature was increased to 150 ° C., and the reaction was terminated when the acid value of the resin produced was 55 (theoretical final acid value was about 50.4). Was obtained and referred to as "component c-1".

[Manufacture Example 1-2]

1 mol of N- (4-hydroxy phenyl) lysineimide and 1 mol of maleic anhydride were dissolved in 500 parts by weight of methyl isobutyl ketone, and then placed in a 1 L round flask equipped with a cooler, a heater and a stirrer while stirring Inject nitrogen and raise the temperature to 115 ° C while replacing the internal air.

After distilling off the distilled methyl isobutyl ketone solvent, the reaction temperature was raised to 150 ° C., and then 1 mole of n-octanol was added dropwise for 30 minutes at the time when the acid anhydride disappeared through IR analysis. When the acid value was 5 (theoretical final acid value was trace), the resultant was decompressed to a vacuum degree of 10 Torr to completely remove unreacted n-butanol and volatiles to obtain a denatured unsaturated monomer, which was referred to as "component c-2".

[Manufacture Example 1-3]

1 mole of itaconic anhydride, 1 mole of phenol, and 0.01 mole of triethylamine were put in a round plastic, heated to 120 ° C. while injecting nitrogen, and then 2 moles of n-butanol when the acid anhydride disappeared through IR analysis. Add, and keep the reaction under reflux.

When the acid value of the resin to be prepared is 105 to decompression to a vacuum degree of 10 Torr to completely remove the unreacted n-butanol and volatiles to obtain a modified unsaturated monomer, which was called "c-3".

[Production Example 2-1 to 2-5]

The solvent a was poured into the flask with the stirrer at the component ratio shown in Table 1, and the temperature was increased while injecting nitrogen at the first reaction temperature of Table 1, followed by the component c, component c ', solvent b, and component of the component ratio shown in Table 1. d, The mixed liquid which consists of initiator a is added dropwise equally over 3 hours.

After the dropwise addition, the reaction was carried out for 30 minutes, and then the mixed solution of the solvent c and the initiator b was added dropwise evenly over 30 minutes, and the temperature was raised to the secondary reaction temperature for the holding reaction.

GPC (gel chromatography) analysis and non-volatile content were measured to terminate the retention reaction when the unreacted monomer was almost disappeared to obtain polymer solutions 1 to 5.

TABLE 1

[Production Example 3-1 to 3-5]

The solvent a of the component ratios shown in Table 2 was added to the flask with a stirrer, and the temperature was raised while adding nitrogen at the first reaction temperature, and then the mixed solution of component a, solvent b, component d, and initiator a of the component ratios shown in Table 2 was added to 3 After dropping the mixture evenly over time and maintaining the reaction for 30 minutes, the mixed solution of the solvent c and the initiator b was added dropwise evenly over 30 minutes and then subjected to the maintenance reaction at the secondary reaction temperature.

The reaction was terminated when the unreacted monomer almost disappeared by GPC analysis and measurement of the nonvolatile content, and then the component b and the solvent d mixture of the component ratios shown in Table 2 were added dropwise at the third reaction temperature for 10 minutes, followed by the maintenance reaction. The reaction was terminated at the primary resin acid value shown in Table 2, and the component b 'of the component ratios shown in Table 2 was further added, and the reaction was carried out at a fourth reaction temperature until the secondary resin acid value shown in Table 2 was measured to carry out a polymer. Solutions 6-10 were obtained.

TABLE 2

[Example 1-15]

Using the polymer solutions 1 to 10 of the preparation example as shown in Table 3 and uniformly dispersed using a high speed dissolver (HSD), and passed through a sand mill to prevent marine organisms antifouling coating composition to a particle size of 40㎛ or less Prepared.

TABLE 3

Comparative Example 1

12 parts by weight of vinyl chloride resin, 5 parts by weight of red iron oxide, 10 parts by weight of titanium dioxide, 10 parts by weight of zinc oxide, 40 parts by weight of copper dioxide were dispersed at 2500 RPM with a high speed dissolver for 1 hour, and then passed through a sand mill to obtain a particle size. Milling is carried out so that it may be 40 micrometers or less.

Into a tank containing 40 parts by weight of xylene, 30 parts by weight of methyl isobutyl ketone, 8 parts by weight of rosin, and 5 parts by weight of tricresyl phosphate, the dispersion was added and stirred for 30 minutes at 1500 RPM with a high speed dissolver to prepare an antifouling coating composition. It was.

Comparative Example 2

15 parts by weight of tributyl tin methacrylate, 35 parts by weight of methyl methacrylate, 40 parts by weight of xylene, 0.5 parts by weight of azobisisobutyronitrile and 10 parts by weight of a mixture of xylene were added dropwise at 80 ° C. for 3 hours. 10 parts by weight of talc, 5 parts by weight of barium sulfate, 10 parts by weight of tributyl tin fluoride, 20 parts by weight of copper oxide, and 40 parts by weight of xylene were added and dispersed in 2500 RPM for 3 hours with a high speed dissolver. The composition was prepared.

The antifouling performance of the antifouling coating compositions prepared in Examples and Comparative Examples was measured by the following method.

Comparative Example 3

1 mole of maleic anhydride and 1 mole of phenol were placed in a circular flask and maintained at 170 ° C., and the reaction was terminated at the point where the acid anhydride disappeared by IR analysis. After cooling to room temperature, 100 parts by weight were taken. 50 parts by weight of xylene, 50 parts by weight of methyl isobutyl ketone and 0.5 parts by weight of azobisisobutyronitrile were added to a circular flask containing 20 parts by weight of xylene, and 100 parts by weight of the polymer solution obtained by dropwise addition at a reaction temperature of 80 ° C for 3 hours. 10 parts by weight of iron oxide, 5 parts by weight of barium sulfate, 40 parts by weight of copper dioxide, 2 parts by weight of aerosol 200 and 40 parts by weight of xylene were added, and dispersed at 2500 rpm for 3 hours using a high speed dissolving bar to prepare an antifouling composition.

Using three kinds of sandblasted specimens according to KS M 5569 method using one kind of rolled steel sheet of KSD 3501 with width × length × thickness of 300 × 300 × 3.2 mm, antirust coating was performed with tar vinyl resin. Next, the antifouling coating compositions of Examples and Comparative Examples are spray-coated twice, so that the dry thickness becomes 150 µm, respectively.

After drying for one week at 75% relative humidity and 25 ° C, a raft was floated off the coast of Ulsan-si, and the soil was deposited at a depth of 1m to check the antifouling condition after 12 months.

Table 4 shows the results of rounding the contaminated area within the effective area of 52,000mm2 in the line down 70mm from the top, the line up 30mm from the bottom, and the effective area of 52,000 mm inside the left and right ends.

In addition, the anticorrosive coating compositions of Examples and Comparative Examples were spray-coated to a dry thickness of 150 μm on a tar rust-coated specimen, and then attached to a drum containing seawater, rotated at a speed of 15 knots, and the wear rate was measured for each elapsed time. The results are shown in Table 4 by rounding off within the range of 1 μm.

TABLE 4

As can be seen from the table, when the antifouling coating composition according to the present invention was used, not only the wear rate was relatively constant but also the antifouling performance was excellent.

Claims (4)

An intermediate prepared by copolymerizing at least one radical polymerizable unsaturated monomer represented by the following general formulas (11)-(18) with an unsaturated monomer containing one acid anhydride group represented by the following general formulas (1)-(3) To the esterification addition reaction of one or more compounds containing one hydroxyl group on the aromatic or hetero ring represented by the following general formulas (4)-(9), the hydroxyl group represented by the following general formula (10) is 1 A method for producing a marine biological pollution prevention copolymer, characterized in that it is produced by esterifying a compound containing a dog to an acid value of 150 or less. General formula (1) General formula (2) General formula (3) General formula (4) General formula (5) General formula (6) General formula (7) Formula (8) Formula (9) In the general formulas (4) to (9), X ₁ to X ₈ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen element, a hydrogen element, a nitro group, a mercapto group, a cyan group, and a A cyan group, a phenyl group or a halogen-substituted phenyl group, and each of Y and Z is a halogen element or a hydrogen element. General formula (10) R'-OH In general formula (10), R 'is a C1-C20 alkyl group, a benzyl group, or a C1-C20 halogen substituted alkyl group. General Formula (11) General Formula (12) Formula (13) Formula (14) General Formula (15) General Formula (16) General Formula (17) General Formula (18) In Formulas (11)-(18), each of R ₁ , R _2, and R ₃ is an alkyl group having 1 to 4 carbon atoms, a halogen element, a hydrogen element, a phenyl group, or a halogen substituted phenyl group, and each of X ₁ to X ₅ is carbon number. 1 to 4 alkyl groups, 1 to 4 carbon alkoxy groups, halogen elements, hydrogen elements, nitro groups, mercapto groups, cyan groups, thiocyanate groups, phenyl groups or halogen substituted phenyl groups, A is an ethylene group or a propylene group, Q is an alkyl group having 1 to 20 carbon atoms or a halogen substituted alkyl group having 1 to 20 carbon atoms, n is an integer of 2 to 4, m is an integer of 1 to 70, and R ₄ is an alkyl group having 1 to 20 carbon atoms or 1 to C 20 halogen substituted alkyl groups. The method of claim 1, wherein the radical polymerizable unsaturated monomer is used in an amount of 10 to 90 parts by weight based on 100 parts by weight of the copolymer. The equivalent ratio of the compound according to claim 1, wherein the compound containing one hydroxyl group on the acid anhydride group / aromatic or hetero ring of the intermediate obtained by copolymerizing a radically polymerizable unsaturated monomer with an unsaturated monomer containing one acid anhydride group is 1 Method for producing a marine biological pollution prevention copolymer characterized in that the esterification addition reaction to /0.5 ~ 1. A marine biological pollution prevention composition, comprising 5 to 50 parts by weight of an auxiliary antifouling agent in 100 parts by weight of the copolymer according to claim 1.