JP3087324B2 - Method for producing resin for antifouling paint and resin composition for antifouling paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention provides a new and useful
The present invention relates to a method for producing a resin for antifouling paint for underwater structures and a resin composition for antifouling paint. More specifically, since the coating film is strong and has an appropriate hydrolyzability, by blending an antifouling agent such as cuprous oxide, it has excellent long-term antifouling properties, The present invention also relates to a method for producing a resin for seawater antifouling paint and a resin composition for antifouling paint, which are useful for underwater structures and the like.

[0002]

2. Description of the Related Art The surface of an object under water is usually covered with a multilayer paint film, and is usually used to prevent the attachment and growth of organisms such as algae and barnacles living in the sea. An antifouling paint is applied as a top coat.

[0003] Incidentally, such antifouling paint contains an antifouling agent which gradually reacts with seawater to form a water-soluble salt, such as cuprous oxide, which itself is a poison. The soiling agent is sequentially eluted from the paint film in the form of a water-soluble salt.

[0004] However, in the process of dissolving the antifouling agent, it is extremely difficult to control the dissolution rate to be uniform. In addition, shortly after the ship with the antifouling paint is put into service or re-started, an undesirably high concentration of toxic substances will be present around the ship, wasting antifouling agents and water. Cause pollution.

[0005] As a conclusion of these facts, development of a resin which can be artificially controlled so that the dissolution rate of the antifouling agent becomes uniform is expected. As a substance which can make the dissolution rate of this kind of antifouling agent uniform to a certain extent and further suppress the growth or promotion of marine organisms for a long term, for example, tributyltin-containing acrylic copolymer There is.

In addition, copolymers having a carboxyl group, a dimethylamino group or a hydroxyl group having excellent water solubility in the side chain are used alone or in combination with a hydrophobic resin. Although it elutes at once in a short period of time or shows a good elution rate at the initial stage, it exhibits a disadvantage that it tends to suddenly stop eluting after a certain period of time.

[0007] Further, a paint using a copolymer having a carboxyl group and / or a hydroxyl group and a metal-based antifouling agent,
Extremely low storage stability. Furthermore, although rosin has been used as a resin component of this kind of top coat for a long time, it has a drawback that it lacks long-term antifouling properties.

Further, as disclosed in JP-A-53-124538 and the like, use of an acrylic resin containing a quaternary ammonium salt is taken up, and benzyl chloride and allyl chloride are used for the resin. Alternatively, a halogen compound such as epichlorohydrin is included as a negative group, that is, a so-called halogen compound is used as a quaternizing agent, and any of them is an effective component of an antifouling agent (antifouling substance). Dissolution rate is large, therefore, the development of antifouling performance over a long period of time cannot be achieved,
The disadvantage is that the effect is not sustainable.

[0009]

SUMMARY OF THE INVENTION However, the present inventors have intensively started research, paying attention to the existence of various unsolved problems in the prior art as described above.

Accordingly, an object of the present invention is to appropriately control the dissolution rate of the effective component (antifouling substance) of the antifouling agent so as to maintain the effect of the antifouling agent for a long period of time. An object of the present invention is to provide an extremely effective antifouling paint resin and a resin composition for an antifouling paint.

[0011]

Means for Solving the Problems Accordingly, the present inventors have:
In view of the various drawbacks in the prior art as described above, the present inventors have conducted intensive studies and have found that a specific antifouling paint resin obtained by grafting a hydrolysable polyester onto a vinyl (co) polymer is coated. After film formation, repeated swelling and hydrolysis from the surface in water, gradually, the coating film surface is polished, found that it is suitable for forming an ideal coating, the present invention It has been completed.

That is, by using such an antifouling paint resin as a part or all of a vehicle, the rate of dissolution of antifouling substances in the coating film is controlled, and the antifouling effect is maintained for a long period of time. Was successfully maintained.

Therefore, the present invention will be briefly described. First, the resin for an antifouling paint of the present invention is obtained by grafting a hydrolyzable polyester to a vinyl (co) polymer. The general formula is added to the side chain of the copolymer.

[0014]

Embedded image

(Where R ₁ in the formula represents a hydroxyl group or a halogen atom, R ₂ represents a hydrogen atom or an alkyl group, and n is an integer of 2 to 500.) Or the general formula

[0016]

Embedded image

(Wherein, R ₂ represents a hydrogen atom or an alkyl group, R ₃ represents a hydrogen atom or an alkali metal atom, and n is an integer of 2 to 500.) ) Is obtained by grafting a hydrolyzable polyester having a specific structure represented by

Here, the hydrolyzable polyester represented by the above general formula (I) is

[0019]

Embedded image

(Wherein R ₁ , R ₂ and R _{3 in the} formula
Are as described above. ),

For example, glycolic acid, lactic acid, 2-hydroxy-isobutyric acid, monofluoroacetic acid, lithium monofluoroacetate, sodium monofluoroacetate, potassium monofluoroacetate, monochloroacetic acid, lithium monochloroacetate, sodium monochloroacetate, potassium monochloroacetate , Monobromoacetic acid, lithium monobromoacetate, sodium monobromoacetate, potassium monobromoacetate, monoiodoacetic acid, lithium monoiodoacetate, sodium monoiodoacetate, potassium monoiodoacetate,

1-fluoro-2-methylacetic acid, lithium 1-fluoro-2-methylacetate, sodium 1-fluoro-2-methylacetate, potassium 1-fluoro-2-methylacetate, 1-chloro-2-methylacetic acid , 1-chloro-2
-Lithium methyl acetate, sodium 1-chloro-2-methyl acetate, potassium 1-chloro-2-methyl acetate, 1-
Bromo-2-methylacetic acid, lithium 1-bromo-2-methylacetate, sodium 1-bromo-2-methylacetate,
-Potassium bromo-2-methylacetate,

1-iodo-2-methyl acetic acid, lithium 1-iodo-2-methyl acetate, sodium 1-iodo-2-methyl acetate, potassium 1-iodo-2-methyl acetate,
1-fluoro-2,2′-dimethylacetic acid, 1-fluoro-2,2′-dimethylacetate, 1-fluoro-
Sodium 2,2'-dimethylacetate, 1-fluoro-
Potassium 2,2′-dimethylacetate, 1-chloro-2,
2′-dimethylacetic acid, 1-chloro-2,2′-dimethylacetate lithium, 1-chloro-2,2′-dimethylacetate,

Potassium 1-chloro-2,2'-dimethylacetate, 1-bromo-2,2'-dimethylacetic acid, lithium 1-bromo-2,2'-dimethylacetate, 1-bromo-
Sodium 2,2′-dimethylacetate, 1-bromo-2,
2'-dimethyl potassium acetate, 1-iodo-2,2'-
At least one compound selected from dimethylacetic acid, lithium 1-iodo-2,2'-dimethylacetate, sodium 1-iodo-2,2'-dimethylacetate, potassium 1-iodo-2,2'-dimethylacetate, and the like Is condensed by dehydration, dehydrochlorination or desalination reaction,

Dimers derived from the various compounds described above, for example, those obtained by ring-opening polymerization of glycolide and lactide, and the like. Further, the vinyl (co) polymer referred to herein is obtained by polymerizing at least one kind of polymerizable unsaturated monomer.

That is, aromatic vinyl monomers such as styrene, α-methylstyrene, chloromethylstyrene, p-tert-butylstyrene and vinyltoluene; methyl (meth) acrylate, ethyl (meth) acrylate, n- Propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert
-Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate or alkoxyalkyl (Meth) acrylates such as (meth) acrylate;

Diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with monohydric alcohols; vinyl esters such as vinyl acetate, vinyl benzoate, "Veoba" (vinyl ester manufactured by Shell Co., The Netherlands) Kinds; "Viscort 8F, 8FM, 17FM, 3
F or 3FM "[fluorinated acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or Ni-propyl perfluorooctanesulfonamidoethyl (meth) (Per) fluoroalkyl group-containing vinyl esters such as acrylates,
Fluorinated polymerizable compounds such as vinyl ethers, (meth) acrylates or unsaturated polycarboxylic esters;

Alternatively, vinyl monomers having no functional group such as olefins such as (meth) acrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; (meth) acrylamide, dimethyl (meth) acrylamide, Vinyl monomers containing an amide bond such as N-tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide, dimethylaminopropyl acrylamide, alkoxylated N-methylolated (meth) acrylamides;

Dialkyl [(meth) acryloyloxyalkyl] phosphates or (meth) acryloyloxyalkyl acid phosphates, dialkyl [(meth) acryloyloxyalkyl] phosphites or (meth) acryloyloxyalkyl acid phosphites Phytes; further, an epoxy group-containing vinyl monomer such as glycidyl (meth) acrylate or methyl glycidyl (meth) acrylate, or an alkylene oxide adduct of (meth) acryloyloxyalkyl acid phosphates or acid phosphites; Phosphoric acid or phosphorous acid or an ester compound thereof with an acidic ester thereof, a phosphorus atom-containing vinyl-based monomer such as 3-chloro-2-acidphosphoxypropyl (meth) acrylate;

Glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, ethylene glycol monoglycidyl vinyl ether, triethylene glycol monoglycidyl vinyl ether, dipropylene glycol monoglycidyl vinyl ether, cyclohexyl vinyl ether, benzyl vinyl ether, 2-ethylhexyl vinyl ether, triethylene glycol divinyl ether , Dipropylene glycol divinyl ether, 1,4-bisdivinyloxymethylcyclohexane, or an addition reaction product in which the molar ratio of isophorone diisocyanate to 4-hydroxybutyl vinyl ether is 1: 2, or hydrogenated xylylene diisocyanate and 4
A molar ratio with hydroxybutyl vinyl ether of 1: 2
An addition reactant;

Dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth)
Acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate or polypropylene glycol, or polyethylene Glycol mono (meth) acrylate, “Placcel F
Hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids or adducts thereof with ε-caprolactone, such as “M, FA monomers” (caprolactone-added monomers manufactured by Daicel Chemical Industries, Ltd.);

(Meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, unsaturated mono- or dicarboxylic acids such as itaconic acid or citraconic acid, and monoesters of these dicarboxylic acids with monohydric alcohols. Α, β-ethylenically unsaturated carboxylic acids, or α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters as described above, and maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, Various types such as tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "Hymic acid" (product of Hitachi Chemical Co., Ltd.), and adducts of polycarboxylic acids such as tetrachlorophthalic acid or dodecynylsuccinic acid with anhydrides Of unsaturated carboxylic acids and "Kajura E" (manufactured by Shell, Netherlands) Glycidyl esters of fatty acids in the form of synthetic resins), monoglycidyl esters of monovalent carboxylic acids such as glycidyl esters of coconut oil fatty acids or glycidyl octylate or adducts with monoepoxy compounds such as butyl glycidyl ether, ethylene oxide or propylene oxide; Or these and ε
Adducts with caprolactone;

Examples of unsaturated mono- or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid, and monoesters of these dicarboxylic acids and monohydric alcohols. Α, β-ethylenically unsaturated carboxylic acids; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3- Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or Polyethylene glycol Α, β-unsaturated carboxylic acid hydroalkyl esters such as mono (meth) acrylate and maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, “Hymic acid” Carboxyl-containing monomers, such as adducts of polycarboxylic acids with anhydrides, such as tetrachlorophthalic acid or dodecynylsuccinic acid;

Silicones such as vinylethoxysilane, α-methacryloxypropyltrimethoxysilane, trimethylsiloxyethyl (meth) acrylate, “KR-215” or “X-22-5002” (product of Shin-Etsu Chemical Co., Ltd.) It refers to those obtained by polymerizing a polymerizable monomer selected from monomers and the like.

The polymerization of the vinyl (co) polymer used in the present invention can be carried out by utilizing the above-mentioned respective raw material components and making full use of a known and common copolymerization reaction method. Isobutyronitrile (AIBN), benzoyl peroxide (BPO), tert-butyl perbenzoate (TBPB), tert-butyl hydroperoxide, di-tert-butyl peroxide, (D
TBPO) or cumene hydroperoxide (CH
A radical-generating polymerization catalyst such as P) is used alone or in combination of several kinds.

Here, as a technique for grafting a hydrolyzable polyester onto a vinyl (co) polymer, an anionic ring-opening polymerization of a cyclic dimer such as glycolide or lactide is carried out, and active hydrogen is used as a reaction terminator. Using a vinyl (co) polymer having a hydroxyl group and / or a carboxyl group
It is a method of dehydrating and condensing a hydroxyl acid such as glycolic acid in the presence of a polymer, or an alkali halide such as sodium monochloroacetate in the presence of a vinyl resin having an alkyl halide such as a chloromethyl group. In the presence of an aprotic polar solvent, a metal salt is subjected to a desalination reaction, or a hydroxyl group such as polyglycolic acid is reacted with isocyanate methyl methacrylate or a carboxyl group is reacted with glycidyl methacrylate. Is obtained by copolymerizing the resulting macromonomer with another polymerizable unsaturated monomer, or a vinyl (co) polymer having an acid anhydride group, an epoxy group or an isocyanate group, a polyglycolic acid or the like. Of course, but of course, the method of grafting It is not limited to the method of supra these.

Here, the above-mentioned acidic compound which is an essential component of the resin composition for antifouling paints includes low molecular weight compounds such as benzoic acid, phosphoric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, sulfuric acid and hydrochloric acid. Acid or rosin, acid group-containing polyester resin, acid group-containing acrylic resin, acid group-containing urethane resin, natural resin-modified phenolic resin, maleic acid resin, natural resin-modified maleic acid resin or phenol resin, etc. To do
It is used for controlling the hydrolyzability of the various antifouling paint resins as described above, and the use of the acidic compound is 0.1 parts by weight based on 100 parts by weight of the antifouling paint resin. -100 parts by weight, preferably 1-30
It is preferable that the amount be within the range of parts by weight.

The antifouling paint resin of the present invention is usually blended with known and common antifouling agents and pigments. First, as antifouling agents, cuprous oxide, zinc chromate,
Strontium chromate, cupric chromate, cupric citrate, cupric ferrocyanate, cupric quinoline, cupric δ-hydroquinoline, cupric olefinate, cupric nitrate, phosphoric acid Cupric, cupric tartrate, cuprous oxide, cuprous iodide, cuprous sulfite or the like; on the other hand, as pigments, titanium oxide, iron oxide, inorganic pigments such as carbon black, or azo-based pigments Although organic pigments such as cyanine, quinacridone and the like are used, inorganic pigments are usually used.

The use of such an antifouling agent with an organic tin compound, a triazine compound, an organic sulfur compound, or the like is not at all hindered. These antifouling agents or pigments can be used alone or in combination of two or more.

The resin for antifouling paint and the resin composition for antifouling paint of the present invention thus obtained are used as ship bottom paint or fishing net paint.

[0041]

EXAMPLES Next, the present invention will be described more specifically with reference examples, examples and comparative examples, but the present invention is not limited to these.

In the following, all parts and percentages are by weight unless otherwise specified. Reference Example 1 500 parts of lactide was charged into a Pyrex polymerization tube having a nitrogen inlet tube, a nitrogen outlet, and a catalyst addition port, and after replacing the system with dry nitrogen, 0.05 part of tin octylate was added through the catalyst addition port. Polyglycolic acid was obtained by the addition.

When the molecular weight was measured by a carboxylic acid end group titration method, the molecular weight of the obtained polyglycolic acid was 5,
800. Reference Example 2 A four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas inlet was charged with 500 parts of glycolic acid, 500 parts of lactic acid, and 0.5 part of dibutyltin oxide. Then, dehydration condensation was performed at the same temperature to obtain a glycolic acid-lactic acid copolymer.

When the molecular weight was measured by a carboxylic acid end group titration method, the molecular weight of the obtained polyglycolic acid-lactic acid copolymer was 3,500. Example 1 A four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas inlet was charged with 850 parts of toluene, heated to 100 ° C., and then heated to 350 ° C. with methyl methacrylate.
, 550 parts of methyl acrylate, 100 parts of chloromethylstyrene, 2 parts of azobisisobutyronitrile and 10 parts of tert-butylperoxy-2-ethylhexanoate were added dropwise over 5 hours. The reaction was continued at the same temperature for 20 hours.

After cooling, N-methyl-2-pyrrolidone 3
Then, 00 parts and 300 parts of sodium monochloroacetate were added, and the reaction was performed again at 100 ° C. for 50 hours. By removing the salt precipitated by the reaction by filtration,
A resin solution having a nonvolatile content of 50% and a Gardner viscosity at 25 ° C. (the same applies hereinafter) of XY was obtained.

Example 2 The same reactor as in Example 1 was charged with 1,100 parts of toluene and heated to 100 ° C., and then 300 parts of methyl methacrylate, 500 parts of methyl acrylate, β-hydroxyethyl A mixture consisting of 200 parts of methacrylate, 5 parts of azobisisobutyronitrile and 8 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise over 5 hours, and further over 20 hours at the same temperature. The reaction was continued.

After cooling, 100 parts of glycolic acid and 0.5 part of dibutyltin oxide were added, the mixture was heated to 120 ° C., and a dehydration condensation reaction was carried out by circulating toluene.

The reaction was continued until the acid value reached 5, to obtain a resin solution having a nonvolatile content of 50% and a viscosity of WX. Example 3 1,300 parts of toluene was charged into the same reactor as in Reference Example 1 and heated to 100 ° C., and then 300 parts of methyl methacrylate, 500 parts of methyl acrylate, and 190 parts of ethyl acrylate A mixture of 10 parts of isocyanatoethyl methacrylate, 8 parts of azobisisobutyronitrile and 5 parts of tert-butylperoxy 2-ethylhexanoate was added dropwise over 5 hours,
The reaction was continued at the same temperature for 20 hours.

After cooling, 300 parts of the polyglycolic acid obtained in Reference Example 1 was charged, the temperature was raised to 80 ° C., and the reaction was continued for 5 hours. The nonvolatile content was 50% and the viscosity was Z. A resin solution was obtained.

Example 4 The same reactor as in Reference Example 1 was charged with 1,300 parts of toluene and heated to 100 ° C., and then 350 parts of methyl methacrylate, 500 parts of methyl acrylate, and 500 parts of ethyl acrylate 135 parts, 15 of glycidyl methacrylate
Part, 8 parts of azobisisobutyronitrile and tert
A mixture consisting of 8 parts of -butylperoxy 2-ethylhexanoate was added dropwise over 5 hours, and the reaction was continued at the same temperature for 20 hours.

After cooling, 300 parts of the glycolic acid-lactic acid copolymer obtained in Reference Example 2 were charged, the temperature was raised to 80 ° C., and the reaction was continued for 5 hours. The nonvolatile content was 50% and the viscosity was 50%. A resin solution Z was obtained.

COMPARATIVE EXAMPLE 1 1,000 parts of toluene were charged into the same reactor as in Reference Example 1, heated to 100 ° C., and then 300 parts of N, N-dimethylacrylamide and 500 parts of methyl acrylate were added.
, A mixture of 200 parts of methyl methacrylate, 8 parts of azobisisobutyronitrile and 8 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise over 5 hours. And the reaction was continued for 20 hours to obtain a control resin solution having a molecular weight of 12,000, a non-volatile content of 50%, and a viscosity of YZ.

Comparative Example 2 The same reactor as in Reference Example 1 was charged with 1,000 parts of toluene and heated to 100 ° C., followed by 300 parts of N, N-dimethylacrylamide and 350 parts of methyl acrylate.
, A mixture of 350 parts of N-vinylpyrrolidone, 5 parts of azobisisobutyronitrile and 5 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise over 5 hours. By continuing the reaction for 20 hours, a control resin solution having a molecular weight of 14,500, a nonvolatile content of 50%, and a viscosity of WX was obtained.

Examples 5 to 8 and Comparative Examples 3 and 4 The respective resins obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were compounded at the following compounding ratio, and kneaded and dispersed. To prepare a resin composition for an antifouling paint, that is, an antifouling paint, and various performances were compared and examined in accordance with a procedure described later.

Resin solution 600 parts Cuprous oxide 650 parts Valve handle 50 parts

Example 5 600 parts of the resin solution obtained in Example 1 was mixed with 650 parts of cuprous oxide, 50 parts of a red stalk and 200 parts of rosin, and the mixture was kneaded and dispersed to obtain an antifouling paint. Was prepared, and various performances were evaluated and determined according to the procedure described later.

Example 6 600 parts of the resin solution obtained in Example 2, 650 parts of cuprous oxide, 50 parts of petiole and "Beckasite F-1"
83 "[natural resin-modified phenolic resin manufactured by Dainippon Ink and Chemicals, Inc .; acid value = 15 to 25] and kneaded and dispersed to prepare an antifouling paint, as described later. According to the outline, various performances were evaluated and determined.

Example 7 600 parts of the resin solution obtained in Example 3, 650 parts of cuprous oxide, 50 parts of petiole and "FINEDIC M
-8830 "(a polyester resin manufactured by Dainippon Ink and Chemicals, Inc .; acid value 70 ± 5).
The antifouling paint was prepared by kneading and dispersing, and various performances were evaluated and determined according to the procedure described later.

Example 8 600 parts of the resin solution obtained in Example 4, 650 parts of cuprous oxide, 50 parts of petiole and "Acridic A-
157 "[Acrylic resin manufactured by Dainippon Ink and Chemicals, Incorporated; acid value 10 to 13], and kneading and dispersing to prepare an antifouling paint, and various properties according to the procedure described later. Was evaluated.

Comparative Example 3 600 parts of the control resin solution obtained in Comparative Example 1, 650 parts of cuprous oxide and 50 parts of a red stalk were blended, kneaded and dispersed, and a control antifouling paint was obtained. Was prepared, and various performances were evaluated and determined according to the procedure described later.

COMPARATIVE EXAMPLE 4 600 parts of the control resin solution obtained in Comparative Example 2, 650 parts of cuprous oxide and 50 parts of a red stalk were blended and kneaded and dispersed to obtain a control antifouling paint. Was prepared, and various performances were evaluated and determined according to the procedure described later.

[Performance test procedure] [1] Rotary test An etching primer was applied to a sand-blasted copper plate of 10 cm × 10 cm × 0.8 mm by 5 μm (μm).
The coating was performed once with a film thickness of a predetermined value, and further, a tar vinyl-based ship bottom rust preventive paint was applied once so as to have a film thickness of 70 μm.
Next, each of the 10 antifouling paints thus prepared was applied three times with a film thickness of 60 μm, and each of the obtained test plates was attached to the outer plate of a rotating drum suspended below the sea surface. Rotate the drum so that the seawater speed becomes 10 knots, perform a rotary test for 3 months, measure the difference between the initial film thickness and the film thickness after aging, and evaluate the self-polishing property. did. The test results are summarized in Table 1.

[2] Simulation Test A tar-epoxy paint as an undercoat rust-preventive paint was applied to a sand-blasted 10 cm × 10 cm × 1 mm copper plate by 12
The coating was performed twice with a film thickness of 5 μm, and the intermediate coating of tar vinyl was further applied once so as to have a film thickness of 70 μm. Then, Examples 1 to 8 and Comparative Examples 1 and 2
Each of the antifouling paints was coated three times with a film thickness of 100 μm, and the above-described rotary test was performed for one month on each of the obtained test plates, and then immersed in a 1.5 m sea for one month. To make one cycle,
A simulation test was performed assuming the operation of a ship.
The rust prevention for each cycle was indicated by the area (%) occupied by adhesion formation on the test coating. The test results are summarized in the second
It is shown in the table.

The measurement results of the copper elution rate at that time are collectively shown in Table 3, and the units in the table are “μg / cm ² / day”.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

The specific graft copolymer according to the present invention can form a coating film which is strong and has an appropriate dispersibility in seawater from the surface.

Therefore, the resin for antifouling paint of the present invention is:
Since the antifouling agent to be incorporated into the paint can be eluted over a long period of time and periodically and regularly, it is possible to prevent marine organisms from adhering to ship bottoms and underwater structures. .

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C09D 1/00-201/10

Claims (4)

(57) [Claims] 1. A vinyl (co) polymer having the general formula : (Wherein R ₁ is a hydroxyl group or a halogen atom
And R ₂ represents a hydrogen atom or an alkyl group
And, also, n represents be an integer der shall comprising 2-500
You. ) Or the general formula : (Wherein, R ₂ in the formula is a hydrogen atom or an alkyl Le group
The, R ₃ also represents a hydrogen atom or an alkali metal atom
To cities, also, n represents assumed to be a integer comprised from 2 to 500
You. Characterized Rukoto by grafting a hydrolyzable polyester having a structure represented by), the antifouling paint resins
Manufacturing method . 2. A compound represented by the formula (I) or (II):
_{2. The} method for producing an antifouling paint resin according to claim 1 , wherein ₂ is a hydrogen atom or a methyl group . 3. A vinyl (co) polymer having the general formula : (Wherein R ₁ is a hydroxyl group or a halogen atom
And R ₂ represents a hydrogen atom or an alkyl group
And, also, n represents be an integer der shall comprising 2-500
You. ) Or the general formula : (Wherein, R ₂ in the formula is a hydrogen atom or an alkyl Le group
The, R ₃ also represents a hydrogen atom or an alkali metal atom
To cities, also, n represents assumed to be a integer comprised from 2 to 500
You. A resin composition for an antifouling paint, which comprises, as active ingredients, an antifouling paint resin obtained by grafting a hydrolyzable polyester having a structure represented by the formula (1), and an acidic compound. 4. A compound represented by the formula (I) or (II):
_The resin composition for an antifouling paint according to claim 3 , wherein ₂ is a hydrogen atom or a methyl group .