JP3161005B2 - Resin composition for antifouling paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful antifouling paint resin composition. More specifically, the present invention relates to a carboxyl group-containing polymer in which the carboxyl group is blocked with an N-hydroxysuccinimide derivative compound, that is, a polymer having a specific group called a succinimide ester group. The present invention relates to a resin composition for an antifouling paint, which is contained as an essential component (film-forming component).

[0002] The composition of the present invention has excellent long-term antifouling properties, and can be particularly applied to antifouling paints used for ship bottoms and fish nets.

[0003]

2. Description of the Related Art A variety of aquatic organisms such as algae and barnacles adhere to the surface of objects that are left in the seawater for a long time, such as underwater objects, structures or ship bottoms.
As they grow and proliferate, their appearance is impaired and corrosion occurs.

[0004] In the case of a ship, it also causes a decrease in ship speed and an increase in fuel efficiency. In addition, the attachment of aquatic organisms to aquaculture nets and wire nets can block the flow of seawater, resulting in a lack of oxygen, which in turn can kill fish and shellfish. ing.

[0005] Therefore, in order to prevent the growth of such aquatic organisms, various antifouling paints are applied as a top coat on the surface of those objects. Such antifouling paint, a hydrophobic resin, a hydrophilic resin or a hydrophilic compound,
Each contains various antifouling agents, such as various organotin compounds and cuprous oxide, which are themselves poisons.

When this coating film comes into contact with seawater, the hydrophilic resin or hydrophilic compound and the antifouling agent elute from the surface. However, when these coatings come into contact with seawater,
Immediately and undesirably quickly, elution of the antifouling agent takes place, resulting in an unnecessarily high concentration of toxicants around the coating, reducing waste of the antifouling agent and contaminating the seawater. It was a place to provoke.

[0007] Then, after the dissolution has progressed to a certain extent, the dissolution rate of the antifouling agent decreases, and there is a problem that the adhesion of aquatic organisms in the sea is resumed. In order to solve this problem, an antifouling coating composition comprising a vinyl polymer having a tributyltin ester group in a side chain has been developed.

[0008] This is because, when a coating film using this polymer as a vehicle comes in contact with seawater, the tributyltin ester group is hydrolyzed to form a carboxylate group soluble in seawater;
Decomposes into tributyltin hydroxide.

The former contributes to dissolution of the coating film in seawater,
The latter is to act as an antifouling agent, so that when the coating comes in contact with seawater, a fresh coating is always formed or formed, and the antifouling agent elutes at a uniform rate, and over a long period of time,
Because of its antifouling effect, it has been widely used in many ship bottoms, underwater structures and fishing nets.

The type in which the coating film itself becomes water-soluble by seawater is called a self-polishing type. However, in recent years, the use of organotin compounds has been restricted due to the problem of adverse effects on organisms and the environment.

Therefore, there is an urgent need to develop a novel antifouling paint composition which is a self-polishing type and contains an antifouling agent which does not adversely affect living organisms and the environment.

For this purpose, a polymer having a hydrophilic group such as a carboxyl group, a dimethylamino group, a hydroxyl group or a quaternary ammonium group in a side chain thereof is used as a vehicle for a resin composition for an antifouling paint. However, it is not possible to maintain a uniform coating film itself and a dissolution rate of an antifouling agent over a long period of time. Further, although a phenyl ester group-containing acrylic resin has been proposed, it is inferior in elution of the coating film itself and the antifouling agent.

[0013]

As described above, an antifouling paint having excellent antifouling properties over a long period of time has not yet been obtained.

In view of the above-mentioned various drawbacks in the prior art, the present inventors have sought a self-polishing type resin which can maintain the elution of an antifouling agent for a long period of time. I started my research diligently.

Therefore, an object of the present invention is to solve the problem that the dissolution rate of the effective component (antifouling substance) of the antifouling agent is controlled uniformly, and the antifouling agent is maintained for a long period of time. In order to maintain the elution of the coating, the coating itself dissolves gradually in seawater and always forms or produces a fresh coating, giving a self-polishing type coating. An object of the present invention is to provide a coating resin composition.

[0016]

To this end, the present inventors have conducted intensive studies with the aim of solving the problems to be solved by the present invention as described above. The polymer (A) having a specific succinimide ester group as the active component is particularly selected from the group consisting of vinyl polymers, polyether polymers, polyester polymers, polyamide polymers and polyurethane polymers. In a seawater treatment using a novel resin composition for an antifouling paint comprising the polymer (A) having the succinimide ester group comprising at least one polymer, Hydrolysis from the part in contact with seawater elutes, and it is found that a fresh coating film is always formed and formed, and the antifouling agent elutes at a uniform rate. It was led to the completion.

That is, the present invention basically provides a novel antifouling paint comprising a polymer (A) having a succinimide ester group having a specific structure as an essential film-forming component. It is intended to provide a resin composition for

More specifically, the polymer (A) contains a succinimide ester group-containing polymer (A) and a hydrophilic resin (B) and / or a hydrophilic compound (C), or contains the polymer (A). Or the polymer (A), the hydrophilic resin (B) and / or the hydrophilic compound (C), and the hydrophobic resin (D). Comprising a resin composition for an antifouling paint,

It is another object of the present invention to provide a resin composition for an antifouling paint, which further comprises an antifouling agent (E) in addition to the above-mentioned various resin compositions.

[Structure] The polymer having the above-mentioned succinimide ester group used in the present invention, in particular, a vinyl-based polymer, a polyether-based polymer, and a polyester containing the succinimide ester group, respectively The term “based polymer, polyamide-based polymer and / or polyurethane-based polymer (A)” means a vinyl-based polymer, a polyether-based polymer, and a polyester-based polymer having a group represented by the following general formula (I), respectively. It refers to a coalesced, polyamide-based and / or polyurethane-based polymer.

Among the vinyl polymers, only typical ones are exemplified, and acrylic polymers, vinyl carboxylate polymers, aromatic vinyl polymers or fluoropolymers are exemplified. Graft copolymers of various polymers other than the so-called vinyl polymers, such as olefin polymers, further, polyester resins, alkyd resins or polyurethane resins, and vinyl polymers. Or block copolymers.

[0022]

Embedded image

Wherein R ₁ and R ₂ independently represent a hydrogen atom or a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, An alkoxycarbonyl group, an alkoxy group, an aryloxy group, an alkanoyl group, an alkanoyloxy group, a nitro group or a cyano group, and R ₁ and R ₂ represent a substituted or unsubstituted alkylene chain, or a substituted or unsubstituted alkylene chain; It may form a substituted aromatic ring. ]

To prepare such vinyl polymers containing a succinimide ester group, the vinyl monomers containing a succinimide ester group may be homopolymerized or copolymerized with another monomer having copolymerizability. The carboxyl group-containing vinyl resin prepared in advance (co)
A method of reacting a polymer with an N-hydroxysuccinimide compound represented by the following general formula (II), for example,

Furthermore, various polymers (A) containing a succinimide ester group, such as polyether polymers, polyester polymers, polyamide polymers and / or polyurethane polymers, respectively. In the same manner as described above, a carboxyl group-containing prepared polyether-based polymer,
Various methods such as a method of reacting a polyester polymer, a polyamide polymer and / or a polyurethane polymer with an N-hydroxysuccinimide compound represented by the following general formula (II) are employed. it can.

[0026]

Embedded image

Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, An alkoxycarbonyl group, an alkoxy group, an aryloxy group, an alkanoyl group, an alkanoyloxy group, a nitro group or a cyano group, and R ₁ and R ₂ represent a substituted or unsubstituted alkylene chain, or a substituted or unsubstituted alkylene chain; It may form a substituted aromatic ring. ]

Among these, the succinimide ester group-containing vinyl monomers used in the preparation by the above-mentioned method are prepared by: a) a carboxyl group-containing monomer; With an N-hydroxysuccinimide compound represented by the general formula (II) in the presence of a dehydrating agent for carbodiimides,

B) Various methods such as reacting a monomer containing an acid chloride group with an N-hydroxysuccinimide compound represented by the above general formula (II) in the presence of a basic substance The method is adopted.

First, only typical examples of the carboxyl group-containing monomers used in the preparation according to the above-mentioned method a) include (meth) acrylic acid and carboxyethyl. Including (meth) acrylate or crotonic acid, furthermore, succinic acid,
Various monobasic acids, such as monovinyl esters of various saturated dicarboxylic acids, such as adipic acid or sebacic acid; various unsaturated dibasic acids, such as maleic acid, fumaric acid or itaconic acid;

Alternatively, monobasic acids such as the above-mentioned half esters of unsaturated dicarboxylic acids and monohydric alcohols; N- [carboxy- (substituted) alkyl] (meth) acrylamides derived from amino acids; or 2-
Carboxyl group-containing derivatives such as addition products of a hydroxyl group-containing monomer represented by hydroxyethyl (meth) acrylate and an acid anhydride such as succinic anhydride or phthalic anhydride; And lactone addition derivatives of various carboxyl group-containing monomers. In the preparation according to the above method b), various acid chlorides of a carboxyl group-containing monomer are used as described above.

Furthermore, if only particularly typical N-hydroxy-succinimide compounds represented by the aforementioned formula (II) are exemplified, N-hydroxy-succinimide, N-hydroxyphthalimide, N-hydroxyphthalimide,
-Hydroxy-methyl-succinimide, N-hydroxy-2,2-dimethyl-succinimide, N-hydroxy-2,3-dimethyl-succinimide, N-hydroxy-chloro-succinimide, N-hydroxy-phthalimide, N-hydroxy-4 -Methyl-phthalimide or N-hydroxy-4-chloro-phthalimide.

Then, if only particularly typical examples of the succinimide ester group-containing monomers obtained by the various methods described above are given, N- (meth) acryloyloxy-succinimide may be used. N- (meth) acryloyloxy-methyl-succinimide, N- (meth) acryloyloxy-chloro-
Succinimide or N- (meth) acryloyloxy-phthalimide,

N- (meth) acryloyloxy-4-methyl-phthalimide, N- (meth) acryloyloxy-4-chloro-phthalimide, N- [3- (meth) acryloyloxy-propionyloxy] -succinimide, N- (meth) acryloyloxy-4-chloro-phthalimide [3- (meth) acryloyloxy-propionyloxy] -methyl-succinimide, N- [3-
(Meth) acryloyloxy-propionyloxy]-
Chloro-succinimide, or N- [3- (meth) acryloyloxy-propionyloxy] -phthalimide;

N- [3- (meth) acryloyloxy-
Propionyloxy] -4-methyl-phthalimide, N
-[3- (meth) acryloyloxy-propionyloxy] -4-chloro-phthalimide, N-[(meth) acryloylaminoacetyloxy] -succinimide,
N-[(meth) acryloylaminoacetyloxy]-
Methyl-succinimide or N-[(meth) acryloylaminoacetyloxy] -chloro-succinimide,

N-[(meth) acryloylaminoacetyloxy] -phthalimide, N-[(meth) acryloylaminoacetyloxy] -4-methyl-phthalimide, N-[(meth) acryloylaminoacetyloxy] -4-chloro -Phthalimide, N-[(meth) acryloylaminopropionyloxy] -succinimide, N-[(meth) acryloylaminopropionyloxy] -methyl-succinimide or N-[(meth)
Acryloylaminopropionyloxy] -chloro-succinimide,

N-[(meth) acryloylaminopropionyloxy] -phthalimide, N-[(meth) acryloylaminopropionyloxy] -4-methyl-phthalimide, N-[(meth) acryloylaminopropionyloxy] -4-chloro -Phthalimide, N- (6-
Acryloyloxy-hexanoyloxy) -succinimide or N- (6-acryloyloxy-hexanoyloxy) -methyl-succinimide,

Alternatively, N- (6-acryloyloxy-
Hexanoyloxy) -chloro-succinimide, N-
(6-acryloyloxy-hexanoyloxy) -phthalimide, N- (6-acryloyloxy-hexanoyloxy) -4-methyl-phthalimide or N-
(6-acryloyloxy-hexanoyloxy) -4
-Chloro-phthalimide and the like.

In order to prepare the vinyl polymer (A) used in the present invention from such succinimide ester group-containing monomers, one or more of such succinimide ester group-containing monomers may be polymerized. Alternatively, it may be copolymerized with other monomers which can be copolymerized therewith.

If only particularly typical examples of such copolymerizable monomers are given, methyl (meth)
Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-
Butyl (meth) acrylate, 2-ethylhexyl (meth) such as acrylate or lauryl (meth) acrylate, C ₁ -C ₂₂ comprising various alkyl (meth) acrylates;

Various nitrogen atom-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate or isobornyl (meth) acrylate Various aralkyl (meth) acrylates, such as benzyl (meth) acrylate or phenethyl (meth) acrylate; various alicyclic alkyl (meth) acrylates, such as methyl crotonate or ethyl crotonate; Alkyl esters of crotonic acid;

Dialkyl esters of various unsaturated dibasic acids, such as dimethyl malate, dibutyl malate, dimethyl fumarate, dibutyl fumarate, dimethyl itaconate or dibutyl itaconate; styrene, p
Various aromatic vinyl monomers such as -tert-butylstyrene, α-methylstyrene, vinyltoluene or vinylpyridine; various cyano group-containing monomers such as (meth) acrylonitrile or crotononitrile Various halogenated olefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl chloride or vinylidene chloride;

Various α-olefins such as ethylene, propylene, isobutylene or 1-butene; or vinyl acetate, vinyl propionate, vinyl pivalate or vinyl versatate, vinyl benzoate,
Various carboxylic acid vinyl esters such as "Veova" (product of Shell, The Netherlands), and various alkyl- or cycloalkyl such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether or cyclohexyl vinyl ether. Vinyl ethers;

Various carbonyl group-containing monomers such as acrolein or methyl vinyl ketone; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methyl (meth) Acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine,
N-vinyl formamide, N-vinyl pyrrolidone, N
-Vinylimidazole, N-vinylcarbazole, N-
Such as vinylquinoline or N-vinylpiperidine,
Various nitrogen-containing monomers;

Various polyether-containing monomers such as "Blemmer PP or PE" (Nippon Oil & Fat Products);
"Viscort 8F, 8FM, 3F or 3FM"
[Osaka Organic Chemicals Co., Ltd.] or a fluoroalkyl group-containing monomer or a monomer such as perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or N-isopropylfluorooctanesulfonamidoethyl (meth) acrylate Perfluoroperalkyl group-containing monomers;

"Light ester PM or PA"
Various phosphoric acid ester group-containing monomers such as [products of Kyoeisha Yushi Kagaku Kogyo Co., Ltd.]; sulfonic acid group-containing monomers such as styrene sulfonic acid or vinyl sulfonic acid, or a metal salt thereof. And various acid anhydride group-containing monomers such as maleic anhydride or itaconic anhydride.

Further, various carboxyl group-containing monomers as described above or 2-hydroxyethyl (meth) can be used in an amount not to impair the characteristics of the present invention.
Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate,
Various hydroxyl group-containing monomers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or 2-hydroxyethyl allyl ether can be copolymerized, and the carboxyl group-containing monomers described above can be used. Metal salts can also be copolymerized.

As a polymerization method for preparing a succinimide ester group-containing vinyl polymer from such monomers, there are various known polymerization methods such as a suspension polymerization method, an emulsion polymerization method, a bulk polymerization method and a solution polymerization method. A conventional polymerization method can be applied, and a target vinyl polymer can also be prepared by making full use of a photopolymerization method, an ionic polymerization method, a radiation polymerization method, or the like.

Among them, from the viewpoint of polymerization operation and the like, the solution polymerization method, that is, the solution radical polymerization method,
Especially desirable. As the polymerization initiator used when performing such solution radical polymerization, of course, known and commonly used radical polymerization initiators are used, but if only typical representatives are illustrated among them, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) or 2,2 ′
Various azo compounds such as -azobis (2-methylbutyronitrile); or

Tert-butyl peroxypivalate,
tert-butyl peroxybenzoate, tert-
Butylperoxy-2-ethylhexanoate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-t-butyl peroxide,
Various peroxides such as dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxycarbonate.

If only typical organic solvents used in the solution polymerization reaction are exemplified, toluene, xylene, cyclohexane, n-hexane, n-hexane
Various hydrocarbons, such as octane, cyclopentane or cyclohexane; various esters, such as ethyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate;

Or various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; various ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether; Methylene chloride,
Various chlorinated hydrocarbons such as carbon tetrachloride, trichloroethane or tetrachloroethane; or N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate. Such solvents may be used alone or in combination of two or more.

In order to prepare various polymers (A) having a succinimide ester group by the method described above, a vinyl (co) polymer, a polyether polymer or a polyester having a carboxyl group can be prepared, respectively. The polymer, polyamide polymer or polyurethane polymer may be reacted with the above-mentioned N-hydroxysuccinimide compound represented by the general formula (II) in the presence of a dehydrating agent such as carbodiimide. Each resin having a carboxyl group used here is prepared by a known and commonly used method.

In order to prepare such a carboxyl group-containing vinyl polymer, as described above, a mixture of one or more carboxyl group-containing vinyl monomers, or a copolymerizable with them. , A mixture with various monomers as described above, by a known and conventional method,
It may be (co) polymerized.

To prepare a carboxyl group-containing polyether polymer, a polyoxyethylene polyether, a polyoxypropylene polyether, or a polyoxybutylene polyether having at least two hydroxyl groups per molecule are used. Various polyethers such as ethers or polyethers derived from various aromatic polyhydroxy compounds such as bisphenol A or bisphenol F, and succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid Alternatively, a polycarboxylic acid such as trimellitic acid or a reactive derivative such as an acid anhydride thereof may be reacted by a known and commonly used method.

To prepare the carboxyl group-containing polyester polymer, polycarboxylic acids as described above or reactive derivatives thereof; ethylene glycol, propylene glycol, butylene glycol, hexanediol, trimethylolpropane, trimethylol Various polyhydroxy compounds such as ethane and glycerin;
Various fatty acids; or various fats and oils, as well as ε-caprolactone, may be reacted by a known and commonly used method.

To prepare a carboxyl group-containing polyamide polymer, ethylenediamine, butylenediamine,
Various diamines such as hexamethylenediamine and dodecamethylenediamine are reacted with various dibasic acids such as succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid and dimer acid by a known and conventional method. Alternatively, various raw materials such as various lactams such as caprolactam or laurolactam may be reacted by a known and commonly used method.

In order to obtain a carboxyl group-containing polyurethane polymer, various polyurethane resins (isocyanate prepolymers) such as a polyether urethane resin or a polyester urethane resin having a hydroxyl group or an isocyanate group can be obtained by multiplying a polyvalent resin as described above. Known and commonly used methods such as reaction with carboxylic acids or anhydrides thereof can be applied.

According to the above-mentioned method, a vinyl (co) polymer, a polyether polymer, a polyester polymer, a polyamide polymer or a polyurethane polymer having a carboxyl group is combined with the above-mentioned general formula (II) When the carboxyl group-containing resin is in a liquid state when the N-hydroxysuccinimide compound represented by the above) is reacted in the presence of a dehydrating agent such as a carbodiimide, the reaction is carried out without a solvent or in a solvent. Can react.

When the carboxyl group-containing resin is solid, it must be reacted in a solvent. An organic solvent having no active hydrogen is used as the organic solvent used in the reaction in the solvent.

Specific examples of such an organic solvent include:
Aromatic hydrocarbons such as benzene, toluene or xylene; aliphatic or alicyclic hydrocarbons such as hexane, heptane, octane, cyclohexane or cyclooctane; diethyl ether, diisopropyl ether or di-n-butyl ether, dimethoxyethane , Tetrahydrofuran, dioxane, various ethers; ester solvents such as ethyl acetate, butyl acetate or amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; or

Halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethane, carbon tetrachloride, and chlorobenzene; aprotic polar solvents such as N-methylpyrrolidone and dimethylformamide; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone; Examples include various ketones such as cyclohexanone. Such solvents may be used alone or in combination of two or more.

As a method for preparing the succinimide ester group-containing polymer (A) by the above-mentioned method, the above-mentioned raw materials are charged together and reacted, or a carboxyl group-containing resin is mixed with a solvent. Or a mixture of a dehydrating agent such as a carbodiimide, an N-hydroxysuccinimide compound, or a resin,
Various reaction methods can be applied such as dropping a mixture of a solvent and a dehydrating agent such as a carbodiimide into a mixture of a solvent and an N-hydroxysuccinimide compound. The reaction temperature is preferably in the range of -40 to 100C, and more preferably in the range of -10 to 70C.

The amount of the succinimide ester group introduced into the polymer (A) thus obtained is preferably at least 5 mmol, more preferably at least 10 mmol, per 100 g of the solid content of the polymer. It is.

The succinimide ester group-containing vinyl copolymer has a number average molecular weight of 500 to 5
It is preferably in the range of 000, and 1,000 to 3
The range of 0000 is more preferable. If it is less than 500, the hydrolysis rate will be too fast and the long-term antifouling property will be inferior. If it exceeds 50,000, the hydrolysis rate will be extremely reduced.

Further, the number average molecular weight of the polyether-based polymer, polyester-based polymer, polyamide-based polymer or polyurethane-based polymer having a succinimide ester group is 250 to 50,0,0 respectively.
00, more preferably 300 to 30,000. If it is less than 250, the hydrolysis rate will be too fast and the long-term antifouling property will be inferior.
When it exceeds 000, the hydrolysis rate becomes extremely low.

In the present invention, as the resin component, the succinimide ester group-containing polymer (A) may be used alone, or a hydrophilic resin may be used to control the hydrolysis rate of (A). (B) or the hydrophilic compound (C) may be used in combination, and further, the hydrophobic resin (D) may be used in combination. The above-mentioned hydrophilic resin (B) refers to resins having high water-solubility or high water-swellability.

Representative examples of (B) include vinyl polymers having a hydrophilic group such as an ether group or an amide group, and polyether resins such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol. No.

Representative examples of the vinyl polymer having a hydrophilic group include methyl vinyl ether, N-vinylpyrrolidone, 2-methoxyethyl methacrylate, (meth) acrylamide or N, N-dimethyl (meth). ) Homopolymers of vinyl monomers having various hydrophilic groups such as acrylamide, or these various monomers, and used in preparing (A) as described above; Copolymers with copolymerizable monomers are mentioned.

The above-mentioned hydrophilic compound (C) refers to a low molecular weight compound having high water solubility or water swellability. Particularly typical examples of the hydrophilic compound (C) include monohydric alcohols, polyhydroxy compounds, monocarboxy compounds and polycarboxy compounds. Among these, monocarboxy compounds are particularly preferable. However, the use of rosin is particularly desirable.

The hydrophobic resin (D) refers to resins that are insoluble in water and have low water swellability.
Among these hydrophobic resins (D), particularly typical ones do not contain a chlorinated olefin polymer or a hydrophilic group such as an ether group or an amide group, or
An acrylic polymer having a very low content of such a hydrophilic group may be mentioned, but the present invention is not limited to these.

To obtain the resin composition for an antifouling paint of the present invention from the components (A), (B), (C) and (D), as described above, The united polymer (A) may be used alone, or the polymer (A) component and at least one of the three components other than the polymer (A) component may be used in combination.

When the polymer (A) component is used in combination with at least one of the three components other than the component (A), the components (B) and (B) are added to 100 parts by weight of the component (A). Component (C) is not more than 200 parts by weight, component (D) is not more than 200 parts by weight, more preferably (B) and / or
Or 100 parts by weight or less of the component (C) and 1
What is necessary is just to mix so that it may become the range which is below 00 weight part.

Further, an antifouling agent (E) can be added to the antifouling paint resin composition of the present invention. Particularly typical antifouling agents include triphenyltin hydroxide, triphenyltin fluoride,
Triphenyltin chloride, triphenyltin nicotinate, triphenyltin versatate, bis (triphenyltin) -α, α'-dibromosuccinate, bis (triphenyltin) oxide, triphenyltin dimethylthiocarbamate, tributyltin hydro Oxide, bis (tributyltin) oxide, tributyltin chloride, tributyltin fluoride, tributyltin acetate, tributyltin nicotinate, tributyltin versatate,
Bis (tributyltin) -α, α'-dibromosuccinate,

Tricyclohexyltin hydroxide, bis (tricyclohexyltin) oxide, tricyclohexyltin chloride, tricyclohexyltin fluoride, tricyclohexyltin acetate, tricyclohexyltin nicotinate, tricyclohexyltin versatate, bis (tricyclohexyltin) -α , Α'-
Various organic tin antifouling agents, such as dibromsuccinate;
Cupric citrate, cupric quinoline, cupric δ-hydroquinoline, cupric oleate, cupric tartrate, copper oxynate, copper naphthenate, copper nonylphenylsulfonate, copper acetate, bis (pentane Various organic copper antifouling agents such as chlorophenolic acid copper; various organic nickel antifouling agents such as nickel acetate and nickel dimethyldithiocarbamate; zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, ethylenebis Various organic zinc antifouling agents, such as zinc (dithiocarbamic acid);

N-trichloromethylthiophthalimide,
Such as N-fluorodichloromethylthiophthalimide;
Various N-trihalomethylthiophthalimide antifouling agents;
Bis (dimethylthiocarbamoyl) disulfide, N-
Various dithiocarbamic acid-based antifouling agents such as ammonium methyldithiocarbamate and ammonium ethylenebis (dithiocarbamate); N- (2,4,6-trichlorophenyl) maleimide, N-4-tolylmaleimide, N- (3- Chlorophenyl) maleimide, N- (4
Various N-arylmaleimide-based antifouling agents such as -n-butylphenyl) maleimide and N- (2,3-xylyl) maleimide;

3-benzylideneamino-1,3-thiazolidine-2,4-dione, 3- (4-methylbenzylideneamino) -1,3-thiazolidine-2,4-dione,
3- (2-hydroxybenzylideneamino) -1,3-
Thiazolidine-2,4-dione, 3- (4-dimethylaminobenzylideneamino) -1,3-thiazolidine-
Various 3-substituted amino-1,3-thiazolidine- such as 2,4-dione, 3- (2,4-dichlorobenzylideneamino) -1,3-thiazolidine-2,4-dione
2,4-dione-based antifouling agents; various dithiocyano-based antifouling agents such as dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene; triazine-based antifouling agents; naphthoquinone-based antifouling agents; Various sulfur antifouling agents, such as thiuram disulfide;

Copper oxide, nickel copper alloy, copper, copper thiocyanate, copper carbonate, copper sulfate, cupric chromate, cupric ferrocyanate, cupric nitrate, cupric phosphate, oxidized copper Copper,
Various copper-based antifouling agents, such as cuprous iodide or cuprous sulfite; various organic antifouling agents, such as zinc sulfate, zinc oxide, nickel sulfate, strontium chromate, and various metal antifouling agents , Is an inorganic antifouling agent. In addition, various fungicides,
Compounds used for algicides, fungicides and the like can also be used.
These antifouling agents may be used alone or in combination of two or more.

The antifouling agent (E) is used in an amount of 1 to 700 parts by weight, more preferably 2 to 700 parts by weight, based on 100 parts by weight of the resin component.
What is necessary is just to mix 500 weight part. If it is less than 1 part by weight, the effect of adding the antifouling agent (E) component is small, and if it exceeds 700 parts by weight, it becomes difficult to mix it into the system, which is not preferable.

Further, the antifouling paint resin composition of the present invention may contain pigments. Typical examples thereof include inorganic pigments such as titanium oxide, iron oxide, and carbon black; and organic pigments such as azo, cyanine, and quinacridone. In general, inorganic pigments are used. These pigments may be used alone or in combination of two or more.

The antifouling paint composition of the present invention thus obtained is used as a paint for ship bottoms, a paint for underwater structures, or a paint for fishing nets.

[0082]

Next, the present invention will be described more specifically with reference examples, examples and comparative examples, but the present invention is not limited to only these examples. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Polymer (A) Having Structure Represented by General Formula (I)] A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel, and a nitrogen gas inlet tube was prepared as follows. 50 parts of ethyl acetate and 50 parts of dimethylformamide were charged, and the temperature was raised to 80 ° C. while passing nitrogen gas.

Then, at the same temperature, 700 parts of N-methacryloyloxy-succinimide monomer, 120 parts of methyl methacrylate and 180 parts of 2-ethylhexyl methacrylate, 450 parts of ethyl acetate and 450 parts of dimethylformamide were added. Part of 2,2'-azobis (2-methylbutyronitrile) and tert
-Butyl peroxy-2-ethylhexanoate 20
Part of the mixture was added dropwise over 4 hours. Thereafter, stirring was continued for 16 hours at the same temperature to obtain a solution of the target polymer having a nonvolatile content of 50%. Hereinafter, this is referred to as A-
Abbreviated as 1.

REFERENCE EXAMPLE 2 (Same as above) A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas introducing tube was charged with 50 parts of ethyl acetate and 50 parts of dimethylformamide. The temperature was raised to 80 ° C. under aeration.

Then, at the same temperature, 700 parts of N-methacryloyloxy-phthalimide, 200 parts of methyl methacrylate and 100 parts of ethyl acrylate, 450 parts of ethyl acetate and 4 parts of dimethylformamide
50 parts, 5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 15 parts of 2,2′-azobis (2-methylbutyronitrile), and tert-butylperoxy-2-ethylhexa A mixture of 40 parts of noate was added dropwise over 4 hours. After that, at the same temperature,
The mixture was stirred for 16 hours to obtain a solution of the target polymer having a nonvolatile content of 50%. Hereinafter, this is abbreviated as A-2.

REFERENCE EXAMPLE 3 (Same as above) 100 parts of xylene was charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas inlet tube, and heated to 90 ° C. under nitrogen gas flow. Warmed.

Next, at the same temperature, "Aronix M-
5300 "(a carboxyl group-containing acrylate monomer manufactured by Toa Gosei Chemical Industry Co., Ltd.), 500 parts of a monomer obtained from N-hydroxy-succinimide, 400 parts of methyl methacrylate, and dimethyl acrylamide. 100 parts, 900 parts of xylene, 2,
A mixture of 25 parts of 2'-azobis (2-methylbutyronitrile) and 25 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise over 4 hours. Thereafter, the mixture was stirred at the same temperature for 16 hours to obtain a solution of the target polymer having a nonvolatile content of 50%.
Hereinafter, this is abbreviated as A-3.

REFERENCE EXAMPLE 4 (Same as above) 100 parts of xylene was charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas inlet tube, and heated to 90 ° C. under nitrogen gas ventilation. Warmed.

Next, at the same temperature, "Aronix M-
5500 "and 500 parts of a monomer obtained from N-hydroxy-phthalimide, 250 parts of methyl methacrylate
Parts and 250 parts of ethyl acrylate, 900 parts of xylene, 25 parts of 2,2'-azobis (2-methylbutyronitrile) and tert-butylperoxy-
A mixture of 25 parts of 2-ethylhexanoate was added dropwise over 4 hours. After that, at the same temperature, 1
After stirring for 6 hours, a solution of the target polymer having a nonvolatile content of 50% was obtained. Hereinafter, this is referred to as A-4.

Reference Example 5 (same as above) 400 parts of toluene and 400 parts of butyl acetate were charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel, and a nitrogen gas inlet tube, and nitrogen gas was introduced. Below, the temperature was raised to 105 ° C.

Then, at the same temperature, 300 parts of methyl methacrylate, 400 parts of ethyl acrylate and 300 parts of methacrylic acid, 200 parts of toluene,
A mixture of 25 parts of 2'-azobis (2-methylbutyronitrile) and 40 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise over 5 hours.

Thereafter, the mixture was stirred at the same temperature for 6 hours. The solution was then cooled to room temperature and 401 parts of N-hydroxy-succinimide were added. Further, in the solution, 19-19 of dicyclohexylcarbodiimide 7 was added.
Parts and 338 parts of tetrahydrofuran at the same temperature
After dropwise addition over a period of time, and the reaction was further continued for 6 hours, the deposited dicyclohexylurea was separated by filtration to obtain a solution of the target polymer having a nonvolatile content of 50%.
Hereinafter, this is referred to as A-5.

Reference Example 6 (same as above) In a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas introducing tube, 1,000 parts of polyethylene glycol having a molecular weight of 1,000 and succinic anhydride were added. Charge 200 parts and stir under nitrogen atmosphere
The temperature was raised to 140 ° C. Then, the mixture was reacted at the same temperature for 4 hours to obtain a polyether polymer.

Thereafter, the mixture was cooled to 30 ° C. and 3
73 parts and 705 parts of tetrahydrofuran, and N-
After adding 326 parts of hydroxy-phthalimide, 412 parts of dicyclohexylcarbodiimide and 412 parts of tetrahydrofuran were added dropwise at the same temperature over 3 hours, and the reaction was continued for 6 hours. Thereafter, the precipitated dicyclohexylurea was separated by filtration to obtain a target polyether resin having a nonvolatile content of 50%. Hereinafter, this is referred to as A-6.

Reference Example 7 (same as above) An adduct having a molar ratio of trimethylolpropane to ε-caprolactone of 1: 3 was added to a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel, and a nitrogen gas inlet tube. Of 4
76 parts and 300 parts of succinic anhydride were charged and heated to 140 ° C. while stirring under a nitrogen atmosphere.

Next, the mixture was reacted at the same temperature for 4 hours to obtain a carboxyl group-containing polyester. After cooling to room temperature, 491 parts of tetrahydrofuran, 267 parts of toluene and 345 parts of N-hydroxy-succinimide were added, and further, 309 parts of tetrahydrofuran and dicyclohexylcarbodiimide 6
18 parts were added dropwise at room temperature over 3 hours.

After that, the reaction was continued for another 4 hours, and the precipitated dicyclohexylurea was separated by filtration to obtain a polyester resin having a nonvolatile content of 50%. Hereinafter, this is abbreviated as A-7.

Reference Example 8 (same as above) In a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas inlet tube, 1,500 parts of polypropylene glycol having a number average molecular weight of 500 and hexamethylene diisocyanate were added. 336 parts and 0.9 parts of dibutyltin dilaurate were charged, and the temperature was increased to 100 ° C. while stirring under a nitrogen atmosphere.

Then, after reacting at the same temperature for 8 hours, 605 parts of butyl acetate, 9 parts of triphenylphosphine and 296 parts of phthalic anhydride were added, and 12 parts of phthalic anhydride were added.
The temperature was raised to 0 ° C., and the mixture was reacted at the same temperature for 6 hours to obtain a carboxyl group-containing polyurethane resin. Thereafter, at room temperature, 1,406 parts of tetrahydrofuran and 326 parts of N-hydroxy-phthalimide were added.
412 parts of tetrahydrofuran and 412 parts of dicyclohexylcarbodiimide were added dropwise at room temperature over 3 hours.

After that, the reaction was continued for another 4 hours, and the deposited dicyclohexylurea was separated by filtration.
The desired urethane polymer having a nonvolatile content of 50% was obtained.
Hereinafter, this is abbreviated as A-8.

Reference Example 9 (same as above) In a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas inlet tube, 776 parts of dimethyl terephthalate, 361 parts of 1,6-hexanediol and ethylene glycol were added. Was added and 2.5 parts of zinc acetate were charged, and a methanol removal reaction was performed at 160 to 210 ° C. under a nitrogen atmosphere.

Next, the reaction mixture was kept at 160 ° C., and 192 parts of trimellitic anhydride and 1 part of succinic anhydride were added.
After adding 00 parts, the reaction was carried out at the same temperature for 3 hours to obtain a carboxyl group-containing polyester resin. 30
C., and at that temperature 861 parts of tetrahydrofuran and 387 parts of N-hydroxy-methyl-succinimide are added, followed by 412 parts of tetrahydrofuran and 412 parts of dicyclohexylcarbodiimide.
Parts were added dropwise over 2 hours.

After that, the reaction was continued for another 4 hours, and the deposited dicyclohexylurea was separated by filtration.
A solution of the target polyester resin having a nonvolatile content of 50% was obtained. Hereinafter, this is referred to as A-9.

Reference Example 10 [Preparation Example of N-vinylpyrrolidone copolymer (B) as hydrophilic resin] Xylene was placed in a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas inlet tube. And 400 parts of n-butanol were charged, and nitrogen gas was blown into the internal solution for 30 minutes.
The temperature was raised to 0 ° C., and 100 parts of xylene, 100 parts of n-butanol, 10 parts of tert-butylperoxy-2-ethylhexanoate, and 80 parts of N-vinylpyrrolidone
0 parts and 200 parts of methyl methacrylate were added dropwise over 5 hours. Thereafter, the reaction was continued at 100 ° C. for 10 hours to obtain a water-soluble target resin. Hereinafter, this is abbreviated as B-1.

Reference Example 11 [Preparation Example of Acrylamide Copolymer (B) as Water-Soluble Resin] 800 parts of xylene was placed in a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas inlet tube. After charging, the temperature was raised to 100 ° C.
0 parts, 20 parts of tert-butylperoxy-2-ethylhexanoate and 5 parts of azobisisobutyronitrile, and 500 parts of N, N-dimethylacrylamide.
, A mixture of 200 parts of methyl methacrylate and 300 parts of ethyl acrylate was added dropwise over 6 hours.

Further, the reaction was continued at the same temperature for 8 hours to obtain a water-soluble target resin. Hereinafter, this is referred to as B-2
Abbreviated as

Reference Example 12 [Preparation Example of Hydrophobic Copolymer (C)] After 800 parts of xylene was charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas inlet tube. After heating to 100 ° C., 20
A mixture of 0 parts, 20 parts of tert-butylperoxy-2-ethylhexanoate, 5 parts of azobisisobutyronitrile, 800 parts of methyl methacrylate and 200 parts of isobutyl acrylate was added for 6 hours. And dropped. Further, the reaction was continued at the same temperature for 8 hours to obtain a hydrophobic target resin. Hereinafter, this is referred to as C-
Abbreviated as 1.

Examples 1 to 9 and Comparative Examples 1 to 5 Based on the composition as shown in Table 1, the respective components were compounded and kneaded and dispersed.
The antifouling paints Nos. 9 to 9 and the control antifouling paints of Comparative Examples 1 to 5 were prepared, and their performances were compared and examined in accordance with the procedure described later.

[0110]

[Table 1]

<< Footnote to Table 1 >> Rosin was used as a 50% toluene solution. As the chlorinated rubber, "ADEKA chlorinated rubber CR-10" (manufactured by Asahi Denka Kogyo KK) was used and used as a 50% ethyl acetate solution.

[0112]

[Table 2]

[0113]

[Table 3]

<< Guidelines for Performance Test >> (I) Rotary Test Sand-blasted, 10 cm × 10 cm × 0.8 m
m on a copper plate with a thickness of 5 microns (μm) with an etching primer,
Furthermore, tar and vinyl based anticorrosive paint for ship bottoms
Coating was performed once so as to be 0 μm.

Next, Examples 1 to 9 and Comparative Examples 1 to
Each of the antifouling paints obtained in 5 was coated with a coating thickness of 60 μm.
m was applied three times. Thereafter, each test plate thus obtained was attached to the outside of a rotating drum suspended below the sea surface, and the drum was rotated with respect to the test plate so that the speed of seawater was 10 knots. A three-month rotary test was performed to measure the initial film thickness and the difference in film thickness after aging to evaluate the self-polishing property. Table 2 summarizes the test results.

[0116]

[Table 4]

<< Footnotes to Table 2 >>"Self-polishingproperty" is indicated by the degree of wear of the coating film (μm / month).

[0118]

[Table 5]

(II) Simulation Test A sand blasted copper plate having a size of 10 cm × 10 cm × 1 mm was firstly coated with tar
Epoxy paint is applied to a thickness of 125 μm.
Coating was performed once, and then a tar-vinyl intermediate coating was applied once so that the coating thickness became 70 μm. Thereafter, each of the antifouling paints obtained in Examples 1 to 9 and Comparative Examples 1 to 5 was coated so that the coating thickness became 100 μm.
I painted three times.

Next, each of the test plates thus obtained was subjected to the rotary test as described above for one month, and then immersed in a 1.5 m sea for one month. Thus, the test period was one cycle. As described above, a simulation test assuming the operation of a ship was carried out, and the rust prevention for each cycle was indicated by the occupied area (%) of the adhered product on the test coating film. Table 3 summarizes the test results.

[0121]

[Table 6]

<< Footnotes to Table 3 >> All the values in the table are indicated by the occupied area (%) of the adhered product.

[0123]

[Table 7]

[0124]

The composition for antifouling paints of the present invention uses a polymer having a specific functional group which is gradually hydrolyzed in sea water, and is therefore strong and moderate in strength. It is possible to form a novel coating film that retains a high water solubility.

Therefore, the composition of the present invention can stabilize the antifouling agent incorporated in the paint over a long period of time,
Because it can be eluted, it can be used for surface coating on various objects to be coated, such as ship bottoms, fish nets or underwater structures.
It is extremely useful.

Continuation of the front page (56) References JP-A-63-107906 (JP, A) JP-A-58-183761 (JP, A) JP-A-51-59931 (JP, A) JP-A-4-261415 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 5/16

Claims (5)

(57) [Claims] 1. A general formula (I) ## STR1 ## Wherein R 1 and R 2 are each independently
Represents a hydrogen atom or a halogen atom, or
Unsubstituted alkyl group having 1 to 18 carbon atoms, aryl
Group, aralkyl group, alkoxycarbonyl group, alcohol
Xy, aryloxy, alkanoyl, alkano
Represents an yloxy, nitro or cyano group
And R1 and R2 are substituted or unsubstituted alkyl groups.
To form a substituted chain or a substituted or unsubstituted aromatic ring
It may be. A resin composition for an antifouling paint, comprising a polymer (A) having a succinimide ester group having a structure represented by the following formula (I) as an essential film-forming component: 2. The resin composition for an antifouling paint according to claim 1, comprising a hydrophilic resin (B) and / or a hydrophilic compound (C). 3. The resin composition for an antifouling paint according to claim 1, which comprises a hydrophobic resin (D). 4. The resin composition for an antifouling paint according to claim 1, further comprising an antifouling agent (E). 5. The polymer (A) having a succinimide ester group is at least one selected from a vinyl polymer, a polyether polymer, a polyester polymer, a polyamide polymer and a polyurethane polymer. The resin composition for an antifouling paint according to any one of claims 1 to 4, which is a polymer.