JPH08218003A - Varnish composition and antifouling coating composition - Google Patents

Abstract

PURPOSE: To obtain a varnish composition containing a specific copolymer, free from dangerous property which e.g. organotin copolymer has, capable of providing a coating film capable of keeping excellent consuming property of coating film and stainproof property for a long period and not gelling even by kneading with a copper compound. CONSTITUTION: This composition contains a copolymer obtained by copolymerizing (A) an unsaturated monomer of formula I [(x) is 0-3; (y) is 1-10; R<1> is H or methyl; R<2> is H, a straight-chain, branched or cyclic alkyl, etc.; R<3> is CH3 , C2 H5 , etc.)] with (B) an unsaturated monomer copolymerizable with the component A [preferably an unsaturated monomer of formula II (R<4> is H or methyl; (x) is 1-6; (y) is 1-100; R<5> is a straight chain, branched or cyclic alkyl, aryl, etc.)]. Furthermore, the components A and B are each preferably used in amounts of 5-35mol% and 50-99.9mol% based on total amount of monomers constituting the copolymer. The composition is preferably blended with 1,2,3-triazole, 1,2,4-triazole, etc., in order to prevent thickening caused by mixing with the copper compound which is an antifouling agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a varnish composition and an antifouling coating composition for the purpose of preventing adhesion of aquatic organisms to underwater structures such as ships, fishing nets and drainage channels.

[0002]

2. Description of the Related Art A large number of marine organisms such as barnacles, ascidians, serpras, blue mussels, and sea lions inhabit seawater. When structures such as ships, fishing nets, drainage channels, etc. are installed or put in service in the sea, marine organisms adhere and grow to cause various damages. For example, if marine organisms adhere to the bottom of the ship, frictional resistance with seawater increases, causing a decrease in navigation speed, and fuel consumption increases to maintain a constant speed, which is not economically preferable. In addition, when marine organisms attach to a fishing net for aquaculture, the net may be closed and the seafood may be killed.

Conventionally, in order to prevent marine organisms from adhering to such marine structures, an antifouling paint containing a homopolymer or copolymer of an organic tin-containing unsaturated monomer as a resin component (Japanese Patent Publication No. 40-21426, Japanese Patent Publication No. 44-957.
9, Japanese Patent Publication No. 46-13392, Japanese Patent Publication No. 49
-20491, Japanese Patent Publication No. 51-11647,
Japanese Patent Publication No. 51-12049, Japanese Patent Publication No. 52-4817
No. 0, etc.) was painted. In these polymers, the organic tin part is hydrolyzed by seawater (pH 8.0 to 8.3), not only the organic tin acts as an antifouling agent, but also the seawater solubilized polymer surface gradually moves to seawater. Is exposed to the surface of a new coating film, thereby exhibiting a long-term stable antifouling effect. However, organotin released from these paints into seawater is not very easy to decompose and accumulates not only in marine organisms but also in the human body due to the food chain, causing damage such as malformation, so it is extremely dangerous, The use of organotin compounds has become limited.

It has been desired to develop a resin for an antifouling paint which can achieve stable antifouling property for a long period of time in place of such a highly dangerous organotin resin. Ideally, it is preferable that the same hydrolysis type as the organic tin-based resin shows the film depletion property,
Proposals using hydrophilic or water-repellent resins have also been made (JP-A-62-290768 and JP-A-62-13).
471, JP-A-58-180565, JP-A-57-67672). However, it is difficult to realize long-term stable antifouling property only by the properties of hydrophilicity and water repellency. Therefore, resins having various special carboxylic acid esters in the side chains as those which are hydrolyzable have been proposed (Tokusho Sho 60-
500452, JP-A-2-69576, JP-A-63-215780, JP-B-55-3927.
No. 1, JP-A-62-57464, JP-B-61
However, the effect is not completely satisfactory.

On the other hand, a copolymer of a maleic anhydride derivative is disclosed in JP-A-2-99567 and JP-A-51-1241.
No. 30, JP-A-62-135575, and JP-A-62-501293 propose to use a copolymer of a derivative having a free carboxyl group for this purpose. It is expected that these copolymers are not toxic per se, unlike the organic tin resins, and are also excellent in coating film depletion.

[0006]

However, when the above-mentioned copolymer is used in an antifouling paint, it causes a thickening-gelation of the paint during storage by kneading with a copper compound currently used as a poison. In addition, it has a fatal drawback that the coating film is less consumable. INDUSTRIAL APPLICABILITY The present invention is capable of forming a coating film which does not have the risk of an organotin copolymer, and which exhibits a comparable coating film depletion property and can further maintain excellent antifouling property for a long period of time. It is possible to provide a varnish composition and an antifouling coating composition which are useful for a coating having excellent storage stability, which does not gel even when kneaded with a copper compound.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have the object of solving the above problems and developing an antifouling paint which is excellent in the property of preventing the adhesion of marine organisms and has no danger. As a result of earnest research, the present invention has been completed.

That is, the present invention has the general formula (I)

[Chemical 4] (In the formula, x is an integer of 0 to 3, y is an integer of 1 to 10, R ¹
Is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group, and R ³ is

Embedded image At least one unsaturated monomer represented by an indole group, an imidazole group or an N-methyl-imidazole group (provided that when y is 2 or more, a plurality of R ^{3 s} may be the same or different) A varnish composition comprising (a) and a copolymer (A) obtained by polymerizing at least one other unsaturated monomer (b) copolymerizable therewith, and the above varnish composition. The present invention relates to an antifouling coating composition containing an antifouling agent.

In the present invention, since the unsaturated monomer (a) represented by the above general formula (I) is used as an essential component, properties such as hydrolyzability are improved. General formula (I)
In, the linear, branched or cyclic alkyl group, aryl group or aralkyl group represented by R ² is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert group. -Butyl group,
Pentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, o-tolyl group, m-tolyl group, p-
Tolyl group, 2,3-xylyl group, 2,4-xylyl group,
Examples thereof include o-cumenyl group, m-cumenyl group, p-cumenyl group, mesityl group, benzyl group, phenethyl group, tolyl group, naphthyl group and norbornyl group.

The unsaturated monomer of the general formula (I) can be produced by various known synthetic routes. Moreover, you may use a commercially available unsaturated monomer. Specific preferred examples of the general formula (I) include the following compounds.

[0011]

[Chemical 6]

[0012]

[Chemical 7]

[0013]

Embedded image

[0014]

[Chemical 9]

[0015]

[Chemical 10]

[0016]

[Chemical 11]

[0017]

[Chemical 12]

[0018]

[Chemical 13]

[0019]

Embedded image

[0020]

[Chemical 15]

[0021]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group)

The unsaturated monomer (a) represented by the general formula (I) is preferably compounded in a proportion of 0.1 to 50 mol%, preferably 0.5 to 40, based on the total amount of monomers. It is more preferably mol%, particularly preferably 5 to 35 mol%. If it is less than 0.1 mol%, there is almost no effect of addition, while if it exceeds 50 mol%, the coating film stability tends to decrease. These unsaturated monomers (a) represented by the general formula (I) can be used alone or in combination of two or more.

The unsaturated monomer (b) copolymerizable with the one or more unsaturated monomers (a) represented by the general formula (I) used in the present invention is not particularly limited. There is no. It is preferable to use an unsaturated acid anhydride or an unsaturated carboxylic acid as one component of the unsaturated monomer (b) because the properties such as hydrolyzability are further improved. As the unsaturated acid anhydride,
Maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, ethyl maleic anhydride, diethyl maleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, bromomaleic anhydride, dibromomaleic anhydride Substance, 1-methyl itaconic anhydride, 1,2-
Dimethyl itaconic anhydride, 1-phenyl maleic anhydride, citraconic anhydride, cyclopentene dicarboxylic acid anhydride, chlorocyclopentene dicarboxylic acid anhydride, nitrocyclopentene dicarboxylic acid anhydride, methyl cyclopentene dicarboxylic acid anhydride, ethyl cyclopentene dicarboxylic acid anhydride, Dimethyl cyclopentene dicarboxylic acid anhydride, diethyl cyclopentene dicarboxylic acid anhydride,
Cyclohexene dicarboxylic acid anhydride, chlorocyclohexene dicarboxylic acid anhydride, nitrocyclohexene dicarboxylic acid anhydride, methyl cyclohexene dicarboxylic acid anhydride, ethyl cyclohexene dicarboxylic acid anhydride, dimethyl cyclohexene dicarboxylic acid anhydride, diethyl cyclohexene dicarboxylic acid anhydride, cyclohep Tendicarboxylic acid anhydride, bicyclo [2.2.1] heptenedicarboxylic acid anhydride, bicyclo [2.2.2] octenedicarboxylic acid anhydride, hexachloro-bicyclo [2.2.1] heptenedicarboxylic acid anhydride , 7-oxabicyclo [2.
2.1] Heptene dicarboxylic acid anhydride and the like. Among these, preferably, maleic anhydride, methylmaleic anhydride, dimethylmaleic anhydride, ethylmaleic anhydride, diethylmaleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, bromomaleic acid. Acid anhydride, dibromomaleic anhydride, 1-
Examples thereof include methyl itaconic anhydride, 1,2-dimethyl itaconic anhydride, 1-phenyl maleic anhydride, and citraconic anhydride. Further, the above-mentioned unsaturated acid anhydrides can be used alone or in combination of two or more kinds. When the unsaturated acid anhydride is used in the present invention, the amount thereof is preferably 1 to 50 mol% with respect to the total amount of the monomers, and particularly preferably 10 to 40 mol%. 1 mol%
If less than, it is difficult to obtain a resin exhibiting sufficient coating film wearability,
If it exceeds 50 mol%, unreacted unsaturated acid anhydride remains,
It tends to adversely affect the stability of the coating film.

Unsaturated carboxylic acids are those having a free carboxyl group, such as acrylic acid, methacrylic acid,
Examples thereof include crotonic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like. Further, a monoester of dicarboxylic acid can also be used. Among these, acrylic acid or methacrylic acid is preferable because of its high effect.
Further, the above unsaturated carboxylic acids can be used alone or in combination of two or more. When an unsaturated carboxylic acid is used in the present invention, its amount is preferably 1 to 99 mol% with respect to the total amount of monomers, and 10 to 95
Mol% is more preferred. If it is less than 1 mol%, it is difficult to obtain a resin exhibiting sufficient coating film exhaustion, and if it exceeds 99 mol%, the stability of the coating film tends to be adversely affected. Incidentally, the unsaturated acid anhydride and the unsaturated carboxylic acid may be used in combination.

As one component of another unsaturated monomer (b) copolymerizable with at least one unsaturated monomer (a) represented by the general formula (I) used in the present invention, General formula (II)

[Chemical 17] (In the formula, R ⁴ represents a hydrogen atom or a methyl group, x represents an integer of 1 to 6, y represents an integer of 1 to 100, and R ⁵ represents a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group. The use of () is preferable because properties such as hydrolyzability are further improved. In the general formula (II), the linear, branched or cyclic alkyl group, aryl group or aralkyl group represented by R ⁵ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec
-Butyl group, tert-butyl group, pentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, o-
Tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,4-xylyl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, mesityl group, benzyl group,
Examples thereof include a phenethyl group, a tolyl group, a naphthyl group, and a norbornyl group.

The unsaturated monomer of the general formula (II) can be produced by various known synthetic routes. Moreover, you may use a commercially available unsaturated monomer. Specific preferred examples of the general formula (II) include the following compounds.

[0027]

Embedded image

[0028]

[Chemical 19]

[0029]

Embedded image

[0030]

[Chemical 21]

[0031]

[Chemical formula 22]

[0032]

[Chemical formula 23] (In the formula, R ⁴ represents a hydrogen atom or a methyl group)

The unsaturated monomer represented by the general formula (II) is
The compounding ratio is preferably 0.1 to 40 mol% and more preferably 0.5 to 25 mol% with respect to the total amount of monomers. If it is less than 0.1 mol%, there is almost no effect of addition, while if it exceeds 40 mol%, the stability of the coating film tends to decrease. These unsaturated monomers represented by the general formula (II) can be used alone or in combination of two or more.

Further, as the unsaturated monomer (b), the above-mentioned unsaturated acid anhydride, unsaturated carboxylic acid and the general formula (I
A monomer other than the unsaturated monomer represented by I) can be used, and examples thereof include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester and isobutyl of acrylic acid or methacrylic acid. Ester, sec-butyl ester, tert-butyl ester, 2-ethylhexyl ester, octyl ester,
Nonyl ester, decyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, pentadecyl ester, hexadecyl ester, heptadecyl ester, octadecyl ester, nonadecyl ester, eicosyl ester, heneicosyl ester, doco Syl ester, cyclohexyl ester, benzyl ester, phenyl ester, dimethylaminoethyl ester, dimethylaminopropyl ester, 2-chloroethyl ester, 2,2,2-trichloroethyl ester, 2-fluoroethyl ester,
2,2,2-trifluoroethyl ester, 2-cyanoethyl ester, trimethylsilyl ester, triethylsilyl ester, tripropylsilyl ester, tributylsilyl ester, trihexylsilyl ester,
(Meth) acrylic acid ester-based monomers such as trimethoxysilyl ester, triethoxysilyl ester, tripropoxysilyl ester, tributoxysilyl ester, trihexyloxysilyl ester, triphenylsilyl ester, triphenoxysilyl ester, styrene, Styrene-based monomers such as α-methylstyrene and pt-butylstyrene, polyolefin-based monomers such as butadiene, isoprene and chloroprene, vinyl-based monomers such as vinyl chloride and vinyl acetate, and other acrylonitrile and methacryloyl Examples thereof include nitrile-based monomers such as nitrile. Preferably, acrylic acid or methacrylic acid methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, 2-ethylhexyl ester, dodecyl ester,
Cyclohexyl ester, benzyl ester and styrene. When an unsaturated monomer other than the unsaturated acid anhydride, the unsaturated carboxylic acid and the unsaturated monomer represented by the general formula (II) is used, the mixing ratio is 5 with respect to the total amount of the monomers. ~ 9
It is preferably 0 mol%. If it is less than 5 mol%, the water resistance tends to be poor, and if it exceeds 90 mol%, the coating film wear resistance tends to be poor.

Further, the mixing ratio of the whole unsaturated monomer (b) including the unsaturated acid anhydride, the unsaturated carboxylic acid and the unsaturated monomer represented by the general formula (II) is the whole unit amount. It is preferably 50 to 99.9 mol% with respect to the body weight from the viewpoint of stability of the coating film and consumption of the coating film. The polymer may be prepared by any polymerization method, but the preparation method is usually different when the component (b) contains an unsaturated acid anhydride and when it does not contain an unsaturated acid anhydride. When the component (b) contains an unsaturated acid anhydride, a solution containing the monomer (a), the other monomer (b) and the radical polymerization catalyst may be added dropwise to the solvent solution for polymerization. Polymerization is preferred. The reaction temperature is usually about 0 to 180 ° C., preferably about 40 to
It is 170 ° C. The dropping time is usually 1 to 10 hours, preferably 2 to 6 hours. As the organic solvent used,
Solvents having low hydrophilicity and having no reactivity with unsaturated acid anhydrides are preferable, and aromatic solvents such as xylene and toluene are particularly preferable.

When the component (b) does not contain an unsaturated acid anhydride, a method of dropping a solution containing the monomer (a), another monomer (b) and a radical polymerization catalyst into a solvent is used. Can be done by. The reaction temperature is usually about 0 to 1
The temperature is 80 ° C, preferably about 40 to 170 ° C. The dropping time is usually 1 to 10 hours, preferably 2 to 6 hours. The organic solvent to be used can be used alone or as a mixture of two or more kinds as long as it has no reactivity with the unsaturated monomer and dissolves the produced copolymer. For example, methanol, ethanol, propanol,
Isopropanol, butanol, isobutanol, alcohol solvents such as benzyl alcohol, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, polyalkylene glycol solvents such as ethylene glycol monoacetate, aromatic hydrocarbon solvents such as toluene and xylene, acetic acid Examples include ester solvents such as ethyl and butyl acetate, ketone solvents such as cyclohexanone and methyl isobutyl ketone, halogen solvents such as carbon tetrachloride and trichloroethane, and water that does not cause environmental pollution is also considered as one of the solvents. be able to.

When the copolymer (A) is a copolymer having a carboxyl group, it has a too high viscosity in an aromatic hydrocarbon-based solvent having a low polarity such as toluene or xylene, and therefore, it is used as a coating material. Since it is difficult to use, it must be diluted with a large excess of solvent in order to make it a low viscosity that is easy to use for paints by using it as a solvent, and only a varnish with a very low resin solid content can be obtained. There are drawbacks. In order to solve this problem, it is preferable to use a solvent having a surfactant action such as alcohols, polyalkylene glycols, and water alone or as a mixed solvent with another solvent. The amount of the solvent used is not particularly limited, but is usually ½ by weight with respect to all the monomers.
It is about 2 times.

As the radical polymerization catalyst to be used, a polymerization initiator which can be used for ordinary radical polymerization such as azo compounds and peroxide compounds can be used. In particular,
2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (cyclopropylpropionitrile), 2,2'-azobis (2,4-
Dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2- Examples are phenylazo-4-methoxy-2,4-dimethylvaleronitrile, benzoyl peroxide, di-tert-butylperoxybenzoate and the like. The amount of the polymerization initiator used is not particularly limited, but it is preferably 0.1 to 5% by weight, more preferably 0.2 to 4% by weight, based on the total amount of the monomers. The number average molecular weight of the obtained polymer is not particularly limited, but from the viewpoint of various properties as a coating resin, it is preferably 3,000 to 200,000, more preferably 5,000.
It is 0 to 50,000. The number average molecular weight in the present invention is a value measured by a gel permeation chromatography method and converted using a standard polystyrene calibration curve.

Further, an appropriate chain transfer agent may be added during the polymerization for the purpose of controlling the molecular weight. Specifically, methanethiol, ethanethiol, n-propanethiol, isopropanethiol, n-butanethiol, 2-methylpropanethiol, 3-methylpropanethiol, 1,
1-dimethylethanethiol, 1-hexanethiol,
1-octanethiol, 1-decanethiol, benzenethiol, 2-methylbenzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, 2-ethylbenzenethiol, 3-ethylbenzenethiol,
4-ethylbenzenethiol, bis (4-hydroxydimethylphenyl) disulfide, bis (2-chloromethylphenyl) disulfide, bis (2-bromomethylphenyl) disulfide, dinaphthyl disulfide, di-
2-benzothiadisulfide, α-methylstyrene dimer, carbon tetrachloride, carbon tetrabromide, chloroform and the like are exemplified. The blending amount of the chain transfer agent can be appropriately selected depending on the molecular weight of the target polymer. The polymerization is performed under an inert gas atmosphere. Examples of the inert gas include nitrogen, argon, helium, neon and the like.

Next, as a component that can be added to the polymer (A) in the coating varnish composition of the present invention, one or more compounds selected from triazole derivatives, thiadiazole derivatives and benzothiazole derivatives (B Is preferable because it has a great effect of preventing thickening due to mixing with the copper compound.

In the present invention, the triazole derivative of the compound (B) is a benzotriazole derivative,
Examples include amino-substituted triazole derivatives and other triazole derivatives. Examples of the benzotriazole derivative include 1,2,3-benzotriazole and 1-methyl-
1,2,3-benzotriazole, 1-phenyl-1,
2,3-benzotriazole, 2-phenyl-1,2,
3-benzotriazole, 4-chloro-1,2,3-benzotriazole, 4-nitro-1,2,3-benzotriazole, 5-methyl-1,2,3-benzotriazole, 5-ethyl-1, 2,3-benzotriazole,
5-propyl-1,2,3-benzotriazole, 5-
Isobutyl-1,2,3-benzotriazole, 5-methoxy-1,2,3-benzotriazole, 5-chloro-1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzo Triazole, 1,2,3-benzotriazolecarboxylic acid and its ester derivative, N
-Dialkylaminomethyl-1,2,3-benzotriazole and the like, and amino-substituted triazole derivatives include 4-amino-1,2,4-triazole and 3-amino-1H-1,2,4-triazole. And other triazole derivatives include 1,2,3-triazole, 1-methyl-1,2,3-triazole, 1
-Phenyl-1,2,3-triazole, 1-benzyl-1,2,3-triazole, 2-methyl-1,2,3
-Triazole, 2-phenyl-1,2,3-triazole, 2-benzyl-1,2,3-triazole, 4-
Methyl-1,2,3-triazole, 4-phenyl-
1,2,3-triazole, 4-hydroxy-1,2,
3-triazole, 4,5-dimethyl-1,2,3-triazole, 4-methyl-2-phenyl-1,2,3-
Triazole, 4,5-dimethyl-2-phenyl-1,
2,3-triazole, 1,5-diphenyl-1,2,
3-triazole, 1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-phenyl-1,
2,4-triazole, 3-methyl-1,2,4-triazole, 3-phenyl-1,2,4-triazole,
3-chloro-1,2,4-triazole, 3-bromo-
1,2,4-triazole, 3,5-dimethyl-1,
2,4-triazole, 3,5-diethyl-1,2,4
-Alkyl, aryl such as triazole, 1,3-diphenyl-1,2,4-triazole, 1,5-diphenyl-1,2,4-triazole and 3,5-diphenyl-1,2,4-triazole; Examples include aralkyl, halogen or hydroxy substituted triazole derivatives.

Among the compounds (B), the benzothiazole derivative is preferably a sulfur-substituted benzothiazole derivative, specifically, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, N-oxydiethylenebenzothiazyl-2-. Sulfenamide, N, N-
Diisopropylbenzothiazyl-2-sulfenamide, N, N-dicyclohexylbenzothiazyl-2-sulfenamide, 3- (2-benzothiazylthio) propionic acid, (2-benzothiazylthio) acetic acid, etc. Further, as the thiadiazole derivative, a sulfur-substituted thiadiazole derivative is preferable, and specifically, 2-mercapto-1,3,4-thiadiazole, 2,5-dimercapto 1,3,4-thiadiazole, 2-amino-5- Mercapto-1,3,4-thiadiazole, 2-methyl-
There are 5-mercapto-1,3,4-thiazole, 2-methylamino-5-mercapto-1,3,4-thiadiazole, 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole and the like.

As these compounds (B), a triazole derivative is preferable because of its high effect of preventing thickening,
Specifically preferred compounds are 1,2,3-benzotriazole, 1,2,4-triazole, 3-amino-1H.
It is selected from -1,2,4-triazole. One or more of these compounds (B) can be used, but the amount used is preferably 0.1 to 50% by weight based on the copolymer (A) (resin solid content) used. , 0.2 to 10% by weight is more preferable. If it is less than 0.1% by weight, the effect of addition is not sufficient and viscosity is likely to increase due to the formation of a coating with a copper compound.
It should be noted that the varnish composition of the present invention may be mixed with a polymer other than the copolymer (A) to the extent that the effects of the present invention are not impaired. The above-mentioned varnish composition can be made into an antifouling coating composition by blending a colorant such as a known pigment, a known antifouling agent, and various additives (a filler, a dispersing agent, an anti-sagging agent, etc.).

The compound (C) in the present invention is added for the purpose of improving the long-term consumption of the coating film. The compound (C) having both a hydrophobic group and a hydrophilic group in the molecule is a compound having no reactivity with all the monomers and having both a hydrophobic group and a hydrophilic group in one molecule. As the hydrophobic group, a linear, branched or cyclic alkyl group which may have a substituent having 4 or more carbon atoms, an aryl group, an aralkyl group, or the like, or a hydrophilic group or the like, which has a carbon number of 4 or more to form a cyclic compound. And a hydrocarbon group which may have a substituent. As a hydrophilic group,

[Chemical formula 24] And other groups.

Specific compounds include dodecanol,
Alcohols such as tetradecanol, hexadecanol, octadecanol, triphenylmethanol, etc., methyl n-caproate, ethyl n-caproate, propyl n-caproate, isopropyl n-caproate, n-caproic acid n- Butyl, isobutyl n-caproate, sec-butyl n-caproate, tert-butyl n-caproate, n
-Methyl caprylate, n-ethyl caprylate, propyl n-caprylate, isopropyl n-caprylate, n-butyl n-caprylate, isobutyl n-caprylate, n-
Sec-Butyl caprylate, tert-n-caprylate
Butyl, methyl n-caprate, ethyl n-caprate, propyl n-caprate, isopropyl n-caprate, n-butyl n-caprate, isobutyl n-caprate, sec-butyl n-caprate, n- Capric acid t
ert-butyl, methyl laurate, ethyl laurate,
Propyl laurate, isopropyl laurate, n-butyl laurate, isobutyl laurate, se laurate
c-Butyl, tert-butyl laurate, methyl myristate, ethyl myristate, propyl myristate, isopropyl myristate, n-butyl myristate, isobutyl myristate, sec-butyl myristate, tert-butyl myristate, palmitate Methyl, ethyl palmitate, propyl palmitate, isopropyl palmitate, n-butyl palmitate, isobutyl palmitate, sec-butyl palmitate, ter palmitate
long-chain carboxylic acid esters such as t-butyl, methyl stearate, ethyl stearate, propyl stearate, isopropyl stearate, n-butyl stearate, isobutyl stearate, sec-butyl stearate, tert-butyl stearate, Phosphate esters such as trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, phosphine oxides such as trioctylphosphine oxide, triphenylphosphine oxide, benzamide, benzanilide, lauric acid amide, lauric acid anilide, myristic acid amide, Myristic acid anilide, palmitic acid amide, palmitic acid anilide, stearic acid amide, stearic acid anilide,
Examples include amides such as ε-caprolactam, ureas such as phenylurea and diphenylurea, and thioureas such as phenylthiourea and diphenylthiourea. Of these, the melting point is 0 ° C or higher, more preferably 10 ° C or higher, and particularly 20.
A compound having a temperature equal to or higher than 0 ° C. is preferable because it has little effect on the strength of the coating film of the antifouling paint when added. Furthermore, methyl myristate, ethyl myristate, methyl palmitate, ethyl palmitate, methyl stearate, ethyl stearate, triphenyl phosphate, tricresyl phosphate, trioctylphosphine oxide, triphenylphosphine oxide, etc. It is preferable because it has a high effect of improving the consumption of the coating film, and particularly preferable are ethyl palmitate, ethyl stearate, triphenyl phosphate, trioctylphosphine oxide and triphenylphosphine oxide. The compound (C) having both a hydrophobic group and a hydrophilic group in these molecules can be used singly or in combination of two or more, and the amount used is the copolymer (A) (resin solid content) to be used. It is preferable to use in the range of 1 to 200% by weight,
Particularly, it is preferably used in the range of 5 to 50% by weight. If it is less than 1% by weight, the effect of addition is not sufficient, and the coating film wearability tends to be poor over a long period of time. If it exceeds 200% by weight, the durability of the coating film in seawater tends to decrease.

The antifouling agent used in the antifouling coating composition of the present invention preferably contains a copper compound, which is an inorganic antifouling agent, as a main component (50% by weight or more of the total antifouling agent). Examples of the copper compound include cupric chromate, cupric ferrocyanate, cupric quinoline, cupric δ-hydroquinone, cupric oleate, cupric nitrate, cupric phosphate, cupric tartrate. , Cuprous oxide, rhodan copper, copper-nickel solid solution alloy, cuprous iodide, cuprous sulfite and the like.

Other typical inorganic antifouling agents include zinc oxide, zinc chromate, and strontium chromate, and organic antifouling agents include 2,4,5,6-tetrachloroisophthalonitrile and N, N-dimethyldichlorophenylurea, 4,5-dichloro-2-n-octyl-3
(2H) -isothiazolone, zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6
-Cyclopropylamino-s-triazine, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt, Tetramethylthiuram disulphide,
2,4,6-trichlorophenylmaleimide, 2,3,
5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatolylsulfone, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, pyridine-triphenylborane, etc. . In addition, the use of an organic tin compound, a triazine compound, an organic sulfur compound or the like as an antifouling agent does not hinder anything. The amount of these antifouling agents used is not particularly limited,
The amount is preferably 1 to 500% by weight based on the total amount of polymer (resin solid content). Particularly, 50 to 450% by weight is preferable. If it is less than 1% by weight, it hardly shows an effect as an antifouling agent.
If it exceeds 100% by weight, a good coating film tends to be difficult to be formed.

As typical pigments, inorganic pigments such as titanium oxide (titanium white), iron oxide and carbon black, and organic pigments such as azo, cyanine, phthalocyanine and quinacridone pigments can be used. Inorganic pigments are usually used. These pigments are used as needed. When used, its amount is not particularly limited, but is preferably 200% by weight or less based on the total amount of polymer (resin solid content). When the pigment is used, if it exceeds 200% by weight, the stability as a coating film tends to be poor. Further, as the extender, there are calcium carbonate, barium sulfate, magnesium oxide, alumina, zeolite and the like. These extenders are used as needed. When used, the amount used is not particularly limited, but it is preferably used within a range of 100% by weight or less based on the total amount of the polymer (resin solid content).
When a filler is used, if it exceeds 100% by weight, the stability as a coating film tends to be poor.

The dispersion or anti-sagging agent may be an inorganic dispersion or anti-sagging agent such as silica gel type, bentonite type, kaolinite type, talc type, hectorite type, montmorillonite type, saponite type, beidellite type, fatty acid amide type, Organic dispersion of fatty acid ester type, polyethylene oxide type, sulfuric acid ester type anion activator, polycarboxylic acid amine salt type, polycarboxylic acid type, polyamide type, high molecular weight polyether type, acrylic copolymer type, special silicone type, etc. Or there is an anti-sagging agent. The amount used is not particularly limited, but it is preferably used in the range of 0.01 to 100% by weight based on the total amount of polymer (resin solid content). If it is less than 0.01% by weight, the effect of addition is difficult to sufficiently appear, and if it exceeds 100% by weight, the stability as a coating film tends to be poor. Further, rosin, gum rosin, wood rosin, tall oil rosin and the like can be used in combination as the dissolution aid. The antifouling paint composition of the present invention thus obtained is useful as a ship bottom paint, a fishing net paint, and the like.

[0050]

EXAMPLES Next, the present invention will be explained with reference to examples, but the present invention is not limited to these. Further, in the following examples, the "antifouling coating composition" is simply abbreviated as "coating composition".

Production Example 1 65.6 g of leucine, 114.0 g of p-toluenesulfonic acid monohydrate and 25 benzyl alcohol were placed in a flask.
Add 0.0 ml and toluene 500.0 ml and add Dean-Stark
The apparatus was heated under reflux. The water formed was removed by azeotroping with toluene. The reaction was carried out until the production of water stopped (refluxed for 5 hours). After allowing to cool, ether and hexane were added to the reaction solution, and the generated crystals were filtered. The crude product (195.5 g) was recrystallized from ethanol and ether to obtain 169.5 g of crystals.

Production Example 2 Toluene 800 was added to a four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introducing tube, a dropping funnel and a thermometer.
0 g, 166.6 g of the compound synthesized in Production Example 1 and 60.9 g of pyridine were added. Next, 36.6 g of methacrylic acid chloride was added dropwise over 1 hour while stirring under a nitrogen gas stream, and the mixture was further stirred for 4 hours. The crystalline substance formed in the reaction solution was removed by filtration. The filtrate was concentrated, washed with water three times, and the solution was dried over magnesium sulfate. After magnesium sulfate was filtered off, the solution was concentrated and dried to obtain 97.6 g of crude crystals. Recrystallization from ethanol and ether to give a purified product 81.3g of Exemplified Compound No. (I-7) (R = CH 3).

Production Example 3 In a four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introduction tube, a dropping funnel and a thermometer, xylene 250.
0 g and 49.64 g of maleic anhydride were added and kept at 95 ° C. with stirring. Next, 125.97 g of n-butyl methacrylate and 2-ethylhexyl methacrylate 12
5.47 g, Example Compound No. (II-9) (R = CH 3) 12
5.69 g, Example Compound No. (I-7) (R = CH 3) 73.
24 g and 2,2'-azobis (isobutyronitrile)
A mixture of 2.00 g (hereinafter abbreviated as AIBN) was added dropwise over 4 hours while stirring under a nitrogen gas stream. After the dropping was completed, the temperature was kept at 95 ° C. for 1 hour while further stirring.
Then, a mixture of 50.0 g of xylene and 1.00 g of AIBN was added dropwise over 1 hour, and after keeping the temperature at 95 ° C. for 30 minutes, a mixture of 50.0 g of xylene and 1.00 g of AIBN was added dropwise over 30 minutes. Then, the temperature was kept at 95 ° C. for 2 hours, 150.0 g of xylene was added, and the mixture was allowed to cool to produce a varnish having a resin solid content of 50% by weight. The number average molecular weight of the polymer in this varnish was 15,300.

Production Example 4 In a four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introducing tube, a dropping funnel and a thermometer, xylene 250.
0 g and 47.29 g of maleic anhydride were added, and the mixture was kept at 95 ° C. with stirring. Next, methyl methacrylate 2
4.14 g, 2-ethylhexyl methacrylate 239.
07G, Exemplified Compound No. (II-9) (R = CH 3) 119.7
4g, Example Compound No. (I-7) (R = CH 3) 69.77g
And AIBN (2.00 g) were added dropwise over 4 hours while stirring under a nitrogen gas stream. After the dropping was completed, the temperature was kept at 95 ° C. for 1 hour while further stirring. Next, a mixture of 50.0 g of xylene and 1.00 g of AIBN was added dropwise over 1 hour, and the mixture was kept warm at 95 ° C. for 30 minutes, and then xylene 5 was added.
A mixture of 0.0 g and AIBN 1.00 g was added dropwise over 30 minutes. Then, incubate at 95 ° C for 2 hours, and then xylene 1
After adding 50.0 g, the mixture was allowed to cool to produce a varnish having a resin solid content of 50% by weight. The number average molecular weight of the polymer in this varnish was 17,800.

Production Example 5 In a four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introducing tube, a dropping funnel and a thermometer, xylene 125.
0 g was added and the temperature was maintained at 95 ° C. with stirring. Next, 187.96 g of n-butyl methacrylate and 1 of methacrylic acid
4.23 g, Example Compound No. (I-7) (R = CH 3) 47.
A mixture of 81 g and AIBN 2.5 g was added dropwise over 3 hours while stirring under a nitrogen gas stream. After the dropping was completed, the temperature was kept at 95 ° C. for 1 hour while further stirring. Then, a mixture of 50.0 g of xylene and 0.5 g of AIBN was added dropwise over 1 hour, and then the mixture was kept warm at 95 ° C. for 2 hours to give 20 parts of xylene.
Then, 0.06 g and then 41.6 g of n-butanol were added, and the mixture was allowed to cool to produce a varnish. The number average molecular weight of the polymer in this varnish was 19,600.

Example 1 A varnish composition was produced by adding 0.5 g of 1,2,3-benzotriazole to 50 g of resin solids of the varnish produced in Production Example 3 and mixing them well.

Example 2 5.0 g of triphenyl phosphate and 1,2,3- per 50 g of resin solids of the varnish produced in the above Production Example 3
0.5 g of benzotriazole was added and mixed well to produce a varnish composition.

Example 3 A varnish composition was produced by adding 5.0 g of ethyl stearate and 0.5 g of 1,2,3-benzotriazole to 50 g of resin solids of the varnish produced in the above Production Example 3 and mixing them well. .

Example 4 0.5 g of 1,2,3-benzotriazole was added to 50 g of resin solids of the varnish produced in the above Production Example 4 and mixed well to produce a varnish composition.

Example 5 5.0 g of triphenyl phosphate and 1,2,3-per 50 g of resin solids of the varnish produced in the above Production Example 4
0.5 g of benzotriazole was added and mixed well to produce a varnish composition.

Example 6 0.5 amino 3-amino-1H-1,2,4-triazole per 50 g of resin solids of the varnish produced in the above Production Example 5
g was added and mixed well to produce a varnish composition.

Examples 7 to 12 45 g of cuprous oxide (purity: 90% by weight or more, powder), calcium carbonate 10 g, red iron oxide (iron oxide) per 15 g of resin solids of each varnish composition produced in Examples 1 to 6 above.
(III)) 5 g, Flownon S as a dispersion and anti-sagging agent
P1000 (Kyoeisha Chemical Co., Ltd.) 1 g, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-
5 g of ON and 4 g of xylene were blended, glass beads (diameter: 2 mm) were further added, and the mixture was kneaded and stirred using a mechanical stirrer, and the glass beads were filtered to prepare a coating composition.

Production Example 6 Based on the method described in JP-A-60-500452,
2,2 in a 500 ml flask equipped with a thermometer and stirrer
2-trifluoroethyl methacrylate 114.6 g,
Methyl methacrylate (14.6 g), butyl acrylate (20.8 g) and xylene (150 g) were charged, AIBN (1.5 g) was added as a polymerization catalyst, and the mixture was heated at 80 ° C. for 1 hour,
Further, polymerization was carried out at 80 ° C. for 6 hours and then allowed to cool to produce a varnish. The number average molecular weight of the polymer in this varnish is 11,
It was 000.

Production Example 7 Based on the method described in JP-A-60-500452.
A 500 ml flask equipped with a thermometer and a stirrer was charged with 118.2 g of p-nitrophenyl acrylate, 13.1 g of methyl methacrylate, 18.6 g of butyl acrylate and 150 g of xylene, and AIBN was used as a polymerization catalyst.
1.5 g was added, the mixture was heated at 80 ° C. for 1 hour, further polymerized at 80 ° C. for 6 hours, and then allowed to cool to produce a varnish. The number average molecular weight of the polymer in this varnish was 12,300.

Comparative Examples 1-2 Resin solids content of 15 of each varnish produced in the above Production Examples 6-7
Cuprous oxide (purity 90% by weight or more, powder) 45 per g
g, calcium carbonate 10 g, red iron oxide (iron (III) oxide)
5g, Flownon SP100 as dispersion and anti-sagging agent
0 (manufactured by Kyoeisha Chemical Co., Ltd.) 1 g, 4,5-dichloro-
2-n-octyl-4-isothiazolin-3-one 5 g
And 4 g of xylene were further added, and glass beads (diameter: 2 mm) were further added. After kneading and stirring using a mechanical stirrer, the glass beads were filtered to prepare a coating composition.

Storage stability test After the coating compositions prepared in Examples 7 to 12 above were stored overnight at room temperature after preparation, the state of the coating composition was observed to determine the viscosity at 25 ° C.
It was measured at. The coating composition was tightly stoppered in a sample bottle and stored in a constant temperature bath at 40 ° C. for 20 days. After storage, the state of the paint was observed and the viscosity was measured at 25 ° C.
Table 1 shows the results.

[0067]

[Table 1] From the experimental results, the coating composition of the present invention (Examples 7 to 1)
In 2), it is shown that the thickening is slight and the storage stability is excellent.

Coating Film Consumability Test After the coating compositions prepared in Examples 7 to 12 and Comparative Examples 1 to 2 were prepared and allowed to stand overnight at room temperature, the dry film thickness was 150 μm on one side of the FRP plate. A coating film was prepared so as to have the above composition and naturally dried overnight at room temperature. These FRP plates with a coating film were attached to a disc rotor plate and rotated at seawater (water temperature 15 ± 2 ° C) at a constant speed (peripheral speed of about 15 knots) for 10 months to observe the surface of the coating film and to check the film thickness of the coating film. The change was measured. The results are shown in Table 2.

[0069]

[Table 2]

As is clear from the results of this experiment, the coating compositions of the present invention (Examples 7 to 12) have very long wear resistance of coating films and are very useful as antifouling coatings. Do you get it. On the other hand, coating compositions using the varnish described in JP-A-60-500452 (Comparative Examples 1 and 2)
Was found to have a significantly low coating depletion property.

Antifouling Test Using the coating compositions of Examples 7 to 12 and Comparative Examples 1 to 2 above, coated steel (100 × 2) to which a rust preventive coating has been applied in advance.
Spray coating was performed twice on both surfaces (00 × 1 mm) so that the dry film thickness was 100 μm on one surface, and naturally dried overnight at room temperature to prepare a test plate. This test plate was attached to an immersion raft installed at Nakaminato Port in Hitachinaka City, Ibaraki Prefecture and immersed in the sea, and the number of adherent organisms (barnacles) on the test plate was observed over time. Table 3 shows the results.

[0072]

[Table 3]

As is apparent from the results of this experiment, the coating composition of the present invention is inferior to the coating composition using the varnish described in JP-A-60-500452 (Comparative Examples 1 and 2). Also, it was excellent in antifouling property, and only a little adherence of organisms was observed.

[0074]

The varnish composition according to claim 1 is suitable as a coating material, does not have the danger of organotin copolymers, and has good coating consumption and antifouling properties for a long time. Can be maintained. Further, it does not gel even when kneaded with a copper compound. The varnish composition according to the second aspect has the effects of the varnish composition according to the first aspect, and further has improved properties such as hydrolyzability. The varnish composition according to claim 3 has the effects of the varnish composition according to claim 1, and further has improved properties such as hydrolyzability. The varnish composition according to the fourth aspect has the effects of the varnish composition according to the first aspect, and particularly has a great effect of preventing thickening due to kneading with the copper compound. The varnish composition according to claim 5 is the composition according to claim 1.
The effect of the varnish composition described above is exerted, and the coating film wearability is improved over a long period of time. The varnish composition according to claim 6 has the effects of the varnish composition according to claim 5, and is less affected by the reduction in coating film strength. The antifouling coating composition according to claim 7 does not have the risk of a coating containing an organotin copolymer, and can maintain good coating film wear resistance and antifouling performance for a long period of time. The antifouling coating composition according to the eighth aspect exhibits the effect of the antifouling coating composition according to the seventh aspect, has no gelation due to kneading with a copper compound, and is excellent in storage stability.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C09D 133/26 PFW C09D 133/26 PFW C09K 3/00 112 C09K 3/00 112Z

Claims (8)

[Claims] 1. A compound of the general formula (I) (In the formula, x is an integer of 0 to 3, y is an integer of 1 to 10, R ¹
Is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group, and R ³ is At least one unsaturated monomer represented by an indole group, an imidazole group or an N-methyl-imidazole group (provided that when y is 2 or more, a plurality of R ^{3 s} may be the same or different) A varnish composition comprising (a) and a copolymer (A) obtained by polymerizing one or more other unsaturated monomers (b) copolymerizable therewith. 2. The varnish composition according to claim 1, wherein one or more unsaturated acid anhydrides or unsaturated carboxylic acids are used as a component of the other unsaturated monomer (b). 3. As a component of another unsaturated monomer (b), the compound represented by the general formula (II): (In the formula, R ⁴ is a hydrogen atom or a methyl group, x is an integer of 1 to 6, y is an integer of 1 to 100, and R ⁵ is a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group.) The varnish composition according to claim 1, wherein one or more unsaturated monomers represented by the formula (1) are used. 4. The method according to claim 1, further comprising at least one compound (B) selected from a triazole derivative, a thiadiazole derivative and a benzothiazole derivative.
Alternatively, the varnish composition according to the above item 3. 5. The varnish composition according to claim 1, further comprising a compound (C) having both a hydrophobic group and a hydrophilic group in the molecule. 6. The varnish composition according to claim 5, wherein the compound (C) has a melting point of 0 ° C. or higher. 7. An antifouling coating composition comprising the varnish composition according to any one of claims 1 to 6 and an antifouling agent. 8. An antifouling coating composition in which the antifouling agent contains a copper compound as a main component.