JP2005060510A - Coating material composition, antifouling coating film, antifouling underwater structure, and antifouling method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a coating material composition causing no coating film defects such as debonding and/or cracking with time after immersed in seawater, running out at a constant rate, exerting good marine organism adhesion-proof effect over a long period, and highly excellent in environmental safety, to prepare an antifouling coating film, to provide an underwater structure, and to provide a method for forming such antifouling coating film for the underwater structure. <P>SOLUTION: The coating material composition comprises a specific diphenylborane compound and a copolymer containing component units derived from a polymerizable unsaturated metal salt compound of the formula:R<SP>5</SP>-(CH<SB>2</SB>)<SB>k</SB>-COO-M-L<SB>q</SB>. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a coating composition, an antifouling coating film, an antifouling underwater structure, and an antifouling method, and more specifically, prevents aquatic organisms from adhering to the surface of an object in contact with seawater or lake water. A coating composition that can easily form an antifouling coating film, and by using the coating composition, aquatic organisms can be prevented from adhering to the surface of an object that contacts seawater or lake water. Antifouling coating film, antifouling underwater structure that can effectively prevent aquatic organisms from adhering to the surface in contact with seawater or lake water by having the antifouling coating film, and underwater organisms adhere It is related with the antifouling method which can prevent effectively.

  Conventionally, barnacles, mussels, bryophytes and sea squirts to underwater structures that come into contact with seawater or fresh water such as ships, buoys, stationary fishnets, aquaculture fishnets, various water pipes, anti-pollution membranes, submerged oil well drilling wells, etc. In order to prevent adhesion of marine organisms such as seaweed, mainly contains organotin hydrolyzed resin and inorganic compounds containing copper such as cuprous oxide and cuprous thiocyanate as marine organism adhesion inhibitors Paint compositions that have been used have been widely used.

  However, in recent years, the use of organotin compounds has been restricted due to the problem of environmental pollution. As an alternative, a coating composition comprising rosin, various hydrolyzable resins, slightly water-soluble resins, and the like and a bioadhesion inhibitor has been used and proposed, but its bioadhesion inhibition ability is still That's not enough.

  The performance required for coating compositions that exhibit the effect of inhibiting the adhesion of marine organisms over a long period of time is that the physiologically active substances used as inhibitors have a high adhesion inhibiting effect on many types of marine organisms. The degradable resin causes the coating film to gradually dissolve from the surface by causing hydrolysis in seawater.

  Furthermore, it is necessary to deplete the coating film so that the affinity of the physiologically active substance with respect to seawater and the affinity of the hydrolyzable resin with respect to seawater can effectively exert the physiologically active substance. Therefore, when a compound as a biofouling inhibitor has a molecular structure having a high adhesion inhibiting effect on marine adhering organisms and is combined with a hydrolyzable resin, the coating is applied to the entire coating film. Development of this composite material is possible for the first time by having an affinity for depleting the marine organism adhesion inhibitor without causing defects in the membrane.

A monomer comprising a monomer (A) obtained by blocking a specific carboxylic acid with —SiR ¹ R ² R ³ and a monomer (B) represented by Y— (CH ₂ CH ₂ O) n—R ⁴ A coating composition containing a copolymer of a mixture and triphenylboronpyridine has been proposed (see Patent Document 1).

  In Patent Document 1, triphenylboronpyridine (also referred to as pyridyl-triphenylborane) is mainly used as a bioadhesion inhibitor, and none of them can maintain its antifouling performance over a long period of time. . Pyridyl-triphenylborane is an effective physiologically active substance, but because of its high affinity with seawater, its elution rate into seawater is high, and it tends to be consumed from the coating in a short period of time. The effect cannot be maintained.

JP-A-8-277372 (Claim 1) Further, diaryl type organic boron compounds are also known as antifouling agents (see Patent Documents 2 and 3). Specifically, the “organoboron compound as an antifouling agent” described in Patent Document 5 is a compound having a specific structure containing diphenylalkylboronpyridine (claim 1 of claim 2 of Patent Document 2). The biocontrol agent for harmful water described in Patent Document 6 contains a diaryl (pyridinio or isoquinolinio) boron complex as an active ingredient ".

  In the antifouling agents described in Patent Documents 2 and 3, an effect as a biofouling inhibitor is recognized, but the antifouling performance has not been maintained for a long time (see Table 11 of Patent Document 2, (See Table 4 of Patent Document 3).

Patent No. 3034053 (Claim 1)

JP-A-9-323909 (Claim 1) Patent Document 4 contains, as an active ingredient, one or more diarylborane-amine complex compounds in which a primary amine residue is bonded to a boron atom. An underwater biofouling agent has been proposed (see claims 1 and 5 of Patent Document 4).

  However, in the technique described in Patent Document 4, it is difficult to efficiently release an organic boron compound into water, and the antifouling performance is exhibited in a certain period of time in a static sea area like a fishing net antifouling agent. However, it can be difficult to release organoboron compounds into water efficiently in the dynamic environment of structures that themselves move over the sea and lake water, such as ships. The expected release difficulty was demonstrated by the long-term antifouling performance results in the seawater with the composition.

The invention described in Japanese Patent Application Laid-Open No. 2001-342192 is disclosed as follows: "(a) Unsaturated carboxylic acid metal linear aliphatic carboxylate compound component-containing copolymer and (b) triphenylboron / amine complex" Is an antifouling paint composition characterized by containing (refer to claim 1 of Patent Document 5). Further, in claim 2, the unsaturated carboxylic acid metal linear aliphatic carboxylate compound component unit-containing copolymer (a) is represented by the general formula [II]: R1-COO-M-Ln. .. [II] [wherein R1 is any one of CH2 = C (CH3)-, CH2 = CH-, HOOC-CH = CH-, HOOC-CH = C (CH3)- An organic group containing an unsaturated bond represented by the formula, wherein —COOH may form a metal salt or ester, M represents a metal atom, and L represents an organic acid residue: -OCOR2 (R2 represents a straight-chain alkyl group or a straight-chain alkenyl group), and n represents the number of valences −1 of the metal M.] Copolymer containing component units derived from a metal salt linear aliphatic carboxylate compound Antifouling paint composition according to any of a claims 1-2. "Is disclosed.

  However, when triphenylboron pyridine is mainly used as a boron-based bioadhesion inhibitor, they cannot maintain their antifouling performance over a long period of time. Pyridyl-triphenylborane is an effective physiologically active substance, but because of its high affinity with seawater, its elution rate into water is high, and it tends to elute from the coating film in a short time. The reason is that it cannot be maintained. In addition, large-sized deposits such as mussels, barnacles, cell plastics, and bryozoans are effective over a period of time, but recent studies have also found that their physiological activity against slime is low.

JP 2001-329228 A

  This invention solves the problems associated with the prior art as described above, and does not cause coating film defects such as peeling after immersing in water, is consumed at a constant rate, and has excellent long-term antifouling properties. A paint composition, antifouling coating film, antifouling underwater structure, and antifouling method that can be applied to aluminum boats and has excellent long-term antifouling properties (18 to 24 months) as a fishing net antifouling agent. It is intended to provide.

  As a result of intensive studies, the inventors have solved the above-mentioned problems by using a specific boron compound together with a specific hydrolyzable resin, and have completed the present invention.

That is, this invention
(1) A) As a component, the following formula (1)

[However, in Formula (1), X shows a halogen atom, a C1-C8 alkyl group, or a C1-C8 alkoxy group. n is independently an integer of 0 to 3, and when n is 2 or 3, X may be the same or different. R represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, a hydroxy group, or a halogen atom.

In the formula (1), R ¹ is the following formula (2), a 5,6,7,8-tetrahydroisoquinoline group, an isoquinoline group which can be substituted with a halogen, any group of the formula (3) or the formula (4) Indicates.

  Formula (2);

(In the formula (2), Y represents a halogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or an acetyl group. M is an integer of 0 to 3, and m is 2 or 3. , Y may be the same or different.)
Formula (3);
—NH ₂ —R ² (3)
(In the formula (3), R ² represents a linear alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms.)
Formula (4);
—NH ₂ —R ³ —O—R ⁴ (4)
(However, in the formula (4), ^{R 3} is a branched alkylene group having a linear or carbon number of 1 to 24 carbon atoms 3-24, or a phenylene group, ^{R 4} is from 1 to 24 carbon atoms A linear or branched alkyl group having 3 to 24 carbon atoms.)] At least one diphenylboron compound,
B) As a component, the following formula (5)
^{_{R 5 - (CH 2) k}} -COO-M-L q ··· (5)
[In the formula (5), R ⁵ represents CH ₂ ═C (CH ₃ ) —,
CH ₂ = CH-,
HOOC-CH = CH-, and _{HOOC-CH = C (CH 3} ) -
The organic group containing an unsaturated bond shown by either formula is shown. -COOH in these formulas may form a metal salt or ester.

  k shows the integer of 0-2.

  M represents a metal atom.

L is —OCOR ⁶ (wherein R ⁶ represents an alkyl group or an alkenyl group) which is an organic acid residue, or —R ⁷ —CO—CH ₂ —CO—R ⁸ (where R ⁷ is linear) Or a divalent group formed by extracting two hydrogen atoms from a branched alkane or phenyl derivative, and R ⁸ represents a monovalent group consisting of an alkyl group or a phenyl derivative. OH is shown.

q represents the number of the valence number-1 of the metal M. ]
And a copolymer containing a component unit derived from a polymerizable unsaturated metal salt compound represented by:
(2) The coating composition according to (1) above, which contains at least one rosin compound selected from the group consisting of rosin, rosin derivatives and rosin metal salts,
(3) The coating composition according to (1) or (2), wherein the metal M in the component B) is a divalent metal.
(4) The coating composition according to any one of (1) to (3), wherein the component A) is a methyldiphenylboron compound,
(5) The component A) is pyridiniomethyldiphenylboron, (3-methylpyridinio) methyldiphenylboron, (3-bromopyridinio) methyldiphenylboron, (4-isopropylpyridinio) methyldiphenylboron, (4-t At least one selected from the group consisting of -butylpyridinio) methyldiphenylboron, (4-phenylpyridinio) methyldiphenylboron, n-octadecylaminemethyldiphenylboron, and 3- (2-ethylhexyloxy) propylaminemethyldiphenylboron It is a coating composition as described in said (1)-(4) which is a methyldiphenyl boron compound of this.

Other means for solving the above problems are as follows:
(6) An antifouling coating film comprising the coating composition according to any one of (1) to (5).

Still other means for solving the above-mentioned problems are:
(7) An antifouling underwater structure having an underwater structure and the antifouling coating film according to (6) formed on the surface thereof.

Another means for solving the above problems is as follows:
(8) An antifouling method characterized in that an antifouling coating film is formed by applying the coating composition described in (6) above to a surface in an underwater structure that can be contacted with water.

  The coating composition of this invention is characterized by comprising as essential components a copolymer containing a component unit derived from a polymerizable unsaturated metal salt compound and at least one of the compounds represented by formula (1). The coating composition, which is a composite material made of these materials, can be used for ship bottoms that require prevention of biofouling in the sea, underwater structures such as fishing nets and cooling water pipes, and antifouling antifouling coatings for offshore civil engineering. Since the coating film does not form a residual layer on the coating surface even after long-term immersion, the coating film properties do not cause defects such as cracks and peeling, and the coating film wear characteristics change over time. Therefore, the antifouling performance can be demonstrated over a long period of time, and as a fishing net antifouling agent, the antifouling performance is excellent over a long period of time. In addition, when other metal-containing antifouling agents are not used in combination, there is no risk of pitting corrosion on aluminum, so it can be applied to aluminum boats. Furthermore, since the paint composition of the present invention can exhibit very excellent antifouling performance without using cuprous oxide in combination, it cannot be vividly colored with a normal cuprous oxide-containing antifouling paint, It is a paint composition that can be colored in any vivid color and has a very good design.

<Coating composition>
In order to obtain the coating composition of this invention, at least one diphenylboron compound represented by the formula (1) is used.

  However, in Formula (1), X shows a halogen atom, a C1-C8 alkyl group, or a C1-C8 alkoxy group. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and octyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, and an octoxy group.

  In the formula (1), n is independently an integer of 0 to 3, and when n is 2 or 3, X may be the same or different.

  In the formula (1), R represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, a hydroxy group, or a halogen. Indicates an atom. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and octyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, and an octoxy group. Examples of the alkenyl group having 2 to 8 carbon atoms include an alkenyl group having a terminal double bond, such as a vinyl group, a female lopenyl group, a butenyl group, a pentenyl group, a hexenyl group, and an octenyl group; Groups and the like.

In the formula (1), R ¹ is any of the following formula (2), a 5,6,7,8-tetrahydroisoquinoline group, an isoquinoline group, a formula (3) or a formula (4) that can be substituted with a halogen. Indicates a group.

  Formula (2);

  However, in Formula (2), Y shows a halogen atom, a C1-C8 alkyl group, a phenyl group, or an acetyl group. m is an integer of 0 to 3, and when m is 2 or 3, Y may be the same or different.

  Examples of the alkyl group in the formula (2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, a hexyl group, and an octyl group. Moreover, when Y in Formula (2) is a phenyl group, the phenyl group may have a substituent.

Formula (3);
—NH ₂ —R ² (3)
However, in Formula (3), R ² represents a linear alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms.

R ² in the formula (3) is not particularly limited as a linear alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms. For example, R ² has 3 to 24 carbon atoms, preferably carbon atoms. 8 to 24, more preferably a linear or branched alkyl group having 8 to 18 carbon atoms such as n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group Group, n-octadecyl group, 2-ethylhexyl group, 3-ethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, and the like.

Formula (4);
—NH ₂ —R ³ —O—R ⁴ (4)
However, in Formula (4), R ³ is a linear alkylene group having 1 to 24 carbon atoms or a branched alkylene group having 3 to 24 carbon atoms, or a phenylene group, and R ⁴ is a straight chain having 1 to 24 carbon atoms. A chain-like or branched alkyl group having 3 to 24 carbon atoms is shown.

Examples of the linear alkylene group having 1 to 24 carbon atoms or the branched alkylene group having 3 to 24 carbon atoms represented by R ³ in the formula (4) include a methylene group, an ethylene group, a trimethylene group, a propylene group, and a tetra group. Methylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, 1-ethylethylene group, pentamethylene group, hexamethylene group, 1-butylethylene group, octamethylene group, 2-ethylhexamethylene group etc. are mentioned, As a C1-C24 linear or branched C3-C24 alkyl group shown by R < ⁴ >, a methyl group, an ethyl group, a propyl is mentioned, for example. Group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, and the like.

  The amount of the diphenylboron compound represented by the formula (1) is usually 0.01 to 60% by mass, preferably 0.1 to 40% by mass in the solid content of the paint. If the amount is too small, the antifouling effect cannot be expected. If the amount is too large, defects such as cracks and peeling tend to occur in the coating film, and a good antifouling effect cannot be obtained.

  In the coating composition according to the present invention, one kind of diphenylboron compound represented by the formula (1) can be used alone, or two or more kinds of diphenylboron compounds can be used in combination. Among the diphenylboron compounds, (4-isopropylpyrrolidio) methyldiphenylboron is particularly preferable.

  Furthermore, in the coating composition according to the present invention, if necessary, in addition to one or more diphenylboron compounds selected from the diphenylboron compounds represented by the formula (1), other protective agents known in the technical field of coatings are used. A soiling agent can be used in combination.

  Examples of such other known antifouling agents include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compounds, There are triazine compounds, copper thiocyanate, pyrithione compounds and others. More specifically, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyl-N′- Dichlorophenylurea, 4,5-dichloro-n-octyl-isothiazolin-3-one, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, tetramethyl Thiuram disulfide, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, diiodomethylparatolylsulfone, 2- (4-thiazolyl) benzo Examples include imidazole, 2-pyridinethiol-1-oxide zinc salt or copper salt.

  The coating composition according to the present invention contains a polymer having a specific structure together with the diphenylboron compound represented by the formula (1).

The polymer having the specific structure is:
^{_{R 5 - (CH 2) k}} -COO-M-L q ··· (5)
It is a copolymer containing the component unit induced | guided | derived from the polymerizable unsaturated metal salt compound represented by these.

However, in the equation (5), ^{R 5} is
_{CH 2 = C (CH 3)} -,
CH ₂ = CH-,
HOOC-CH = CH-, and _{HOOC-CH = C (CH 3} ) -
The organic group containing an unsaturated bond shown by either formula is shown. -COOH in these formulas may form a metal salt or ester. k shows the integer of 0-2. M represents a metal atom. L is an organic acid residue —OCOR ⁶ (where R ⁶ represents an alkyl group or an alkenyl group), or —R ⁷ —CO—CH ₂ —CO—R ⁸ (where R ⁷ is a straight chain) A divalent group formed by extracting two hydrogen atoms from a linear or branched alkane or phenyl derivative, R ⁸ represents a monovalent group consisting of an alkyl group or a phenyl derivative, or a group represented by: -OH is shown.

  q represents the number of the valence number-1 of the metal M.

In the above formula (5), when L is a carboxylic acid residue (—OCOR ⁶ ), as the carboxylic acid (HOCOR ⁶ ) capable of deriving such a group, R ⁶ is an alkyl group (saturated hydrocarbon), Or a carboxylic acid which is an alkenyl group (unsaturated hydrocarbon group-containing group) having one or more carbon-carbon double bonds, and a carbon-carbon atom in the main chain constituting R ⁶ May contain an ether bond (eg, C—O—C, C—S—C), an ester bond (—COO—), or the like through the interposition of another atom, and the carboxyl group thereof. Examples of the number of carboxylic acids may be one (monovalent) or plural (multivalent).

Examples of the carboxylic acid from which the carboxylic acid residue L can be derived include acetic acid, propionic acid (C ₂ H ₅ COOH), butanoic acid (CH ₃ (CH ₂ ) ₂ COOH), which are monovalent saturated carboxylic acids, valeric acid _{(CH 3 (CH 2) 3} COOH), versatic acid, lauric acid _{(CH 3 (CH 2) 10} COOH), palmitic acid _{(CH 3 (CH 2) 14} COOH), stearic acid _(C 17 _{H 35} COOH) and other monovalent unsaturated carboxylic acids such as acrylic acid, 2-butenoic acid (CH ₃ CH═CHCOOH), oleic acid [CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ COOH], linole acid _{[CH 3 (CH 2) 4} CH = CHCH 2 CH = CH (CH 2) 7 COOH], linolenic acid _{[CH 3 CH 2 (CH =} CHCH 2) 3 (C _{2) 5} COOH], and the like.

Examples of the divalent or higher valent carboxylic acid capable of deriving the carboxylic acid residue L include fumaric acid (HOOCCH = CHCOOH), azelaic acid (HOOC (CH ₂ ) ₇ COOH), and the like. In the present invention, among these carboxylic acids, carboxylic acids having 1 to 25 carbon atoms, preferably 1 to 18 carbon atoms are desirable. These carboxylic acids can be used alone or in combination of two or more. When two or more carboxylic acids are used in combination, the carbon number of R ^{5 in} the above formula (5) is an average value. Show.

In the above formula (5), when L is a group represented by _{^{-R 7 -CO-CH 2 -CO-}} R 8, for example acetylacetone, be given residue such as 1-phenyl 1,3-butanedione it can.

  In the formula (5), k is preferably 0.

  When L in the formula (5) is —OH, any resin such as polyester, polyurethane, natural resin, vinyl polymer, etc. can be used as the resin having a carboxyl group in the molecule. A vinyl polymer is preferred because of its freedom. In addition, if the molecular weight of the resin is low, it may contain one carboxyl group per molecule, but when it has a high molecular weight, the acid value is preferably in the range of 30 to 300. Two or more are required per molecule.

  The synthesis method is not particularly limited. For example, a divalent metal oxide or hydroxide to be added with 0.5 to 5% by weight of water is added to a resin having a carboxyl group in the molecule. The reaction is carried out at a temperature of ˜200 ° C. for 1 to 20 hours. If the system appears to be cloudy due to the presence of water, a minimal amount of polar solvent needs to be added.

  Examples of polar solvents include alcohol solvents such as n-butanol and isopropyl alcohol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate; cellosolve, butyl cellosolve, diethylene glycol, And ether solvents such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether. Initially, the powdered metal compound does not dissolve, but the system becomes transparent as the reaction proceeds.

  Examples of the metal atom in the formula (5) include group Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, VIb, VIIb, and VIII metal atoms in the periodic table. , Cu, Ni, Co, Pb, Al, Mg, Sn, Ge, and the like. Among them, divalent metal atoms such as Cu, Zn, and Mg are preferable, and Cu and Zn are particularly preferable. .

  The number average molecular weight of the polymerizable unsaturated metal salt compound represented by the formula (5) is usually 4,000 to 100,000, and the glass transition temperature is usually −30 ° C. to + 70 ° C. Further, the method for producing the polymerizable unsaturated metal salt compound represented by the formula (5) is not particularly limited. For example, the polymerizable unsaturated metal salt compound can be copolymerized with the polymerizable unsaturated metal salt compound as necessary. Other polymerizable monomers can be mixed and the mixture can be reacted in the presence of a radical initiator at a reaction temperature of 60 to 180 ° C. for 5 to 14 hours. As the polymerization method, in addition to solution polymerization performed in an organic solvent, an emulsion polymerization method, a suspension polymerization method, and the like can be adopted, but toluene, xylene, methyl isobutyl ketone, n-butyl acetate, propylene glycol monomethyl ether, n-butanol. Adopting a solution polymerization method using a general organic solvent such as the above is advantageous in terms of productivity.

  The copolymer as the component B) in this invention is a copolymer obtained by copolymerizing two or more polymerizable unsaturated metal salt compounds represented by the formula (5) and a polymerization represented by the formula (5). Examples thereof include a copolymer obtained by copolymerizing at least one kind of polymerizable unsaturated metal salt compound and another polymerizable monomer copolymerizable therewith.

  Examples of the other polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). ) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxypropyl (Meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxy Aliphatic monomers such as tylene glycol (meth) acrylate, alicyclic monomers such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. Aromatic monomers, monomers such as diethyl malate, diisopropyl fumarate, dibutyl itaconate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) Hydroxyl group-containing unsaturated monomers such as unsaturated monomers having one hydroxyl group such as acrylate and 2-hydroxybutyl (meth) acrylate, monomers having a plurality of hydroxyl groups such as glycerol (meth) acrylate, ( (Meth) acrylamide, butylaminoethyl (meth) acrylate, etc. Amino group or amide group-containing monomer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethyl Monomers having first to third amino groups or amide groups such as aminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, styrene, vinyltoluene, α-methylstyrene, (meth) acrylonitrile, vinyl acetate , Vinyl propionate, (meth) acrylic acid, 2-butenoic acid, oleic acid, linolenic acid, linoleic acid, maleic acid, fumaric acid, itaconic acid, propionic acid, valeric acid, butanoic acid, palmitic acid, myristic acid, Laurin It can stearic acid and its metal salts are exemplified.

  The copolymer as the component B) in this invention is obtained by polymerizing the polymerizable unsaturated metal salt compound represented by the formula (5) and another polymerizable monomer copolymerizable therewith. Can do.

  The polymerization reaction may be any of solution polymerization reaction, bulk polymerization reaction, emulsion polymerization reaction and the like. However, a preferable polymerization reaction is a solution polymerization reaction.

  When the copolymer which is component B) is obtained by a solution polymerization reaction, the polymerizable unsaturated metal salt compound represented by the above formula (5) and other polymerizable monomers copolymerizable therewith are dissolved as the solvent. The solvent which can be used can be used suitably. The solvent is not particularly limited. For example, hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane, white spirits, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Ethers such as glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monoethyl ether, esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ketones such as methyl isobutyl ketone and ethyl isobutyl ketone; n -Alcohols, such as butanol and propanol, can be mentioned. These solvents can be used alone or in combination of two or more. In order to perform solution polymerization suitably, a mixed solvent of esters and alcohols is preferable.

  In the polymerization reaction, an ordinary polymerization initiator, for example, a radical polymerization initiator is added to a mixture of the polymerizable unsaturated metal salt compound represented by the formula (5) and another polymerizable monomer copolymerizable therewith. However, it progresses when heated to a predetermined temperature.

  The coating composition concerning this invention contains the diphenylboron compound which is said A) component, and the copolymer which is said B) component. The content of the diphenylboron compound in the coating composition is generally 0.01 to 60% by mass, preferably 0.1 to 40% by mass in the solid content in the coating composition. If the content of this diphenylboron compound is less than the lower limit, the resulting coating film may be inferior in antifouling properties, and if it exceeds the upper limit, problems such as cracking and peeling may occur in the coating film. May occur. Moreover, content which can be in the coating composition of the copolymer as said B component is 0.1-80 mass% normally in solid content in a coating composition, Preferably it is 1-60 mass%. If the content of the copolymer as the component B) is less than the lower limit value, the resulting coating film may be inferior in antifouling properties, and if the upper limit value is exceeded, the coating film cracks. Inconvenience such as peeling may occur.

  The coating composition according to the present invention may contain a rosin compound as component C) as necessary.

  Examples of the rosin compound that is the component C) include rosin, rosin derivatives, and rosin metal salts. Examples of rosins include tall rosin, gum rosin, and wood rosin, and examples of rosin derivatives include hydrogenated rosin, maleated rosin obtained by reacting rosin with maleic anhydride, formylated rosin, and polymerized rosin. Examples include rosinate, gincrozinate, copper rosinate, magnesium rosinate, and a reaction product of other metal compound and rosin.

  In the present invention, one or two or more kinds of such rosin compounds can be selected and used. The amount of the rosin compound used relative to the copolymer as the component B) is as follows. The solid content ratio is 0.1 to 90% by mass, preferably 0.1 to 80% by mass. If the amount of the rosin compound is excessive, the coating film forming ability is lowered, and defects such as cracking and peeling are likely to occur in the coating film, and it may be difficult to obtain effective antifouling performance.

  Oil components such as silicone oil and liquid paraffin can be added to the coating composition of the present invention as needed for the purpose of adjusting the dissolution rate. Specific examples include dimethyl silicone oil, methylphenyl silicone oil, polyether-modified silicone oil, petrolatum, polybutene, and the like.

  The coating composition of the present invention includes petals, zinc oxide, coloring agents such as pigments and dyes such as talc, water binders, sagging agents commonly used in coatings, chlorinated paraffin, dioctyl phthalate, tricresyl Various additives such as plasticizers such as phosphates, UV absorbers such as benzophenone compounds and benzotriazole compounds, anti-color separation agents, anti-settling agents, antifoaming agents, silanols, polysiloxanes, alkoxysilanes, etc. It can mix | blend suitably.

  The coating composition according to the present invention comprises a polymerization product solution obtained by synthesizing the diphenylboron compound as component A) and the copolymer as component B), or a copolymer obtained by isolation from the polymerization product solution It can be obtained by mixing a copolymer solution obtained by adding a solvent to the rosin compound and other various additives as component C) added as necessary.

<Anti-fouling coating film and anti-fouling method>
The antifouling coating film using the coating composition according to the present invention is formed on at least the draft surface of the underwater structure. Examples of the coating method include spray coating, brush coating, roller coating, and dip coating. After coating by these methods, the solvent may be volatilized and removed at room temperature or under heating, and a dry antifouling coating film can be easily formed on the draft surface by this method.

<Anti-fouling underwater structure>
Examples of the antifouling underwater structure according to the present invention include an underwater structure formed by forming the antifouling coating film according to the present invention on the draft surface.

  Examples of the underwater structure include, for example, ships, fishing materials (eg, ropes, fishing nets, floats, buoys), underwater structures such as water supply / drainage ports of thermal power / nuclear power plants, coastal roads, submarine tunnels, port facilities, canals, Various base materials such as a waterway and a sludge diffusion prevention film for offshore civil engineering can be listed. In addition, ships, buoys, various water pipes, antifouling membranes, subsea oil well drilling wells, piers, pipelines, submarine cables, heat exchangers, dams, water absorption screens and the like can be mentioned.

  The antifouling underwater structure having these antifouling coatings has an antifouling coating excellent in antifouling properties over a long period of time and excellent in crack resistance even when thickly applied.

  That is, the antifouling coating film obtained by applying and curing the coating composition of the present invention on the surface of various substrates continuously adheres to aquatic organisms such as mussels, barnacles, cell plastics, bryophytes, aosa, aonori and slime for a long period of time. Excellent antifouling properties such as prevention. In particular, the coating composition adheres well to the substrate surface even when the substrate is steel, FRP, wood, aluminum alloy or the like. The coating composition may be overcoated on the surface of an existing coating film.

  Further, when the coating composition of the present invention is applied to the surface of an underwater structure, it is possible to prevent the adhesion of marine organisms and to maintain the function of the structure for a long period of time. Moreover, if the coating composition of this invention is applied to fishing materials such as fishing nets or fishing gears, the fishing nets or fishing gears can be prevented from being polluted, and there is little risk of environmental pollution. The antifouling coating film of the present invention, that is, the coating film applied to the surface of the water-contacting part of the ship or underwater structure is formed from the coating composition described above, and is less likely to cause environmental pollution. Has excellent long-term antifouling properties against attached organisms.

  Next, the present invention will be specifically described with reference to production examples, examples and comparative examples. In addition, the part in an example is a weight part.

  First, a production example of a copolymer containing component units derived from the polymerizable unsaturated metal salt compound of component B) will be described.

<Production Example 1>
A monomer mixture consisting of 14 parts by weight of zinc acrylate, 26 parts by weight of zinc oleate, 15 parts by weight of methyl methacrylate and 45 parts by weight of ethyl acrylate (a total of 40 parts by weight of these copolymerizable monomers) was added to a solvent (40 parts by weight of butyl acetate). , 20 parts by weight of n-butanol), and a copolymerization reaction is carried out at 100 ° C. for 6 hours in the presence of the polymerization initiator AIBN to obtain a polymer having a molecular weight (Mw) of about 8000. Solution 1 (solid content 40% by mass) was obtained. Table 1 shows the monomer composition at the time of preparing the polymer solution 1, the physical properties of the obtained polymer solution 1, and the like.

<Production Examples 2-8>
A polymer solution shown in Table 1 was obtained in the same manner as the polymer solution 1 except that the raw material having the monomer composition shown in Table 1 was used instead of the monomer for the polymer solution 1. The monomer composition and the like are shown in Table 1.

<Production Example 9>
In a 50% by weight butyl acetate solution of a copolymer having a number average molecular weight of 40,000 consisting of 7.2 parts by weight of acrylic acid, 50 parts by weight of methyl methacrylate and 42.8 parts by weight of ethyl acrylate, 8 g of zinc oxide, 5 g of butanol and water 1 g was added and reacted at 120 ° C. for 10 hours to obtain a transparent polymer solution 9 having a solid content of 49.2% by mass.

<Production Example 10>
A reactor was equipped with a thermometer, thermostat, stirrer, reflux condenser, and dropping pump, and 46 parts of butyl acetate and 42 parts of n-butanol were charged. While stirring, 7.3 parts of zinc oxide and 5.0 parts of water were added. Zinc oxide was dispersed in the solvent. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 15.3 parts of methacrylic acid, 44.7 parts of ethyl acrylate, 40.0 parts of methoxyethyl acrylate, and 2,2′-azobis (2-methylbutyrate) which is a polymerization initiator. While maintaining 8.0 parts of (ronitrile) at 100 ° C., it was dropped at a constant rate over 4 hours using a dropping pump. After completion of dropping, the temperature was kept at 100 ° C. for 30 minutes and stirring was continued. Thereafter, 1 part of 2,2′-azobis (2,4-dimethylpentyronitrile), which is an additional polymerization initiator, was dissolved in 6 parts of butyl acetate and 6 parts of n-butanol at a constant rate over 1 hour. It was dripped at. Further, stirring was continued at 100 ° C. for 6 hours to obtain a uniform and transparent polymer solution 10 having a nonvolatile content of 50% by mass.

(Examples 1 to 26)
Using the polymer solutions 1 to 10, each component was mixed according to the composition shown in the following Tables 2 to 4 (the values in the table are% by mass), and mixed and dispersed with a 2,000 rpm homomixer. A variety of coating compositions were prepared. In each table, “Laroflex MP-45” (trade name manufactured by BASF) is a vinyl chloride resin, “TSF-4445” (trade name manufactured by Toshiba Silicone Co., Ltd.) is a polyether-modified silicone oil, “ “Dispalon A630-20XN” (trade name, manufactured by Enomoto Kasei Co., Ltd.), “Dispalon 4200-20” (trade name, manufactured by Enomoto Kasei Co., Ltd.), and “Benton SD-2” (manufactured by National Red Co., Ltd.) [Product name] is an additive for sagging prevention.

(Comparative Example 1)
"Laroflex MP-45" (trade name, vinyl chloride resin, manufactured by BASF) 15 parts, rosin 10 parts, chlorinated paraffin 2 parts, pyridiniomethyldiphenyl boron 30 parts, zinc oxide 4 parts, Bengala 6 parts Aerosil # 200 (trade name, manufactured by Nippon Aerosil Co., Ltd.) 1 part, 32 parts of xylene and 5 parts of methyl isobutyl ketone were mixed, and mixed and dispersed with a 2,000 rpm homomixer to prepare a coating composition.

(Comparative Example 2)
15 parts acrylic resin (trade name, 50% xylene solution, manufactured by Hitachi Chemical Co., Ltd.), 7 parts rosin, 2 parts tricresyl phosphate, silicone oil TSF-4445 (trade name, polyether manufactured by Toshiba Silicone Co., Ltd.) Modified silicone oil) 2 parts, 20 parts of n-octadecylamine triphenyl boron, 15 parts of talc, 1 part of zinc oxide, 8 parts of Bengala and 30 parts of xylene are mixed and dispersed with a 2,000 rpm homomixer. A composition was prepared.

(Comparative Examples 3 to 7)
Each component was mixed by the composition shown in the following Table 5 (the numerical value in the table is% by mass), and mixed and dispersed with a 2,000 rpm homomixer to prepare a coating composition.

  About each coating composition of the above Examples 1-26 and Comparative Examples 1-7, a coating film consumption test, an antifouling performance test, an adhesion test, a crack resistance test, a recoat property test, and a fishing net prevention according to the following procedures. A soil performance test was conducted. These results were as shown in Tables 6 to 12.

<Coating film wear test>
Each coating composition was sprayed twice on the surface of a steel plate (100 mm x 100 mm x 1 mm) with anti-corrosion coating on both sides so that the dry film thickness would be 200 μm at a time. A test piece was prepared by drying for one week.

  After fixing the above test piece to the outer surface of a cylindrical drum with a diameter of 50 cm, it is immersed in 1 m below the sea surface in Yura Bay, Sumoto City, Hyogo Prefecture, and rotated with a motor so that the peripheral speed of the drum is 16 knots. The consumed coating thickness was measured every 3 months for 24 months. Moreover, the average thickness consumption rate (μm / month) was calculated for a period of up to 6 months and a period of from 6 months to 24 months. The average coating thickness consumption rate is 3 μm / month, which correlates with good antifouling performance. In addition, if the average thickness consumption rate of the coating film from 6 months to 24 months is within the range of the average coating thickness consumption rate ± 1 (μm / month) up to 6 months, the coating film is consumed at a constant rate. It is shown that.

<Anti-fouling performance test>
Each coating composition was applied twice on both sides of an FRP plate (100 mm × 200 mm × 1 mm) by spray coating so that the dry film thickness was 240 μm on one side, and placed in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75%. And dried for 1 week to prepare a test piece. This test piece was immersed in seawater for 1.5 months in Osaka Bay, Takaishi City, Osaka Prefecture, underwater for 24 months. The degree of adhesion of underwater plants such as Aosa and slime was measured over time. In addition, the adhesion amount of the underwater animal and underwater plant in a table | surface was shown by the ratio (attachment area) of the occupation area which the adhering organism adhering on the test coating film occupied. The amount of slime adhered was indicated by the value calculated according to the following evaluation criteria.
0: No slime adherence 1: Slime adherence to a slight extent 2: Slime adherence to a small extent 3: Slime adherence to a moderate extent 4: Slime adherence to a moderate extent 5: Slime adherence to a large extent

<Adhesion test>
The blast steel plate was coated with an epoxy-based anticorrosive paint twice by spray so that the dry film thickness was 125 μm per time, and further the sealer coat was applied so that the dry film thickness was 70 μm. On top of this, each coating composition was applied twice with a spray so that the dry film thickness was 100 μm at a time, and dried in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% for one week. A piece was made.

  This test piece was immersed in artificial seawater and pulled up after 3 months, 6 months, 12 months, 18 months, and 24 months, and a gobang eye test at 2 mm intervals was performed. In the evaluation of adhesion, the case where the number of peels by this test was 0/25 was evaluated as ◯ (pass), and the case where the number of peels was 1 or more / 25 was evaluated as x (failed).

<Crack resistance test>
In the adhesion test, when the test piece was pulled up from the artificial seawater, the coating film was visually observed to check for the occurrence of cracks. The thing without a crack was set as (circle) (pass), and the thing with a * (fail).

<Recoatability test>
Each coating composition was sprayed twice on the surface of a steel plate (100 mm × 100 mm × 1 mm) with anticorrosive coating on both sides so that the dry film thickness per time was 100 μm, and the temperature was 20 ° C. and the humidity was 75. The test piece was dried for 1 week in a constant temperature and humidity room of 2% to prepare two test pieces for each coating composition.

  This test piece was immersed in artificial seawater, pulled up after 12 months and 24 months, washed with distilled water, and dried in a room at a temperature of 20 ° C. for 1 week. Thereafter, the same coating composition was applied to the surface of each test piece twice by spray coating so that the dry film thickness was 100 μm per time, and was dried in a room at a temperature of 20 ° C. for one week. After fixing these test pieces to the outer surface of a cylindrical drum with a diameter of 50 cm, they were immersed in 1 m below the sea surface in Yura Bay, Sumoto City, Hyogo Prefecture, and rotated with a motor so that the peripheral speed of the drum was 16 knots. It was. One week later, this was pulled up, and the presence or absence of peeling was confirmed between the new coating film and the old coating film. The thing without peeling was set as (circle) (pass), and the thing with x (failed).

<Fishing net antifouling performance test>
Each coating composition was coated with 0.4 g per 1 g of net weight on a test fishing net consisting of 24 vertices of horizontal X width: 50 cm × 25 cm and 10 sections of 24 440 decitex polyethylenes. These were air-dried for 3 days, and immersed in Sagami Bay, Odawara City, Kanagawa Prefecture, at a position 1.5 m below the sea surface for 24 months, and the amount of living organisms was measured over time. Similar to the antifouling performance test, underwater animals such as barnacles, sea squirts, cell plastics, mussels, mussels, green mussels, and chrysanthemum moths, as well as underwater plants such as Aonori and Aosa, and the degree of slime adhesion were measured over time. In addition, the adhesion amount of the underwater animal and underwater plant in a table | surface was shown by the ratio (attachment area) of the occupancy area of the adhesion organism on a test coating film. The amount of slime adhered was indicated by the value calculated according to the following evaluation criteria.
0: No slime adherence 1: Slime adherence to a slight extent 2: Slime adherence to a small extent 3: Slime adherence to a moderate extent 4: Slime adherence to a moderate extent 5: Slime adherence to a large extent

  As is apparent from the results in Tables 6 to 12, the coating composition of Comparative Example 1 using a vinyl chloride resin as a blend polymer (corresponding to the example of JP-A-9-323909), non-hydrolysis In the coating composition of Comparative Example 2 (corresponding to the example of JP-A-2001-342192) and the coating composition of Comparative Example 3 using a functional acrylyl resin, both coating films are good for several months after the start of immersion. Some may exhibit wear, but after a long period of immersion, the paint wear will be lost, resulting in unsatisfactory results in both paint wear rate and antifouling performance, adhesion test, crack resistance test, recoat test, and fishing net There were also defects in the antifouling performance test. Also, a coating composition of Comparative Example 5 using a hydrolyzable resin and pyridine triphenylboron (corresponding to the example of JP-A-2001-329228), the hydrolyzable resin and the component A) described in the present invention In the coating compositions of Comparative Examples 4, 6, and 7 using antifouling agents other than these compounds, there are some paint films that exhibit good film wear, but the antifouling performance can be exhibited only for a short period of time. The defect was also observed in the property test, crack resistance test, recoat property test and fishing net antifouling performance test. On the other hand, in each coating composition of Examples 1 to 26 using the compound of component A) described in the present invention and a hydrolyzable resin, satisfactory results were shown in any test. From the results, it can be seen that the coating composition of the present invention has excellent performance.

Claims (8)

A) As a component, the following formula (1)

[However, in Formula (1), X shows a halogen atom, a C1-C8 alkyl group, or a C1-C8 alkoxy group. n is independently an integer of 0 to 3, and when n is 2 or 3, X may be the same or different. R represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, a hydroxy group, or a halogen atom.
In the formula (1), R ¹ is the following formula (2), a 5,6,7,8-tetrahydroisoquinoline group, an isoquinoline group which can be substituted with a halogen, any group of the formula (3) or the formula (4) Indicates.
Formula (2);

(In the formula (2), Y represents a halogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or an acetyl group. M is an integer of 0 to 3, and m is 2 or 3. , Y may be the same or different.)
Formula (3);
—NH ₂ —R ² (3)
(In the formula (3), R ² represents a linear alkyl group having 1 to 24 carbon atoms or a branched alkyl group having 3 to 24 carbon atoms.)
Formula (4);
—NH ₂ —R ³ —O—R ⁴ (4)
(However, in the formula (4), ^{R 3} is a branched alkylene group having a linear or carbon number of 1 to 24 carbon atoms 3-24, or a phenylene group, ^{R 4} is from 1 to 24 carbon atoms A linear or branched alkyl group having 3 to 24 carbon atoms.)] At least one diphenylboron compound,
B) As a component, the following formula (5)
^{_{R 5 - (CH 2) k}} -COO-M-L q ··· (5)
[In the formula (5), R ⁵ represents CH ₂ ═C (CH ₃ ) —,
CH ₂ = CH-,
HOOC-CH = CH-, and _{HOOC-CH = C (CH 3} ) -
The organic group containing an unsaturated bond shown by either formula is shown. -COOH in these formulas may form a metal salt or ester.
k shows the integer of 0-2.
M represents a metal atom.
L is —OCOR ⁶ (wherein R ⁶ represents an alkyl group or an alkenyl group) which is an organic acid residue, or —R ⁷ —CO—CH ₂ —CO—R ⁸ (where R ⁷ is linear) Or a divalent group formed by extracting two hydrogen atoms from a branched alkane or phenyl derivative, and R ⁸ represents a monovalent group consisting of an alkyl group or a phenyl derivative. OH is shown.
q represents the number of the valence number-1 of the metal M. ]
And a copolymer containing a component unit derived from a polymerizable unsaturated metal salt compound represented by the formula:   The coating composition according to claim 1, comprising at least one rosin compound selected from the group consisting of rosin, rosin derivatives and rosin metal salts.   The coating composition according to claim 1 or 2, wherein the metal M in the component B) is a divalent metal.   The said A) component is a methyl diphenyl boron compound, The coating composition in any one of Claims 1-3.   The component A) is pyridiniomethyldiphenylboron, (3-methylpyridinio) methyldiphenylboron, (3-bromopyridinio) methyldiphenylboron, (4-isopropylpyridinio) methyldiphenylboron, (4-t-butylpyridinio) At least one methyldiphenyl selected from the group consisting of methyldiphenylboron, (4-phenylpyridinio) methyldiphenylboron, n-octadecylaminemethyldiphenylboron, and 3- (2-ethylhexyloxy) propylaminemethyldiphenylboron The coating composition according to claim 1, which is a boron compound.   An antifouling coating film formed from the coating composition according to any one of claims 1 to 5.   An antifouling underwater structure comprising the underwater structure and the antifouling coating film according to claim 6 formed on the surface thereof. An antifouling method comprising applying the coating composition according to claim 6 to a water-contactable surface of an underwater structure to form an antifouling coating film.