JP3208956B2 - Antifouling paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel antifouling paint composition capable of preventing the attachment of organisms to the surface of an underwater object.

[0002]

2. Description of the Related Art Underwater structures such as ship bottoms, buoys, fishing nets (aquaculture nets, stationary nets, etc.) immersed in the sea, various suction and drainage pipes for cooling, and films for preventing mud from spreading in marine civil engineering works. Barnacles, serpula,
Various obstacles occur due to the attachment of organisms such as mussels and algae. It is well known that in order to prevent fouling by these organisms, paints are applied which prevent the organisms from adhering to the surface of the underwater objects. As an initial antifouling paint to prevent the adhesion of organisms, the resin that forms the coating film does not dissolve in seawater, but only the antifouling agent dissolves in seawater, preventing the adhesion of marine organisms. It was a paint of the type to prevent. This type of paint generally has a good initial antifouling effect, but has a drawback in that the antifouling effect is insufficient for a long period of time.

The antifouling paint put on the market as an improved type is a so-called hydrolyzable self-polishing type paint in which both the resin forming the coating film and the antifouling agent dissolve in seawater. Since the film surface is eluted, the surface of the active antifouling coating film is always maintained, and it is recognized that the antifouling effect may be easily maintained.

[0004] One of the hydrolyzable self-polishing paints is an organosilyl ester group on the resin side chain which can be gradually eluted from the surface in seawater to remove fouling organisms from the viewpoint of prevention of marine biological pollution. And a coating composition containing a resin having a hemiacetal ester group as a hydrolyzable group (JP-A-63-215780, JP-A-4-103671). However,
The coating composition containing a resin having the above-mentioned organosilyl ester group or hemiacetal ester group has the following problems. (1) Since the rate of hydrolysis of the organosilyl ester group and the hemiacetal ester group in the resin is very high, in the dispersion step in the production of paint, the moisture contained in the air and the water contained in the pigment, the antifouling agent, etc. A carboxyl group is generated on the side chain of the resin. This carboxyl group forms a complex with a pigment or a metal such as cuprous oxide, causing gelation. As a solution to this problem, the use of a water binder has been proposed, but it is still insufficient to prevent gelation. . (2) Hydrolysis of the organosilyl ester group and the hemiacetal ester group in the resin generates a carboxyl group on the side chain of the resin on the coating film surface. For this reason, when the Tg of the resin itself increases, hardening and embrittlement of the coated surface, whitening, cracking, and peeling of the coated surface are likely to occur. (3) After the antifouling agent on the coating film surface elutes, a resin residue layer having a carboxyl group in the side chain forms a thick resin residue layer. The rate of dissolution of this resin residue layer into the sea is slow, preventing the dissolution of the antifouling agent in the deep part of the coating film into the sea, and the antifouling effect is insufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and has a good dispersion process during the production of paint and a good stability during storage, and has an excellent property for a long time after coating. An object of the present invention is to provide a hydrolyzable self-polishing coating composition that exhibits an antifouling effect.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, the resin contains a resin having a hydrolyzable acetal group or monothioacetal group in the main chain of the resin. The coating composition has good stability during the dispersion process and storage during the manufacture of the coating material, and does not cause cracking or peeling of the resin coating film even if it is hydrolyzed by seawater after coating. And found that the present invention was completed.

That is, the present invention provides a compound represented by the general formula (1)
It is intended to provide an antifouling paint composition characterized by containing a resin component having a repeating unit represented by the formula (1) and an antifouling agent as essential components.

[0008]

Embedded image

(Wherein R ¹ is a residue of a divalent phenol, R ² is a divalent organic group having 1 to 25 carbon atoms,
Y is an oxygen atom or a sulfur atom. Hereinafter, the present invention will be described in detail.

[0010] The resin component used in the present invention is composed of a repeating unit represented by the above general formula (1). R ¹ in the formula is a residue of a dihydric phenol. 2
The residue of a divalent phenol is a residue obtained by removing two hydroxyl groups from an aromatic compound having two hydroxyl groups such as phenol, and specific examples thereof include, for example, phenylene, naphthylene, oxonaphthylene, and divalent bivalent. Anthracene residue, divalent anthraquinone residue, alkanediphenylene, sulfonyldiphenylene, and alkyl-substituted products thereof. In addition, these residues may be substituted with a halogen atom such as chlorine, bromine and iodine or other substituents. Preferable examples of the residues of these phenols include phenylene, naphthylene, alkanediphenylene, oxonaphthylene residues and alkyl-substituted products thereof.

Examples of the alkyl group substituted on the aromatic ring include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n
-Pentyl, isopentyl, neopentyl, tert-
Pentyl, 2-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, 3-methylheptyl, n-nonyl, methyloctyl, ethylheptyl, n-decyl , N-undecyl, n-dodecyl, n-
Tetradecyl, n-heptadecyl, n-octadecyl,
And a cyclohexyl group.
To 8 alkyl groups, specifically, for example, methyl,
Ethyl, n-propyl, n-octyl and the like. The number of alkyl groups substituted on these aromatic rings may be one, or two or more.

The phenylene and its alkyl-substituted product include, for example, o-phenylene, m-phenylene, p-
Each isomer of tolylene such as phenylene, 4-methyl-o-phenylene, 5-methyl-m-phenylene, 5-methyl-p-phenylene, 3,4-dimethyl-o-phenylene, 4,5-dimethyl-m Each isomer of xylylene such as -phenylene, 2,5-dimethyl-p-phenylene,
Each isomer of ethylphenylene such as -ethyl-o-phenylene, 4-ethyl-m-phenylene, 2-ethyl-p-phenylene, each isomer of n-propylphenylene, each isomer of isopropylphenylene, n-butyl Each isomer of phenylene, each isomer of t-butylphenylene, each isomer of amylphenylene, each isomer of hexylphenylene, each isomer of nonylphenylene, and the like are preferable. Preferred are o-phenylene, m -Phenylene,
p-phenylene, 4-methyl-o-phenylene, 5-methyl-m-phenylene, 5-methyl-p-phenylene.

Examples of naphthylene and its alkyl-substituted product include 1,2-naphthylene, 1,3-naphthylene,
1,4-naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene,
2,3-naphthylene, 2,6-naphthylene, 2,7-naphthylene and their methyl-substituted isomers, dimethyl-substituted isomers, ethyl-substituted isomers, and isopropyl-substituted isomers , N-butyl-substituted isomers and the like, and preferred are 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene,
5-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,3-naphthylene, 2,
6-naphthylene and 2,7-naphthylene are mentioned.

Examples of oxonaphthylene and its alkyl-substituted product include 1,2-naphthoquinone-5,8-position residue, 1,4-naphthoquinone-5,8-position residue, and 2,6-naphthoquinone-5,8-position residue. Groups and their methyl-substituted isomers, ethyl-substituted isomers, isopropyl-substituted isomers, n-butyl-substituted isomers, and the like, preferably 1,2-naphthoquinone- Residues at positions 5,8, 1,4-naphthoquinone-5,8, and 2,6-naphthoquinone-5,8 can be mentioned.

The divalent anthracene residue is a residue obtained by removing two hydrogen atoms from anthracene. Specific examples of the anthracene residue and its alkyl-substituted product include, for example, a 1,2-anthracene residue and a 1,2-anthracene residue. 1,3-anthracene residue, 1,4-anthracene residue, 1,5-anthracene residue, 1,6-anthracene residue, 1,7-anthracene residue, 1,8-anthracene residue, 2,3 Anthracene residues, 2,6-anthracene residues, 2,7-anthracene residues, and isomers of these methyl-substituted products,
Each isomer of an ethyl substituent, each isomer of an isopropyl substituent, each isomer of an n-butyl substituent, and the like, preferably a 1,2-anthracene residue, a 1,3-anthracene residue, 4-anthracene residue, 1,5-anthracene residue, 1,6-anthracene residue, 1,7-anthracene residue, 1,8-anthracene residue, 2,3-anthracene residue, 2,6- Anthracene residues and 2,7-anthracene residues are exemplified.

The divalent anthraquinone residue is a residue obtained by removing two hydrogen atoms from anthraquinone, and specific examples of the anthraquinone residue and its alkyl-substituted product include, for example, 9,10-anthraquinone-5,8 Position residue,
9,10-anthraquinone-1,5-position residue, 1,2-anthraquinone-6,9-position residue, 1,4-anthraquinone-6,9-position residue and their methyl-substituted isomers,
Examples include ethyl-substituted isomers, isopropyl-substituted isomers, and n-butyl-substituted isomers, and preferably 9,10-anthraquinone-5,8-position residues,
10-anthraquinone-1,5-position residue, 1,2-anthraquinone-6,9-position residue, 1,4-anthraquinone-
Residues at positions 6 and 9 are mentioned.

Examples of the alkanediphenylene and its alkyl-substituted product include propane-2,2-diphenylene, 2-methylpropane-3,3-diphenylene, methylcyclohexylmethane-diphenylene, and isomers of these methyl-substituted products. Examples include ethyl-substituted isomers, isopropyl-substituted isomers, and n-butyl-substituted isomers, and preferably propane-2,2-diphenylene.

Examples of the sulfonyl diphenylene and its alkyl-substituted product include sulfonyl diphenylene and their methyl-substituted isomers, ethyl-substituted isomers, isopropyl-substituted isomers, and n-butyl-substituted isomers. Each isomer of the compound is preferable, and sulfonyl diphenylene is preferable.

R ² is a divalent organic group having 1 to 25 carbon atoms, preferably a divalent organic group having 1 to 15 carbon atoms,
Particularly preferred is a divalent organic group having 1 to 8 carbon atoms. Examples of these organic groups include alkenylene groups such as alkylene groups, oxyalkylene groups, cycloalkylene groups, and vinylene; cycloalkenylene groups such as a cyclohexene residue obtained by removing two hydrogen atoms from cyclohexene; and divalent aromatic compounds such as phenylene. Group residues and the like. These organic groups may be substituted with halogen atoms such as chlorine, bromine and iodine, and other substituents. Preferred among these organic groups are an alkylene group, an oxyalkylene group, and a cycloalkylene group.

The alkylene group is a linear or branched divalent hydrocarbon group, preferably an alkylene group having 1 to 10 carbon atoms. Specifically, for example, methylene, ethylene, trimethylene, methylmethylene, Ethyl methylene,
Methylethylene, ethylethylene, 2-methyltrimethylene, tetramethylene, 1-methyltrimethylene, pentamethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, Hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene and the like can be mentioned.

Examples of the oxyalkylene group include oxyethylene, polyoxyethylene, oxypropylene, polyoxypropylene and the like.

The cycloalkylene group includes, for example, a cyclopentane residue, a cyclohexane residue, a cycloheptane group, and one or two bonds of these residues further bonded to the above-mentioned alkylene group such as a methylene group or an ethylene group. And alkyl-substituted isomers such as methyl-substituted isomers, ethyl-substituted isomers, isopropyl-substituted isomers, and n-butyl-substituted isomers. Examples include a pentane residue and a cyclohexane residue.

Alkenylene groups are straight-chain or branched 2
A hydrocarbon group, preferably an alkenylene group having 1 to 10 carbon atoms, specifically, for example, vinylene, propenylene, 2-butenylene, 1-methylpropenylene,
3-methyl-2-butenylene, 3,3-dimethylpropenylene, 2-pentenylene, 3-methyl-2-butenylene, 3-methyl-3-butenylene, 2-hexanylene,
3-Heptenylene, 4-octenylene, 3-nonenylene, 3-decenylene and the like can be mentioned.

As the cycloalkenylene group, for example, a cyclopentene residue, a cyclohexene residue, a cycloheptene residue, and one or two bonds of these residues further bonded with the above-mentioned alkylene group such as a methylene group or an ethylene group And their methyl-substituted isomers, ethyl-substituted isomers, isopropyl-substituted isomers, n
Alkyl-substituted products such as each isomer of -butyl-substituted product, etc., are preferred, and a cyclopentene residue and a cyclohexene residue are preferred. The alkyl group substituted on the cycloalkyl ring and the cycloalkenyl ring may be the same as the alkyl group substituted on the aromatic ring.

The divalent aromatic residue is the same as the above-mentioned phenolic residue, and one or two bonds of these residues further include the above-mentioned alkylene group such as a methylene group or an ethylene group. And the isomers of these methyl substituents, the isomers of the ethyl substituents, the isomers of the isopropyl substituents, the isomers of the n-butyl substituents, etc. Substitutes with a halogen atom such as bromine and iodine are exemplified.

The resin component used in the present invention may have only one kind of the repeating unit represented by the general formula (1) or may have two or more kinds of the repeating unit. ) May be included. The resin component usually preferably contains the repeating unit represented by the general formula (1) in an amount of 10% by weight or more, particularly preferably 30% by weight or more. Examples of the other repeating unit contained in the resin component include a repeating unit constituting a polyester resin, a repeating unit constituting a urethane resin, and the like. The weight average molecular weight of the resin component used in the present invention is not particularly limited, but is usually 500 to 1
In the range of 0.00000, preferably
It is in the range of 0 to 50,000. The resin component used in the present invention may be used alone or in combination of two or more.

The hydrolyzable resin having a repeating unit represented by the general formula (1) of the present invention is represented by the general formula (2)

[0028]

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(Wherein R ¹ is a residue of a dihydric phenol) and a compound having two phenolic hydroxyl groups represented by the following general formula (3):

[0030]

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(Wherein R ² is a divalent organic group having 1 to 25 carbon atoms, and Y is an oxygen atom or a sulfur atom), or an addition with a divinyl ether compound or a divinyl thioether compound. It can be easily formed by the reaction.

The compound having two phenolic hydroxyl groups represented by the general formula (2) used for producing the resin component used in the present invention includes, for example, catechol,
Hydroquinone, 4-tert-butylcatechol, 2-
tert-butylhydroquinone, resorcinol, 1,4-
Dihydroanthraquinone, leuco-1,4-diaminoanthraquinone, bisphenol A, bis (4-hydroxyphenyl) sulfone, dihydroxynaphthalene, 5,
8-dihydroxy-1,4-naphthoquinone and the like.

Specific examples of the divinyl ether compound represented by the general formula (3) used in the production of the resin component used in the present invention include, for example, trimethylene glycol divinyl ether, 1,4-bisvinyl Oxymethylcyclohexene, ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol divinyl ether, pentanediol divinyl ether, hexanediol divinyl ether,
Examples thereof include 1,4-cyclohexanedimethanol divinyl ether, divinylthioether corresponding thereto, and aliphatic vinyl ether compounds such as 2,2-bis (vinylthio) propane.

In the resin component used in the present invention,
A plurality of compounds each having two phenolic hydroxyl groups represented by the general formula (2) and a divinyl ether compound represented by the general formula (3) may be used. In addition, a compound having one phenolic hydroxyl group or a monoalcohol may be used in addition to the compound having two phenolic hydroxyl groups in order to adjust the molecular weight and the properties of the coating film. Such compounds include, for example, those having 1 to 25 carbon atoms.
Phenols and alcohols. The reaction between the compound having two phenolic hydroxyl groups and the divinyl ether compound is usually carried out in the presence of an acidic catalyst without a solvent or in a suitable solvent at a temperature ranging from room temperature to 100 ° C.

The antifouling agent used as an essential component in the coating composition of the present invention is not particularly limited.
Various antifouling agents having antifouling properties can be used.
Antifouling agents are roughly classified into inorganic compounds, metal-containing organic compounds, and metal-free organic compounds. Examples of the inorganic compound include cuprous oxide, copper powder, copper compounds such as copper thiocyanate, copper carbonate, copper chloride, and copper sulfate, zinc sulfate, zinc oxide, nickel sulfate, and a copper-nickel alloy.

Examples of the organic compound containing a metal include an organic tin compound, an organic copper compound, an organic nickel compound, an organic zinc compound, and the like, and also include maneb, manseb, propineb, and the like.

Among the organic compounds containing metals, the organotin compounds include triphenyltin halides such as triphenyltin chloride and triphenyltin fluoride; tricyclohexyltin halides such as tricyclohexyltin chloride and tricyclohexyltin fluoride; Tributyltin halide such as tributyltin chloride, tributyltin fluoride, triphenyltin hydroxide, tricyclohexyltin hydroxide, bis (triphenyltin)-
α, α-dibromosuccinate, bis (tricyclohexyltin) -α, α-dibromosuccinate, bis (tributyltin) -α, α-dibromosuccinate, bis-
(Triphenyltin) oxide, bis- (tricyclohexyltin) oxide, bis- (tributyltin) oxide,
Examples include triphenyltin acetate, tricyclohexyltin acetate, tributyltin acetate, triphenyltin monochloroacetate, triphenyltin versatate, triphenyltin dimethyldithiocarbamate, and triphenyltin nicotinate.

Examples of the organic copper compounds include rhodan copper, oxine copper, copper nonylphenolsulfonate, copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper acetate, copper naphthenate, and bis (pentachlorophenolic acid). Copper and the like. further,
Examples of the organic nickel-based compound include nickel acetate, nickel dimethyldithiocarbamate, and the like, and examples of the organic zinc-based compound include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, zinc ethylenebisdithiocarbamate, and 2-pyridinethiol-1.
-Zinc oxide oxide and the like. Other examples of the organic compound containing a metal include manganese ethylenebisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride, and pyridinetriphenylborane.

The organic compounds containing no metal include N-
Trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3
-Thiazolidine-2,4-dione, dithiocyano compounds and the like. N-trihalomethylthiophthalimides among metal-free organic compounds include N-
Trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, N- (fluorodichloromethylthio) phthalimide and the like. Examples of dithiocarbamic acid include bis (dimethylthiocarbamoyl).
Examples thereof include disulfide, ammonium N-methyldithiocarbamate, ammonium ethylenebis (dithiocarbamate), and milneb. Examples of N-arylmaleimide include N- (2,4,6-trichlorophenyl) maleimide and N-4-tolylmaleimide , N-3-chlorophenylmaleimide, N- (4-n-butylphenyl)
Maleimide, N- (anilinophenyl) maleimide, N
-(2,3-xylyl) maleimide and the like.
In addition, 2,4,5,6 tetrachloroisophthalonitrile, N, N-dimethylchlorophenylurea, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro -2-n-
Octyl-3 (2H) isothiazolone, tetramethylthiuram disulfide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, 2,3,5,6-tetrachloro-4- (methyl Sulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatolylsulfone, 2- (4-thiazolyl) -benzimidazole and the like.

In the coating composition of the present invention, one of the above various antifouling agents may be used, or two or more of them may be used in combination. In addition, the amount used
In the formulation of the paint, the proportion of the antifouling agent is desirably 0.1 to 80% by weight, particularly desirably 40 to 80% by weight. When the amount of the antifouling agent is less than 0.1% by weight, the antifouling effect cannot be expected. It becomes difficult.

The coating composition of the present invention thus constituted may contain, if necessary, an organic solvent, an elution aid, a red iron oxide, a coloring agent such as a pigment or dye such as titanium dioxide or talc, a water binder, An anti-sagging agent, an anti-segregation agent, an anti-settling agent, an antifoaming agent, etc., which are commonly used in paints, can be added. The organic solvent is used for adjusting viscosity, improving coating workability, etc., for example, aromatic hydrocarbon solvents such as xylene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, and acetic acid. Ester solvents such as ethyl and butyl acetate; alcohol solvents such as isopropyl alcohol and butyl alcohol; ether solvents such as dioxane and diethyl ether; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. These may be used alone or in combination of two or more and used as a mixed solvent.

The dissolution aid is used for the purpose of finely controlling the dissolution amount of the resin component and the antifouling agent from the paint. For example, synthetic waxes such as polyethylene, polypropylene, polybutene and polybibutadiene, Silicon oils such as methylsiloxane, polymethylphenylsiloxane, polyethylene glycol-modified silicone oil, polypropylene glycol-modified silicone oil, and rosins

The antifouling coating composition of the present invention can be produced by blending the above-mentioned essential components and, if necessary, various additives. The method of mixing each component and the method of adding various additives are not particularly limited, and can be performed by various methods, and the mixing order and the addition order can be performed in various mixing orders and the addition order. The coating method of the antifouling paint of the present invention can be performed by applying the above composition to a substrate. The substrate on which the antifouling coating composition of the present invention is applied is not particularly limited, and various substrates can be used, for example,
Examples include organic and inorganic materials such as wood, glass, metal, cloth, plastic, foam, elastic, paper, ceramic, concrete, and gypsum board.

The above coating composition can be applied by directly applying the above coating composition on the surface of a base material or by applying primers such as wash primer and zinc epoxy shop primer, oil-based rust preventive, chlorinated rubber, epoxy A single-layer coating or two or more coatings formed by applying one of the top-coating paints in primers such as base coats, long oil phthalate resin bases, chloride rubber bases, and epoxy bases. The coating is performed on the formed multilayer coating film by means such as brush coating, roller coating, spray coating, and dipping. The coating amount is generally in the range of 40 to 500 μm as a dry film thickness. Drying of the coating film is usually carried out by removing the solvent by evaporation at room temperature or under heating.

[0045]

Next, the present invention will be described more specifically with reference to examples. Note that the present invention is not limited by these examples.

Production Examples 1 to 3 Production of Hydrolyzable Resins A-1 to A-3 In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, a monomer having the composition shown in Table 1 was prepared. The polymerization initiator mixture was charged and stirred while maintaining the temperature at 60 ° C. The time point at which the infrared absorption spectrum at 3543 cm ^-1 due to the hydroxyl group disappeared was regarded as the end point of the reaction, and solutions of hydrolyzable resins A-1 to A-3 having the characteristic values shown in Table 1 were obtained.

[0047]

[Table 1]

The components and abbreviations in the table indicate the following. (1) Phosphoric acid (2-ethylhexyl) ester: mono (2-ethylhexyl) phosphate and di (2-ethylhexyl) phosphate
Ethylhexyl) ester mixture, acid equivalent 176 (2) Nonvolatile content: Determined from the difference in weight before and after standing at 50 ° C. and 0.1 mmHg for 3 hours. (3) TEGDVE: triethylene glycol divinyl ether (4) VOMCH: 1,4-bisvinyloxymethylcyclohexene

Test Examples 1 to 3 The hydrolyzable resins obtained in Production Examples 1 to 3 were subjected to the following resin solubility test, resin molecular weight measurement, and visual inspection of the painted surface according to the procedures described later. The result was obtained.

Resin solubility test Each sample was applied to one side of a glass plate (30 × 50 × 1 mm) degreased with acetone so that the dry film thickness was 200 μm, and was sufficiently dried in a desiccator. Pieces were made. After immersing each test piece in sterile filtered seawater for a predetermined period, immersing it in distilled water for about 10 seconds to remove salt,
Let dry. The resin dissolution rate in seawater during the immersion period of each test piece was determined from the difference in dry weight before and after seawater immersion.

Measurement of Resin Molecular Weight The coating film of the test piece on the 7th and 60th days of immersion in seawater used for the resin solubility test was scraped off and dissolved in tetrahydrofuran to obtain a sample for measurement of resin molecular weight. The weight average molecular weight was determined by gel permeation chromatography in terms of polystyrene. Visual test The coating film of the test piece on the 7th and 60th days of seawater immersion used in the above resin solubility test was visually observed, and those without cracks, whitening, and peeling were evaluated as good.

[0052]

[Table 2]

The results shown in Table 2 will be described. According to the results of gel permeation chromatography, the molecular weight of the resin was reduced because the main chain was hydrolyzed by immersion in artificial seawater, and thus a constant dissolution rate was exhibited over a long period of time. Further, as shown in the condition of the coating film, in Test Examples 1 to 3, no increase in hardness of the coating film before and after immersion in seawater, and no accompanying embrittlement or cracking of the coating film was observed.

Examples 1 to 3 Hydrolyzable resins A-1 to A-3 prepared in Production Examples 1 to 3
And coating compositions B-1 to B-3 having the compositions shown in Table 3
Was prepared respectively. The mixing was performed using a homomixer at 2000 rpm.

[0055]

[Table 3]

The subscripts in the table indicate the following. 1): Dispalon A630-20X, manufactured by Kusumoto Kasei Co., Ltd., anti-sagging agent, trade name

Test Examples 4 to 6 The coating compositions B-1 to B-3 described in Examples 1 to 3 were used
The following resin residue layer measurement test, antifouling performance test and visual test were performed, and the results shown in Table 4 were obtained. Resin residue layer measurement test On one side of a sandblasted steel plate (50 x 100 x 1 mm), a tar vinyl-based rust-preventive paint is applied in advance and dried, and then each paint composition is applied twice in a dry film thickness. 120
spray coating to a thickness of 20 μm, humidity 7 ° C
Each test piece was prepared by drying for 1 week in a 5% constant temperature and humidity room. After hanging each test piece in sterile filtered seawater and immersing it for a predetermined period, immersing it in distilled water for about 10 seconds to remove salt,
Dried and embedded in epoxy resin. Then polish,
The cross section of the coating film was observed with a microscope to confirm the presence or absence of a resin residue layer.

Antifouling performance test A tar vinyl-based anticorrosive paint was previously applied to both sides of a sandplast-treated steel sheet (50 × 100 × 1 mm) and dried, and each paint composition was dried on one side. 1 with 2 coats
Spray paint on both sides to 20 μm, temperature 20
Each specimen was dried in a constant temperature and humidity chamber at 75 ° C. and a humidity of 75% for one week. Each test piece was immersed in seawater for two months in Aioi Bay, Aioi City, Hyogo Prefecture, and the proportion of the area occupied by the attached organisms on each test piece was measured.

[0059]

[Table 4]

As is evident from the results of Test Examples 4 to 6 shown in Table 4, the coating film formed from the coating composition using the hydrolyzable resin of Test Examples 4 to 6 has a resin residue after immersion in seawater. No layers were observed and no biofouling was observed after soaking for 2 months. In addition, when the film was immersed in seawater for two months, no abnormality such as cracking or whitening was observed on the surface of the coating film. From the above results, the coating composition of the present invention,
It can be easily understood that excellent antifouling performance is exhibited over a long period of time without causing defects such as crack peeling due to seawater immersion.

[0061]

The antifouling coating composition of the present invention has a good dispersion step in the production of the coating composition and good stability during storage, and the coating formed by the coating has problems such as cracks and peeling due to hydrolysis. , And furthermore, it is uniformly dissolved in the sea at an appropriate speed and no resin residue layer remains, so that an excellent antifouling effect can be exhibited for a long period of time.
Therefore, underwater structures such as ship bottoms, buoys, fishing nets (aquaculture nets, stationary nets, etc.) and various suction and drain pipes for cooling,
Furthermore, it is extremely useful for preventing biological contamination of underwater objects such as sludge diffusion prevention films in marine civil engineering works.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-103671 (JP, A) JP-A-61-120829 (JP, A) JP-A-59-36157 (JP, A) JP-A-7-120 82351 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 5/16 C09D 171/00-171/14 C09D 181/00-181/10 C09D 201/02-201/10 C08G 65/00-65/48 C08G 75/00-75/32

Claims (1)

(57) [Claims] 1. An antifouling paint composition comprising a resin component having a repeating unit represented by the general formula (1) and an antifouling agent as essential components. Embedded image (In the formula, R ¹ is a residue of a divalent phenol, R ² is a divalent organic group having 1 to 25 carbon atoms, and Y is an oxygen atom or a sulfur atom.)