JPH0782351A - New hydrolyzable resin and antifouling coating composition - Google Patents

Abstract

PURPOSE:To provide a hydrolyzable resin having hemi(monothio)-acetal ester groups in the main chain and to provide a hydrolyzable self-abrading antifouling coating composition showing a persistent effect in sea water by adding an antifouling agent to this resin. CONSTITUTION:This resin comprises repeating units represented by formula I (wherein R<1> and R<2> are each 1-25C bivalent organic group; and Y is O or S). The antifouling coating composition essentially consists of this resin and an antifouling agent. The resin used is desirably one containing at least 10wt% repeating units of formula I. Examples of the other repeating units include repeating units constituting a polyester resin or a urethane resin. The repeating unit represented by formula I is obtained by the addition reaction of a dicarboxylic acid compound represented by formula II with a divinyl (thio)ether compound of formula III. The amount of the antifouling agent used is desirably 0.1-80wt.% based on the composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydrolyzable resin and a novel antifouling coating composition containing the same, which can prevent organisms from adhering to the surface of objects in the sea. .

[0002]

2. Description of the Related Art Undersea structures such as ship bottoms, buoys, fishing nets (culture nets, stationary nets, etc.) and various intake and drainage pipes for cooling, as well as mud diffusion prevention films for marine civil engineering work, etc. On the surface of underwater objects, barnacles, serpra,
Various obstacles occur due to the attachment of organisms such as mussels and algae. It is well known that paints are applied to the surface of underwater objects to prevent the organisms from adhering to them in order to prevent their contamination. As an early antifouling paint to prevent the adhesion of living organisms, the resin forming the coating film does not dissolve in seawater, but only the antifouling agent dissolves in seawater to prevent the adhesion of marine organisms. It was a type of paint to prevent. This type of coating generally has a good initial antifouling effect, but has a drawback that the antifouling effect is insufficient for a long period of time.

The antifouling paint marketed as the above improved type is a so-called hydrolyzable self-polishing type paint in which both the resin forming the coating film and the antifouling agent are dissolved in seawater. Since the film surface elutes, the active antifouling coating film surface is always maintained, and it is recognized that the durability of the antifouling effect can be easily obtained.

As one of the hydrolyzable self-polishing type paints, from the viewpoint of prevention of marine organism pollution, organosilyl ester groups on the resin side chain can be gradually eluted from the surface in seawater to remove the organisms polluting. A coating composition containing a resin having a hemiacetal ester group as a hydrolyzable group has been proposed (JP-A-63-215780, JP-A-4-103671). However,
The coating composition containing the above-mentioned resin having an organosilyl ester group or a hemiacetal ester group has the following problems. (1) Since the hydrolysis rate of the organosilyl ester group and hemiacetal ester group in the resin is very fast, due to moisture in the atmosphere and water contained in the pigment, antifouling agent, etc. A carboxyl group is generated in the side chain of the resin. The carboxyl group forms a complex with a pigment or a metal such as cuprous oxide to cause gelation. The use of a water binder has been proposed as a solution to this problem, but it is still insufficient to prevent gelation. . (2) Hydrolysis of the organosilyl ester group and hemiacetal ester group in the resin produces a carboxyl group in the side chain of the resin on the coating film surface. Therefore, the Tg of the resin itself rises, so that the coating surface is likely to be hardened, embrittled, whitened, cracked, or peeled off. (3) After the antifouling agent on the surface of the coating film is eluted, a resin residue layer having a thick resin having a carboxyl group as a side chain is formed. The rate of elution of this resin residue layer into the sea is slow, the elution of the antifouling agent in the deep part of the coating film is prevented, and the antifouling effect is insufficient.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and has good stability during the dispersion process during coating and during storage, and is excellent over a long period after coating. It is an object of the present invention to provide a novel hydrolyzable resin useful for a hydrolyzable self-polishing type paint exhibiting an antifouling effect and a coating composition containing the same.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the resin main chain has a hydrolyzable hemiacetal ester group or hemimonothioacetal ester group. Specified resin has good stability during dispersion process during coating production and storage, and does not cause cracks or peeling in the resin coating film even if it is hydrolyzed by seawater after coating, and has an excellent antifouling effect for a long time. They have found that they can exert their effects and have completed the present invention.

That is, the present invention is based on the general formula (1)
The present invention provides a hydrolyzable resin having a repeating unit represented by:

[0008]

[Chemical 3]

(In the formula, R ¹ and R ² are divalent organic groups having 1 to 25 carbon atoms, and Y is an oxygen atom or a sulfur atom.)
Further, the present invention provides an antifouling coating composition characterized by containing a resin component having a repeating unit represented by the general formula (1) and an antifouling agent as essential components. Hereinafter, the present invention will be described in detail.

The hydrolyzable resin of the present invention is composed of the repeating unit represented by the above general formula (1).
In the formula, R ¹ and R ² are divalent organic groups having 1 to 25 carbon atoms, preferably divalent organic groups having 2 to 20 carbon atoms,
Particularly preferably, it is a divalent organic group having 6 to 20 carbon atoms.
R ¹ and R ² may be the same or different. Examples of these organic groups include alkylene groups such as trimethylene, cycloalkylene groups such as cyclohexane residues obtained by removing two hydrogen atoms from cyclohexane, alkenylene groups such as vinylene, and cyclohexene residues obtained by removing two hydrogen atoms from cyclohexene. Such as cycloalkenylene group, divalent aromatic residue such as phenylene, the following general formula (4)

[0011]

[Chemical 4]

(R ³ and R ⁴ in the formula are divalent organic groups having a total carbon number of 1 to 25 in the formula) and the like. These organic groups may be substituted with a halogen atom such as chlorine, bromine or iodine, or another substituent. Among these organic groups, preferred are alkylene groups, cycloalkylene groups such as cyclohexane residues, and 2
A valent aromatic residue and an organic group represented by the general formula (4).

The alkylene group is a linear or branched divalent hydrocarbon group, preferably an alkylene group having 1 to 10 carbon atoms, specifically, methylene, ethylene, trimethylene, methylmethylene, ethyl. Methylene, methylethylene, ethylethylene, 2-methyltrimethylene, tetramethylene, 1-methyltrimethylene, pentamethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpenta Examples include methylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene and the like.

The cycloalkylene group includes, for example, a cyclopentane residue, a cyclohexane residue, a cycloheptane residue, one or two of the bonds of these residues, and a alkylene group such as a methylene group or an ethylene group. Examples thereof include those bonded and alkyl-substituted products thereof, preferably cyclohexane residue, cycloheptane residue, and alkyl-substituted products thereof.

The alkenylene group has a linear or branched 2 group.
A valent hydrocarbon group, preferably an alkenylene group having 1 to 10 carbon atoms, specifically 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.

The cycloalkenylene group is, for example, a cyclopentene residue, a cyclohexene residue, a cycloheptene residue, or one or two bonds of these residues to which the above alkylene group such as a methylene group or an ethylene group is further bonded. Examples thereof include alkyl substitution products thereof, and cyclopentene residue and cyclohexene residue are preferred.

The divalent aromatic residue is a residue obtained by removing two hydrogen atoms from an aromatic compound, and specific examples thereof include phenylene, naphthylene, oxonaphthylene, divalent anthracene residue, and the like. Divalent anthraquinone residue, alkanediphenylene, sulfonyldiphenylene and alkyl-substituted products thereof, wherein one or two bonds of these residues are further bound to the above alkylene groups such as methylene group and ethylene group , And even chlorine,
Examples include substitution products with halogen atoms such as bromine and iodine. Preferred as these aromatic residues are phenylene, naphthylene, alkanediphenylene,
Examples include oxonaphthylene residues and alkyl substitution products thereof.

Examples of the alkyl group for substituting the cycloalkyl ring, cycloalkenyl ring or aromatic ring include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 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, cyclohexyl group and the like can be mentioned, preferably an alkyl group having 1 to 8 carbon atoms. Yes, specifically, for example, methyl, ethyl, n
-Propyl, n-octyl group and the like. The number of alkyl groups substituting the cycloalkyl ring, cycloalkenyl ring or aromatic ring may be one or two or more.

Examples of the above-mentioned phenylene and its alkyl-substituted products include o-phenylene, m-phenylene and p-phenylene.
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 -Phenylene, 2,5-dimethyl-p-phenylene and other xylylene isomers, 4
-Ethyl-o-phenylene, 4-ethyl-m-phenylene, 2-ethyl-p-phenylene and other ethylphenylene isomers, n-propylphenylene isomers, isopropylphenylene isomers, 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, and preferable ones are o-phenylene, m -Phenylene,
Examples thereof include p-phenylene, 4-methyl-o-phenylene, 5-methyl-m-phenylene, and 5-methyl-p-phenylene.

Examples of naphthylene and its alkyl-substituted products are 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 respective isomers of methyl-substituted compounds, isomers of dimethyl-substituted compounds, isomers of ethyl-substituted compounds, isomers of isopropyl-substituted compounds And n-butyl-substituted isomers, and the like, with preference given to 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,
Examples include 6-naphthylene and 2,7-naphthylene.

Examples of oxonaphthylene and its alkyl-substituted compounds include 1,2-naphthoquinone-5,8-position residues, 1,4-naphthoquinone-5,8-position residues, 2,6-naphthoquinone-5,8-position residues. Group and each isomer of these methyl-substituted compounds, each isomer of ethyl-substituted compounds, each isomer of isopropyl-substituted compounds, each isomer of n-butyl-substituted compounds, and the like, preferably 1,2-naphthoquinone- 5,8-position residues, 1,4-naphthoquinone-5,8-position residues, 2,6-naphthoquinone-5,8-position residues are mentioned.

The divalent anthracene residue is a residue obtained by removing two hydrogen atoms from anthracene, and specific examples of the anthracene residue and its alkyl-substituted product include, for example, 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 residue, 2,6-anthracene residue, 2,7-anthracene residue, and isomers of these methyl-substituted compounds,
Examples thereof include ethyl-substituted isomers, isopropyl-substituted isomers, n-butyl-substituted isomers, and the like, preferably 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 residue, 2,6- Examples thereof include anthracene residue and 2,7-anthracene residue.

The divalent anthraquinone residue is a residue obtained by removing two hydrogen atoms from anthraquinone. Specific examples of the anthraquinone residue and its alkyl-substituted product include 9,10-anthraquinone-5,8. Residue,
9,10-anthraquinone-1,5 position residue, 1,2-anthraquinone-6,9 position residue, 1,4-anthraquinone-6,9 position residue and their respective isomers of methyl substitution products,
Examples thereof include ethyl-substituted isomers, isopropyl-substituted isomers, and n-butyl-substituted isomers, preferably 9,10-anthraquinone-5,8-position residues,
10-anthraquinone-1,5-position residue, 1,2-anthraquinone-6,9-position residue, 1,4-anthraquinone-
The 6th and 9th residues are included.

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 thereof include ethyl-substituted isomers, isopropyl-substituted isomers, and n-butyl-substituted isomers, and preferably propane-2,2-diphenylene.

Examples of the sulfonyldiphenylene and its alkyl-substituted products include sulfonyldiphenylene and their respective isomers of methyl-substituted compounds, isomers of ethyl-substituted compounds, isomers of isopropyl-substituted compounds, and n-butyl-substituted compounds. Each isomer of the body and the like, and preferably sulfonyldiphenylene.

R ³ and R ⁴ in the general formula (4) are divalent organic groups having a total carbon number of 25 or less in the formula. Left and right R ³ and R ⁴ in the formula may be the same or different. Specific examples of R ³ and R ⁴ include those similar to the organic groups other than the organic group of the general formula (4) among R ¹ and R ² described above.

The hydrolyzable resin of the present invention may have only one type of repeating unit represented by the above general formula (1), may have two or more types, and may have the above general formula (1). It may contain a repeating unit other than the repeating unit represented by. This resin is usually of the general formula (1)
The content of the repeating unit represented by is preferably 10% by weight or more, and particularly preferably 20% by weight or more. Examples of the other repeating unit contained in the hydrolyzable resin of the present invention include a repeating unit constituting a polyester resin and a repeating unit constituting a urethane resin. The weight average molecular weight of the hydrolyzable resin of the present invention is not particularly limited, but is usually 500.
The range is from 100 to 100,000, preferably 1,
It is in the range of 000 to 50,000.

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

[0029]

[Chemical 5]

A dicarboxylic acid compound represented by the formula (R ¹ in the formula is a divalent organic group having 1 to 25 carbon atoms),
General formula (3)

[0031]

[Chemical 6]

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

Examples of the dicarboxylic acid compound represented by the general formula (2) used in the production of the hydrolyzable resin of the present invention include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid and chlorinated maleic acid. C2-C25 aliphatic dicarboxylic acids such as acid, het acid, succinic acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, diclophthalic acid, dichloroisophthalic acid, Aromatic dicarboxylic acids such as tetrachlorophthalic acid, tetrachloroisophthalic acid and tetrachloroterephthalic acid, alicyclic compounds such as tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, hexahydroisophthalic acid and hexahydroterephthalic acid Dicarboxylic acid etc. are mentioned.

Instead of the dicarboxylic acid, a half ester of dicarboxylic acid obtained by addition reaction of 1 mol of diol and 2 mol of acid anhydride can be used. Examples of such a diol include ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-. Hexanediol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A, bisphenol A, neopentyl glycol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 2
-Methyl-1,3-propanediol and the like. As the acid anhydride used for the half ester form,
For example, succinic acid, glutaric acid, phthalic acid, maleic acid,
Examples thereof include acid anhydrides of dicarboxylic acids such as dichlorophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, methyl hexahydrophthalic acid and hexahydrophthalic acid.

Specific examples of the divinyl ether compound represented by the general formula (3) used for producing the hydrolyzable resin of the present invention include, for example, trimethylene glycol divinyl ether and 1,4-bisvinyloxy. Methylcyclohexene, ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol divinyl ether, pentanediol divinyl ether, hexanediol divinyl ether, 1,4
-Cyclohexanedimethanol divinyl ether and their corresponding divinyl thioethers, and 2,2
And aliphatic vinyl ether compounds such as bis (vinylthio) propane.

In the hydrolyzable resin of the present invention, plural kinds of dicarboxylic acid compounds or half ester compounds represented by the general formula (2) and divinyl ether compounds represented by the general formula (3) may be used. . Further, in order to adjust the molecular weight and the physical properties of the coating film, a monofunctional carboxylic acid compound, a phenol or a monoalcohol may be used in combination with the above dicarboxylic acid compound or half ester. Examples of such compounds include, for example, 1 to 20 carbon atoms.
Synthetic resin acids, natural fatty acids having 10 to 32 carbon atoms, rosin, phenols having 1 to 25 carbon atoms, alcohols and the like. The reaction of the above-mentioned dicarboxylic acid compound or half ester compound with the divinyl ether compound is usually carried out at room temperature to 1 in the absence of a solvent or a suitable solvent in the presence of an acidic catalyst.
It is carried out at temperatures in the range of 00 ° C.

Next, the antifouling coating composition of the present invention will be described. The antifouling coating composition of the present invention contains the above-mentioned hydrolyzable resin as a resin component and further contains an antifouling agent. The hydrolyzable resin may be used alone or in combination of two or more. The antifouling agent used as an essential component in the coating composition of the present invention is not particularly limited, and various antifouling agents having antifouling properties can be used. The 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, copper-nickel alloy, and the like.

Examples of the organic compound containing a metal include organic tin compounds, organic copper compounds, organic nickel compounds and organic zinc compounds, and manneb, manceb, propineb and the like.

Among the organic compounds containing a metal, the organic tin compounds include triphenyltin halides such as triphenyltin chloride and triphenyltin fluoride, tricyclohexyltin halides such as tricyclohexyltin chloride and tricyclohexyltin fluoride, and the like. Tributyltin halides such as tributyltin chloride and 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 thereof include triphenyltin acetate, tricyclohexyltin acetate, tributyltin acetate, triphenyltin monochloroacetate, triphenyltin versatic acid ester, triphenyltin dimethyldithiocarbamate and triphenyltin nicotinic acid ester.

The organocopper compounds include rhodan copper, oxine copper, nonylphenol sulfonate copper, copper bis (ethylenediamine) -bis (dodecylbenzene sulfonate), copper acetate, copper naphthenate, bis (pentachlorophenolic acid). Examples include copper. further,
Examples of organic nickel compounds include nickel acetate and nickel dimethyldithiocarbamate, and examples of organic zinc compounds include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, zinc ethylenebisdithiocarbamate, and 2-pyridinethiol-1.
-Zinc oxide oxide and the like. Other organic compounds containing a metal include manganese ethylene bisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride, pyridine triphenylborane, and the like.

As the organic compound containing no metal, N-
Trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3
-Thiazolidine-2,4-dione, dithiocyano compounds and the like can be mentioned. Among the organic compounds containing no metal, N-trihalomethylthiophthalimide includes N-trihalomethylthiophthalimide.
Examples thereof include trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, N- (fluorodichloromethylthio) phthalimide, and the dithiocarbamic acid includes bis (dimethylthiocarbamoyl).
Examples thereof include disulfide, ammonium N-methyldithiocarbamate, ammonium ethylenebis (dithiocarbamate), and milneb. Examples of the 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
Examples include-(2,3-xylyl) maleimide.
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 Examples include sulfonyl) pyridine, 3-iodo-2-propynylbutyl carbamate, diiodomethyl paratolyl sulfone, and 2- (4-thiazolyl) -benzimidazole.

In the coating composition of the present invention, one kind of the various antifouling agents described above may be used, or two or more kinds thereof may be used in combination. Also, the amount used is
The proportion of the antifouling agent in the coating composition is preferably 0.1 to 80% by weight, and particularly preferably 40 to 80% by weight. If the antifouling agent is less than 0.1% by weight, the antifouling effect cannot be expected, and if it exceeds 80% by weight, defects such as cracks and peeling are likely to occur in the formed coating film, and an effective antifouling effect is obtained. It gets harder.

If necessary, the coating composition of the present invention thus constituted contains an organic solvent, an elution aid, a pigment such as rouge, titanium dioxide or talc, a colorant such as a dye, a water binder, Anti-sagging agents, anti-color separation agents, anti-settling agents, anti-foaming agents and the like which are commonly used in paints can be added. The organic solvent is used for adjusting viscosity, improving coating workability, etc., for example, xylene, an aromatic hydrocarbon solvent such as toluene, hexane, an aliphatic hydrocarbon solvent such as heptane, acetic acid. Examples thereof include 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 as a mixed solvent.

The elution aid is used for the purpose of delicately controlling the elution amount of the resin component and the antifouling agent from the coating material. For example, synthetic waxes such as polyethylene, polypropylene, polybutene, polybibutadiene, and poly wax. Examples include silicone oils such as methyl siloxane, polymethylphenyl siloxane, polyethylene glycol modified silicone oil, polypropylene glycol modified silicone oil, and rosin.

The antifouling coating composition of the present invention can be produced by mixing 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 various methods can be used, and the mixing order and the addition order can also be performed in various mixing orders and addition orders. The method for applying the antifouling paint of the present invention can be carried out by applying the above composition to a substrate. The substrate to 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 materials and inorganic materials such as wood, glass, metal, cloth, plastics, foams, elastic bodies, paper, ceramics, concrete and gypsum board.

The above coating composition can be applied by directly coating the above coating composition on the surface of the substrate or on the surface of the substrate such as wash primer, zinc epoxy type shop primer, oil-based rust preventive, chlorinated rubber type, epoxy. Undercoat primer, long oil phthalate resin system, chlorinated rubber system, epoxy system, etc., a single layer coating formed by applying one of the topcoat paints, or sequentially applying two or more types. The formed multilayer coating film is applied by a means such as brush coating, roller coating, spray coating or dipping. The coating amount is generally in the range of 40 to 500 μm as a dry film thickness. The coating film is usually dried by volatilizing and removing the solvent at room temperature or under heating.

[0047]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The present invention is not limited to these examples.

Production Examples 1 to 4 Production of dicarboxylic acid compound half-esters A-1 to A-4 A 4-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with the mixture having the composition shown in Table 1, respectively. Preparation, 60 ℃
It stirred, maintaining. The reaction was terminated when the reaction rate of the mixture reached 98%. After washing with xylene, it is dried under reduced pressure to obtain a dicarboxylic acid half ester compound A-1 which is a half ester compound of a diol and an acid anhydride.
A-4 was obtained.

[0049]

[Table 1]

Examples 1 to 5 Production of Hydrolyzable Resins B1 to B5 A 4-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with a mixture of the monomer and the polymerization initiator having the compositions shown in Table 2, respectively. Was charged, and the mixture was stirred while maintaining 60 ° C. Acid value is 5
Below, or when the disappearance of the infrared absorption spectrum at 3543 cm ⁻¹ due to the hydroxyl group is taken as the end point of the reaction, B1 to B of the hydrolyzable resin having the characteristic values shown in Table 2 respectively.
Five solutions were obtained.

[0051]

[Table 2]

The components and abbreviations in the table show the following. (1) Phosphoric acid (2-ethylhexyl) ester: phosphoric acid mono (2-ethylhexyl) ester and phosphoric acid di (2-
Ethylhexyl) ester mixture, acid equivalent 176 (2) Nonvolatile matter: Determined from the difference in weight before and after standing for 3 hours at 50 ° C. and 0.1 mmHg. (3) 1,4BD / HHPA: 1,4-butanediol and hexahydrophthalic anhydride half ester (4) NPG / HHPA: neopentyl glycol and hexahydrophthalic anhydride half ester (5) NPG / phthalic acid: neo Half ester of pentyl glycol and phthalic anhydride (6) 1,4BD / tetrachlorophthalic anhydride: 1,4
-Half ester of butanediol and tetrachlorophthalic anhydride (7) VOMCH: 1,4-bisvinyloxymethylcyclohexene

Test Examples 1 to 5 The hydrolyzable resins obtained in Examples 1 to 5 were subjected to the following resin solubility test, resin molecular weight measurement, and visual inspection of the coating surface according to the procedure described below. I got the result.

Resin Solubility Test Each sample was coated on one surface of a glass plate (30 × 50 × 1 mm) degreased with acetone so that the dry film thickness was 200 μm, and sufficiently dried in a desiccator, and then subjected to each test. Created a piece. After immersing each test piece in sterilized filtered seawater for a predetermined period of time, after immersing in distilled water for about 10 seconds to remove salt,
Dried. 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 immersion in seawater.

Measurement of resin molecular weight After removing the coating film of the test piece on the 7th and 60th day of immersion in seawater used for the resin solubility test, it was dissolved in tetrahydrofuran to obtain a resin molecular weight measurement sample. The weight average molecular weight was determined by gel permeation chromatography in terms of polystyrene. Visual test The coating films of the test pieces on the 7th day and 60th day of seawater immersion used in the above resin solubility test were visually observed, and those having no cracks, no whitening, and no peeling were considered good.

[0056]

[Table 3]

The results shown in Table 3 will be described. As a result of gel permeation chromatography, the main chain was hydrolyzed by immersing it in artificial seawater, and the molecular weight of the resin was reduced. Therefore, the dissolution rate was constant over a long period of time. Further, as shown in the situation of the coating film, in Examples 1 to 5 (especially 2 to 4), the hardness increase of the coating film before and after the immersion in seawater, and the accompanying brittleness and cracking of the coating film were not observed.

Examples 6 to 10 Coating compositions C-1 to C-5 having the compositions shown in Table 4 were prepared using the hydrolyzable resins B1 to B5 prepared in Examples 1 to 5, respectively. The mixing was performed using a 2000 rpm homomixer.

[0059]

[Table 4]

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

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

Antifouling performance test A tar vinyl-based anticorrosive paint was applied in advance on both sides of a Sandplast treated steel plate (50 × 100 × 1 mm) and dried, and then each coating composition was coated with a dry film thickness on one side. 1 in 2 coats
Spray paint on both sides to 20 μm,
Each test piece was prepared by drying for 1 week in a thermo-hygrostat at a temperature of 75 ° C. and a humidity of 75%. Each test piece was immersed in seawater for 2 months in Aioi Bay, Aioi City, Hyogo Prefecture, and the ratio of the area occupied by the attached organisms on each test piece was measured.

[0063]

[Table 5]

As is clear from the results of Test Examples 6 to 10 shown in Table 5, the coating film formed from the coating composition using the hydrolyzable resin of Test Examples 6 to 10 had a resin residue after immersion in seawater. No layer was observed and no biofouling was observed after soaking for 2 months. Further, upon immersion in seawater for 2 months, no abnormalities such as cracks or whitening were observed on the surface of the coating film. From the above results, it can be easily understood that the coating composition of the present invention exhibits excellent antifouling performance for a long period of time without causing defects such as crack peeling due to immersion in seawater.

[0065]

INDUSTRIAL APPLICABILITY The hydrolyzable resin of the present invention is hydrolyzed at an appropriate rate and has excellent solubility of the hydrolyzate in water. The antifouling coating composition has good stability during the dispersion step and storage during coating production, and the coating film formed by coating has
The problem of cracking and peeling due to hydrolysis does not occur, and further, it dissolves in the sea at an appropriate rate and uniformly, and the resin residue layer does not remain, so that an excellent antifouling effect can be exhibited for a long period of time. Therefore, for example, to prevent biofouling of undersea structures such as ship bottoms, buoys, fishing nets (aquaculture nets, stationary nets, etc.) and various intake and drainage pipes for cooling, as well as marine objects such as sludge diffusion prevention membranes for marine civil engineering work. Extremely useful.

Claims (2)

[Claims] 1. A hydrolyzable resin having a repeating unit represented by the general formula (1). [Chemical 1] (R ¹ and R ² in the formula are divalent organic groups having 1 to 25 carbon atoms, and Y is an oxygen atom or a sulfur atom.) 2. An antifouling coating composition comprising a resin component having a repeating unit represented by the general formula (1) and an antifouling agent as essential components. [Chemical 2] (R ¹ and R ² in the formula are divalent organic groups having 1 to 25 carbon atoms, and Y is an oxygen atom or a sulfur atom.)