JP2018003002A - Antifouling coating - Google Patents

Abstract

[PROBLEMS] To maintain a self-polishing property and a flexible coating film structure over a long period of time, exhibit good antifouling performance over a long period of time without causing embrittlement and cracking of the coating film. Polyester for antifouling paints that can obtain a paint film with excellent adhesion between the newly used paint and the old paint film, and maintains a good paint state even for long-term storage It is to provide a resin and an antifouling coating composition containing the resin. An antifouling paint comprising an antifouling paint polyester resin and an antifouling agent, wherein the antifouling paint polyester resin comprises a dicarboxylic acid component (A) and a trihydric or higher polyhydric alcohol component (B And a monovalent glycol ether component (C) represented by the following chemical formula 1 as an essential constituent component. [Chemical Formula 1] R1O-[(EO) m (PO) n] -H (wherein R1 is a linear or branched alkyl group having 1 to 5 carbon atoms, EO is an oxyethylene group, PO Represents an oxypropylene group, m and n are 0 or a positive integer representing the average number of repetitions of EO and PO, respectively, and 2 ≦ m + n ≦ 50, and (EO) m and (PO) n are random or Copolymerization component added in block form.) [Selection] None

Description

  The present invention relates to an antifouling paint, and more particularly to an antifouling paint characterized by its coating film components.

  Aquatic organisms such as barnacles, mussels and slime are attached to fishing equipment such as the bottom of the boat and fishing nets, or water intake and drainage pipes installed in the sea, which increases resistance, reduces strength, damages, etc. In order to prevent this, it is known to apply an antifouling paint to the surface of an underwater structure.

  As such an antifouling paint, a resin having a tin carboxylate has been widely used, but due to the problem of toxicity, there is a strong demand for conversion to other resin systems, mainly having a carboxylate of copper or zinc. A resin (Patent Document 1) or a silyl resin (Patent Document 2) that appropriately dissolves a coating film holding an antifouling agent is known.

  Antifouling paints containing these resins can be used for marine structures such as ship bottoms, buoys, fishing nets (cultured nets, stationary nets, etc.), various intake and drainage pipes for cooling, and anti-mud diffusion films for offshore civil engineering. When used in the sea for a long period of time, the coating film becomes gradually harder and more brittle, which tends to cause practical problems.

  In addition, antifouling paints containing these resins will gradually wear out and become damaged when used for a long period of time, and the antifouling performance will deteriorate due to peeling off of the coating film, so it is necessary to repaint regularly. is there.

  In such a repainting operation, in order to improve economic efficiency or work efficiency, a new paint is usually repainted on an old coating film.

  By the way, when applying a new paint layer on the surface of an old paint film, a spongy skeleton layer may be formed on the old antifouling paint film to be repaired. Adhesiveness cannot be sufficiently obtained even if the antifouling paint is applied repeatedly to an old coating film.

  In particular, as a technique for improving the top coat adhesion of paints, it is effective to allow a carboxyl group to coexist in a polyester resin whose terminal is mainly a hydroxyl group, and to efficiently produce a polyester resin. In addition, there is known a method for producing a polyester resin for coating, in which an acid component mainly composed of an aromatic dicarboxylic acid and an alcohol component mainly composed of an aliphatic glycol are subjected to an esterification reaction and a polycondensation reaction at a predetermined blending ratio. (Patent Document 3).

JP-A-8-209005 JP-A-4-264169 JP 2002-275255 A

However, it is essential that the coating film forming component employing the polyester resin obtained by the manufacturing method described in Patent Document 3 described above is subjected to high-temperature baking, and the coating film formed is mostly in seawater. Since it does not melt | dissolve, there exists a problem that antifouling property falls at the time of long-term use.
In addition to solving the above problems, it is also necessary for commercialization to keep the paint in a stable storage state.

  Accordingly, an object of the present invention is to solve the above-mentioned problems and to allow the surface of the coating film to be gradually dissolved in seawater while giving the paint having a polyester resin a coating-forming component with good topcoat adhesion characteristics. Anti-fouling paint that dissolves antifouling agent at an appropriate rate due to its self-polishing property, and the antifouling property lasts for a long time. It is to make it an excellent antifouling paint.

  In other words, the object of the present invention is that the polyester resin for antifouling paints maintains self-polishing properties and a flexible coating structure over a long period of time, and does not cause embrittlement or cracks in the coating film. The antifouling paint using this polyester resin exhibits good antifouling performance for a long period of time. Even if a paint film is formed on the surface of an old paint film, a new paint and an old paint film are used. The adhesion is good, and the paint should be stored for a long time.

  The inventors of the present application, as a result of intensive studies in order to solve the above problems, are antifouling paints containing an antifouling paint polyester resin and an antifouling agent, wherein the antifouling paint polyester resin comprises: The above-mentioned problem is characterized by being a polyester resin comprising a dicarboxylic acid component (A), a trihydric or higher polyhydric alcohol component (B), and a monovalent glycol ether component (C) as essential constituent components. The present invention has been completed.

  The antifouling paint of the present invention constituted as described above is an antifouling paint containing a polyester resin having a dicarboxylic acid component, a trihydric or higher polyhydric alcohol component, and a monovalent glycol ether component as essential constituent components. Therefore, it is possible to maintain a self-polishing property and a flexible coating structure over a long period of time, and it exhibits good antifouling performance over a long period of time without causing embrittlement and cracking of the coating film. A coating film with excellent adhesion can be obtained by newly applying a coating on the surface, and a good coating state can be maintained even in a long-term storage state. The monovalent glycol ether component (C) is preferably a glycol ether represented by the following chemical formula 1 so that the above-described action is reliably exhibited.

[Chemical 1]
R ¹ O — [(EO) _m (PO) _n ] —H
(Wherein R ¹ is a linear or branched alkyl group having 1 to 5 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and m and n are averages of EO and PO, respectively. (It is an integer of 0 or more representing the number of repetitions, and 2 ≦ m + n ≦ 50, and (EO) _m and (PO) _n are copolymer components added in a random or block form.)

By using the monovalent glycol ether component (C) represented by the formula 1 as a constituent component of the polyester resin of the present invention, self-polishing properties and a flexible coating structure can be maintained over a long period of time.
And the surface of the coating film gradually dissolves in seawater, good self-polishing properties are exhibited, and the antifouling agent retained in the resin is eluted at an appropriate rate, and the antifouling property is stable for a long time. Maintained in a state.

  It is preferable that the antifouling paint uses a glycol ether represented by the following chemical formula 2 instead of the glycol ether represented by the chemical formula 1 so that the above-described action is more reliably exhibited. .

[Chemical 2]
R ¹ O — [(EO) _m (PO) _n ] —H
(Wherein R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and m and n are averages of EO and PO, respectively. 0 or a positive integer representing the number of repetitions, 2 ≦ m + n ≦ 40, and (EO) _m and (PO) _n are copolymerization components added in a random or block form.)

  In addition, in order to achieve the above-described effect more reliably, the dicarboxylic acid component (A) includes phthalic anhydride, phthalic acid, isophthalic acid, 1,2,3,6-tetrahydrophthalic anhydride, 1,2 , 3,6-tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydrophthalic acid, 3,4,5,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic acid, succinic anhydride, succinic acid And at least one dicarboxylic acid selected from biosuccinic acid.

  For the same reason as above, the trihydric or higher polyhydric alcohol component (B) is selected from the group consisting of glycerin, diglycerin, trimethylolpropane, trimethylolethane, pentaerythritol and tris (2-hydroxyethyl) isocyanurate. One or more polyhydric alcohols are preferred.

Furthermore, it is preferable to contain 3 to 30% by mass of polyvinyl alkyl ether in 100% by mass of the resin solid content of the antifouling paint of the present invention so that the self-polishing property is further promoted.
Further, the resin solid content of 100% by mass of the antifouling paint of this invention is selected from the group consisting of tall rosin, gum rosin, wood rosin, hydrogenated rosin and polymerized rosin so that the antifouling property of the coating film is better. It is preferable to contain one or more rosin resins, that is, rosin or rosin derivatives in the range of 5 to 70% by mass.

  Further, in order to further promote the self-polishing property, the antifouling paint is composed of one or more polymers of the monomer (D) represented by the following general formula 3 and / or An organosilyl group comprising a polymer of one or more of the monomers (D) and one or more polymerizable monomers (E) other than the monomer (D) It is preferable to contain the (meth) acrylic acid ester copolymer in the range of 5 to 95% by mass in 100% by mass of the resin solid content of the antifouling paint of the present invention.

  Furthermore, the antifouling paint has 2,4,6-trichlorophenylmaleimide, N-phenylmaleimide, N- (2-ethyl-6methylphenyl) as an antifouling agent so that the self-polishing property is further promoted. 1 to 100 parts by mass of one or more maleimide compounds selected from -2,3 dichloromaleimide and N- (2,6-diethylphenyl) -2,3 dichloromaleimide It is preferable to include in a range.

  In addition, the antifouling paint of the present invention is usually produced in a state containing a solvent, and the solvent is either a reflux solvent at the production of the polyester resin for the antifouling paint or a dilution solvent in the paint. For example, an antifouling paint containing at least one solvent selected from alkylcyclohexane, o-xylene, m-xylene and p-xylene can be obtained.

  In the present invention, the dicarboxylic acid component (A) and the monovalent glycol ether component (C) are combined with the trihydric or higher polyhydric alcohol component (B) as components of the antifouling paint polyester resin. By blending, self-polishing properties and a flexible coating film structure are maintained over a long period of time, and the coating film does not become brittle or cracked. The antifouling paint using the polyester resin for the antifouling paint exhibits a good antifouling performance for a long period of time, and is a paint that is newly used even when a coating film is formed on the surface of an old coating film. There is an advantage that the adhesion between the coating film and the old coating film is good, and the long-term storage state of the paint is also good.

  The antifouling paint of the embodiment is an antifouling paint containing a polyester resin for an antifouling paint and an antifouling agent, and the polyester resin for the antifouling paint comprises a dicarboxylic acid component (A) and a trivalent or higher polyvalent The alcohol component (B) and the monovalent glycol ether component (C) are essential components.

  The organisms attached to water tanks to be controlled by antifouling agents are microorganisms including animals, plants and fungi that live in seawater, brackish water, and freshwater, and adhere to solids that exist in the living environment in part or all of their life history. It is.

  Examples of such aquatic organisms include shellfish such as barnacles, mussels, cell plastics, limpets, and lobsters, or animals including sponges, hydro, squirts, sea anemones, etc. Examples include diatoms and other microorganisms and plants.

  The object to which the antifouling paint of the present invention is applied is not particularly limited. For example, the main part of the ship, the bottom part of the ship, and other facilities and structures such as piers and waterways installed in an environment that comes into contact with water, such as the water surface and water. Examples include surfaces of objects and devices. An example of the above-described antifouling agent for chickenpox attached organism will be described later.

  The antifouling paint is composed of phthalic acid, phthalic anhydride, isophthalic acid, 1,2,3,6-tetrahydrophthalic anhydride, 1,2,3 as dicarboxylic acid component (A) among the constituent components of the polyester resin. 6-tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydrophthalic acid, 3,4,5,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic acid, tetrahydromethylphthalic acid, tetrahydromethylphthalic anhydride Examples thereof include acid, 4-methylhexahydrophthalic acid, 4-methylhexahydrophthalic anhydride, succinic acid, succinic anhydride, and biosuccinic acid produced by fermenting and purifying plant-derived raw materials.

These can be used alone or in combination of two or more. Among them, phthalic anhydride, phthalic acid, isophthalic acid, 1,2,3,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydrophthalic acid, 3, 4,5,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic acid, succinic anhydride, succinic acid, and biosuccinic acid component are more preferred from the viewpoint of antifouling properties of the resulting coating film.
The dicarboxylic acid component (A) preferably constitutes 70 mol% or less in the constituent components of the antifouling paint polyester resin. These ranges are preferable from the viewpoint of antifouling properties of the resulting coating film.

The trihydric or higher polyhydric alcohol component (B), which is a constituent component of the polyester resin for antifouling paints of this invention, may be either aliphatic or aromatic. For example, those having about 3 to 15 carbon atoms The coating film is preferable because it has the desired effects such as top coat adhesion characteristics, appropriate self-polishing properties, and coating storability, and more preferably has 3 to 10 carbon atoms.
Specific examples of the trihydric or higher polyhydric alcohol component (B) include glycerin, diglycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,3-butanetriol, 1 , 2,4-butanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butane Triol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 3-methylpentane-1,3,5-triol, 2,4-dimethyl-2,3,4-pentane Triol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 1,3,5-cyclohexanetriol, etc. Examples include trihydric alcohols, tetramethyl alcohols such as pentamethylglycerin, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like. In addition to the above examples, aliphatic polyhydric alcohols or aliphatics that are selectively known A polyhydric alcohol containing a ring or a trihydric or higher polyhydric alcohol containing an aromatic ring can be used.

  These can be used alone or in combination of two or more. Among these, glycerin, diglycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, and pentaerythritol are more preferable from the viewpoint of the antifouling property of the obtained coating film.

  The trihydric or higher polyhydric alcohol component (B) preferably constitutes 20 mol% or more in the constituent components of the polyester resin for antifouling paint. These ranges are preferable from the viewpoints of self-polishing properties, crack resistance, antifouling properties, old paint film adhesion, and long-term paint storage stability.

Moreover, it is preferable that the monovalent glycol ether component (C), which is a constituent component of the antifouling paint polyester resin, is a glycol ether represented by the formula 1 shown above.
Specific examples of the monovalent glycol ether component (C) represented by the formula 1 include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol. Monopentyl ether, diethylene glycol monoisopentyl ether, triethylene glycol monomethyl ether triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monoisobutyl ether , Triethylene glycol monopentyl ether, triethylene glycol monoisopentyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monoisopropyl ether, tetraethylene glycol monobutyl ether, tetra Ethylene glycol monoisobutyl ether, tetraethylene glycol monopentyl ether, tetraethylene glycol monoisopentyl ether, pentaethylene glycol monomethyl ether, pentaethylene glycol monoethyl ether, pentaethylene glycol monopropyl ether, pentaethylene glycol monoisopropyl ether, pentaethylene Recall monobutyl ether, pentaethylene glycol monoisobutyl ether, pentaethylene glycol monopentyl ether, pentaethylene glycol monoisopentyl ether, pentaethylene glycol monomethyl ether, pentaethylene glycol monoethyl ether, hexaethylene glycol monopropyl ether, hexaethylene glycol mono Isopropyl ether, hexaethylene glycol monobutyl ether, hexaethylene glycol monoisobutyl ether, hexaethylene glycol monopentyl ether, hexaethylene glycol monoisopentyl ether, polyethylene glycol monomethyl ether (commercially available from NOF Corporation (trade name): Uni Ox M400, M550, M10 00. ), Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether dipropylene glycol monoisobutyl ether, dipropylene glycol monopentyl ether, dipropylene Glycol monoisopentyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monoisobutyl ether, tripropylene glycol mono pen Ether, tripropylene glycol monoisopentyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monoisopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monoisobutyl ether, Tetrapropylene glycol monopentyl ether, tetrapropylene glycol monoisopentyl ether, pentapropylene glycol monomethyl ether, pentapropylene glycol monoethyl ether, pentapropylene glycol monopropyl ether, pentapropylene glycol monoisopropyl ether, pentapropylene glycol Monobutyl ether, pentapropylene glycol monoisobutyl ether, pentapropylene glycol monopentyl ether, pentapropylene glycol monoisopentyl ether, hexapropylene glycol monomethyl ether, hexapropylene glycol monoethyl ether, hexapropylene glycol monopropyl ether, hexapropylene glycol monoisopropyl Ether, hexapropylene glycol monobutyl ether hexapropylene glycol monoisobutyl ether, hexapropylene glycol monopentyl ether, hexapropylene glycol monoisopentyl ether, polypropylene glycol monobutyl ether (commercially available from NOF Corporation (trade name): Unilube MB7, MB 11, M14, MB19, MB38, MB370. ), And polyoxyethylene polyoxypropylene monobutyl ether (commercially available from NOF Corporation (trade name): Unilube 50MB2, 50MB5, 50MB11, and 50MB26).

  These can be used alone or in combination of two or more. Among these, the glycol ether represented by the formula 2 is more preferable from the viewpoint of the antifouling property of the obtained coating film.

  The blending ratio of the monovalent glycol ether component (C) described above is such that 10 mol% or more is included in the constituent component of the polyester resin for antifouling paint, and the self-polishing property and crack resistance of the resulting coating film are obtained. It is preferable from the viewpoint of antifouling properties, old film adhesion, and long-term paint storage stability.

  The polyester resin for antifouling paints used in the present invention includes the dicarboxylic acid component (A) in addition to the dicarboxylic acid component (A), the trihydric or higher polyhydric alcohol component (B), and the monovalent glycol ether component (C). A mono- or higher-valent carboxylic acid component excluding and / or a mono- or higher-valent alcohol component other than the monovalent glycol ether component (C) may be contained.

  Examples of the monovalent carboxylic acid component include those generally known as monocarboxylic acids, such as benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, caproic acid, and capryl. Examples include acids, lauric acid, myristic acid, palmitic acid, stearic acid, alginic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, γ-linolenic acid, α-linolenic acid, and ricinoleic acid.

  Examples of the divalent carboxylic acid excluding the dicarboxylic acid component (A) include dimer acid, hydrogenated dimer acid, terephthalic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, and anhydrides thereof. Examples of the trivalent polyvalent carboxylic acid component include trimer acid, trimer anhydride, trimellitic acid, hemimellitic acid, trimesic acid, naphthalene tricarboxylic acid, anthracentricarboxylic acid, and anhydrides thereof.

  Examples of the tetravalent or higher polyvalent carboxylic acid component include pyromellitic acid, merophanic acid, planitic acid, and anhydrides thereof. These can be used alone or in combination of two or more.

  Examples of the monovalent alcohol component other than the monovalent glycol ether component (C) include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and oleyl alcohol. These can be used alone or in combination of two or more.

  The dihydric or higher alcohol component includes monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, trimethyloloctane, Examples include ditrimethylolpropane, dipentaerythritol, tripentaerythritol and the like. These can be used alone or in combination of two or more.

  The polyester resin used in the antifouling paint of this invention has a solid content acid value of 0 from the viewpoints of self-polishing properties, crack resistance, antifouling properties, old paint adhesion or long-term paint storage stability of the resulting paint film. It is preferable that it is -100 mgKOH / g, More preferably, it is the range of 0-50 mgKOH / g.

The polyester resin used in the antifouling paint of this invention has a number average molecular weight of 500 to 500 in terms of the self-polishing property and crack resistance, antifouling property, old paint adhesion or long-term paint storage stability of the resulting paint film. It is preferably 10,000, and more preferably 1,000 to 5,000.
In addition, the number average molecular weight used for description of this invention including what was mentioned above was measured on condition of the following using GPC method.
“Measurement apparatus: JASCO Corporation, column; Shodex GPC KF-806M, mobile phase; tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI, UV”

As a method for producing the polyester resin for antifouling paint used in the present invention, a general method for producing a polyester resin can be employed.
For example, phthalic anhydride corresponding to the dicarboxylic acid component (A), glycerin corresponding to the trihydric or higher polyhydric alcohol component (B), and diethylene glycol monoester corresponding to the monovalent glycol ether component (C) Butyl ether and, if necessary, refluxing organic solvent and catalyst are charged into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel in a batch or in any order, and heated to 150 to 250 ° C. to form an ester. The reaction can be carried out by terminating the reaction at an arbitrary time.

  This reaction can be carried out under solvent reflux, if necessary. At that time, a mixture of C9 and C10 alkylcyclohexane (manufactured by Maruzen Petrochemicals (trade name): Swaclean 150), ethylbenzene, o-xylene, m-xylene, p-xylene, toluene, etc. should be used as the solvent. Swaclean 150, o-xylene, m-xylene, and p-xylene are preferable. These solvents do not correspond to specific chemical substances in the Industrial Safety and Health Law, and are more preferable from the viewpoint of environmental response.

The antifouling paint contains an antifouling agent having an effect on lethality or repelling of varicella adhering organisms or both together with the polyester resin described above.
As such an antifouling agent, legally usable and well-known biocides and repellents can be selectively employed. For example, cuprous oxide, copper powder, cuprous thiocyanate, copper carbonate , Copper compounds such as copper chloride and copper sulfate, zinc sulfate, zinc oxide, nickel sulfate, copper-nickel alloy, rhodan copper, trialkylboron pyridine salt such as triphenylboron pyridine salt, 2-mercaptopyridine-N-oxide copper Organic zinc compounds such as 2-mercaptopyridine-N-oxide zinc, zinc ethylene bisdithiocarbamate, bis (dimethyldithiocarbamate) zinc, bis (dimethyldithiocarbamate) ethylenebis (dithiocarbamate) dizinc, and the like, 2,4,6-trichlorophenylmaleimide, N-phenylmaleimide, N- (2-ethyl-6methylphenol) ) Maleimide compounds such as -2,3 dichloromaleimide, N- (2,6-diethylphenyl) -2,3 dichloromaleimide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, etc. Isothiazoline compounds, nitrile compounds such as tetrachloroisophthalonitrile, benzothiazol compounds, triazine compounds, urea compounds, N-haloalkylthio compounds, tetracycline compounds, tetrachloromethylsulfonylpyridine, etc. .

  The blending amount of the antifouling agent is preferably included in the range of 1 to 500 parts by mass, more preferably 5 to 300 parts by mass with respect to 100 parts by mass of the resin solid content of the antifouling paint of the present invention. If it is set as this range, sufficient antifouling property can be obtained even in the sea area where the fouling is severe, and the coating film properties after immersion in seawater will be good.

  In particular, 2,4,6-trichlorophenylmaleimide, N-phenylmaleimide, N- (2-ethyl-6methylphenyl) -2,3 dichloromaleimide, N- (2,6-diethylphenyl) -2,3 dichloro The amount of maleimide compound such as maleimide is 1 to 100 parts by mass with respect to 100 parts by mass of the resin solid content of the antifouling paint. It is preferable at points, such as property, More preferably, it is the range of 5-50 mass parts.

The antifouling paint of the present invention may further contain a resin other than the polyester resin as an additional component as a coating film forming component, as long as it does not contradict the object of the present invention.
Examples of such resins include acrylic resins, acrylic silicone resins, unsaturated polyester resins, organic silyl ester resins, fluororesins, polybutene resins, silicone rubbers, urethane resins, polyamide resins, and vinyl chloride-vinyl isobutyl ether copolymers. , Vinyl chloride-vinyl acetate copolymer, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, chlorinated olefin resin, styrene / butadiene copolymer resin, epoxy resin, phenol resin, alkyd resin, coumarone resin , Petroleum resin, tall rosin, gum rosin, wood rosin, rosin derivatives as hydrogenated rosin, polymerized rosin, rosin metal salts as zinc chloride, calcium rosinate, copper rosinate, magnesium rosinate, other metals Reaction products of compounds and rosin, and the like. These can be used alone or in combination of two or more.

  Among them, tall rosin, gum rosin, wood rosin, rosin derivatives include hydrogenated rosin, polymerized rosin, rosin metal salts such as zinc rosinate, calcium rosinate, copper rosinate, magnesium rosinate, other metal compounds and rosin. A reaction product or the like is more preferable from the viewpoint of the antifouling property of the obtained coating film. These can be used singly or in combination of two or more, and the content thereof is rosin based on rosin or rosin derivative in 100% by mass of resin solid content of the antifouling paint of the present invention. The ratio of the resin is preferably in the range of 1 to 99% by mass, and more preferably in the range of 5 to 70% by mass.

  The antifouling paint of the present invention may further contain polyvinyl alkyl ether as a self-polishing promoting component, if necessary. Specific examples include polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl isopropyl ether, polyvinyl isobutyl ether and the like. These can be used alone or in combination of two or more. Of these, polyvinyl methyl ether and polyvinyl ethyl ether are preferable.

The content of such a polyvinyl alkyl ether is preferably such that the proportion of the polyvinyl alkyl ether is in the range of 1 to 50% by mass, more preferably 3 to 100% by mass of the resin solid content of the antifouling paint of this invention. It is in the range of 30% by mass.
As described above, the antifouling paint of the present invention contains a polyester resin as a main component and may contain other resins as an additive component, but the antifouling paint (solid content) of all these resins is 100% by mass. The content of is preferably 5 to 95% by mass in order to ensure the effects of the present invention, and more preferably 10 to 70% by mass.

The antifouling paint of this invention may further contain an organosilyl group-containing (meth) acrylic acid ester copolymer as a self-polishing property promoting component, if necessary.
Specific examples of the organic silyl ester group-containing monomer (D) represented by the general formula of Chemical Formula 3 include trinormalpropylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, and trinormalbutylsilyl (meth). Acrylate, triisobutylsilyl (meth) acrylate, trisecondary butylsilyl (meth) acrylate, trinormal amylsilyl (meth) acrylate, trinormal hexylsilyl (meth) acrylate, trinormal octylsilyl (meth) acrylate, trinormal dodecylsilyl Examples include (meth) acrylate and tribenzylsilyl (meth) acrylate.
Other examples having a (meth) acryloyloxy group in the molecule include diisopropyl normal butyl silyl (meth) acrylate, normal octyl dinormal butyl silyl (meth) acrylate, diisopropyl stearyl silyl (meth) acrylate, and the like. These can be used alone or in combination of two or more. Of these, triisopropylsilyl (meth) acrylate is preferable.

The polymerizable monomer (E) other than the monomer (D) is another monomer copolymerizable with the above monomer (D), and examples thereof include acrylic acid, methyl acrylate, and acrylic acid. Ethyl, normal butyl acrylate, tertiary butyl acrylate, secondary butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, 2-acrylate Acrylic esters such as methoxyethyl and 2-ethoxyethyl acrylate, methacrylic acid and methyl methacrylate, normal butyl methacrylate, tertiary butyl methacrylate, secondary butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, methacrylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, 2-methoxyethyl methacrylate, and the like methacrylic acid esters such as methacrylic acid 2-ethoxyethyl.
Other examples of the polymerizable monomer (E) include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate, styrene, acrylonitrile and the like.

  In the organosilyl group-containing (meth) acrylic acid ester copolymer of the present invention, the proportion of the monomer (D) and the other polymerizable monomer (E) used depends on the intended use of the coating composition. Although it can set suitably, generally it is good to make it a monomer (D) be 0-100 mass% and a polymerizable monomer (E) other than this will be 20-80 mass%.

  As a method for producing an organosilyl group-containing (meth) acrylic acid ester copolymer used in the antifouling paint according to the present invention, a general method for producing an acrylic acid ester copolymer can be employed.

  For example, triisopropylsilyl acrylate corresponding to the organic silyl ester group-containing monomer (D) represented by the general formula of Chemical Formula 3, methyl methacrylate corresponding to the polymerizable monomer (E), organic solvent, polymerization catalyst Are prepared in a batch or in any order in a reaction vessel equipped with a stirrer, condenser, thermometer, dripping device, nitrogen inlet tube, heating / cooling jacket, and heated to react at 60-120 ° C. under a nitrogen stream. be able to.

  Examples of the polymerization catalyst include azo compounds such as azobisisobutyronitrile and triphenylmethylazobenzene, peroxides such as benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, and t-butyl peroxyisopropyl carbonate. Is mentioned.

Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene, and a mixture of C9 and C10 alkylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd .: (Trade name) Swaclean 150) non-aromatic hydrocarbon solvent, alcohol solvents such as isopropanol, n-butanol, propylene glycol monomethyl ether, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, butyl acetate, isobutyl acetate, An ester solvent such as ethyl acetate can be used. Preferred are propylene glycol monomethyl ether, butyl acetate, Swaclean 150, o-xylene, m-xylene, and p-xylene.
These solvents do not correspond to specific chemical substances in the occupational safety and health law, and are preferable from the viewpoint of environmental measures. These solvents may be used alone or in combination of two or more.

  The content of such an organosilyl group-containing (meth) acrylic acid ester copolymer is contained in the range of 5 to 95% by mass in 100% by mass of the resin solid content of the antifouling paint of the present invention. preferable. In order to reliably achieve the effects of the present invention, the content is more preferably 10 to 90% by mass.

  The organosilyl group-containing (meth) acrylic acid ester copolymer used in the antifouling paint of this invention has a number average molecular weight of 500 to 100 from the viewpoint of self-polishing properties, crack resistance and antifouling properties of the resulting coating film. Is preferably 1,000, 20,000, more preferably 1,000 to 20,000.

In addition, the number average molecular weight used for description of this invention including what was mentioned above was measured on condition of the following using GPC method.
“Measurement apparatus: JASCO Corporation, column; Shodex GPC KF-806M, mobile phase; tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI, UV”

The antifouling paint of the present invention usually contains an appropriate amount of solvent so that it is convenient to use.
As such a solvent, a known organic solvent can be selectively used. For example, aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene, C9 and C10 Non-aromatic hydrocarbon solvent of a mixture of alkylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd .: (trade name) Swaclean 150), alcohol solvents such as isopropanol, n-butanol, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketone solvents, and ester solvents such as butyl acetate, isobutyl acetate, and ethyl acetate can be used. Preferred are propylene glycol monomethyl ether, butyl acetate, Swaclean 150, o-xylene, m-xylene, and p-xylene. These solvents do not correspond to specific chemical substances in the occupational safety and health law, and are preferable from the viewpoint of environmental measures. These solvents may be used alone or in combination of two or more.

  The antifouling paint of the present invention may further contain pigments, plasticizers, dispersants, antifoaming agents, solvents, and other usual additives used in antifouling paints, if necessary.

  There are no particular restrictions on the object for forming the coating film using the antifouling paint of the present invention and the coating method, and as an effective object, an underwater structure (for example, power generation facility, ship, port facility, buoy, pipe) Such as lines, bridges, submarine bases, aquaculture nets, stationary nets, etc.), or paint directly on the surface of the base material, or primers such as wash primers, zinc epoxy shop primers, etc .; vinyl tar, oily rust A single-layer coating film can be formed by applying a primer, chlorinated rubber-based, epoxy-based undercoat paints;

  In addition, a primer and primer coating are applied to form a multilayer coating film, or a primer coating, primer coating, and intermediate coating are applied in sequence to form a multilayer coating film on the surface of the substrate and directly onto Alternatively, it can be applied directly to the surface of the old coating film of the antifouling paint by a coating means such as brush coating, spray coating, roller coating or dipping.

  The application amount of these antifouling paints is generally 40 to 500 μm as a dry film thickness, and preferably in the range of 80 to 300 μm.

[Synthesis example 1 of polyester resin (solution)]
A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was charged with 100 parts of Swclean 150 as a reflux solvent (parts are parts by mass, the same applies hereinafter), and the blending ratios are shown in Table 1. As indicated by the number of moles, 1036 parts (7 moles) of phthalic anhydride, 368 parts (4 moles) of glycerin, and 648 parts (4 moles) of diethylene glycol monobutyl ether were charged, and the temperature was raised to 150 ° C. to form a transparent solution. Obtained. Next, 2 parts of dibutyltin oxide was added as a catalyst, the temperature was gradually raised to 230 ° C., the reaction was carried out at 230 ° C. for 3 hours, and the solution was cooled to 40 ° C. when the solid acid value became 25 or less. Thereto, propylene glycol monomethyl ether was charged as a diluent solvent, and a polyester resin solution 1 having a number average molecular weight of 2200, adjusted to have a solid content of 75%, was produced.

  In addition, the measurement of solid content acid value was performed as follows. A sample (10 g) was accurately weighed in a stoppered flask, and 100 mL of ethanol / toluene mixed solution (50:50) was added and dissolved. To this, a few drops of phenolphthalein test solution was added as an indicator, and titrated with an ethanol solution of 0.1 mol / L potassium hydroxide until a pale red color lasting 30 seconds was obtained. The solid content acid value was calculated from the amount of an ethanol solution of 0.1 mol / L potassium hydroxide required for titration by the following equation (1).

[Equation 1]
Solid content acid value = a × F × 5.611 × 100 / m × NV
a: Amount of ethanol solution of 0.1 mol / L potassium hydroxide (mL)
F: Potency of ethanol solution of 0.1 mol / L potassium hydroxide m: Mass of sample (g)
NV: heating residue (%), measured according to JIS K5601-1-2

[Synthesis Examples 2 to 21 of polyester resin (solution)]
Using a dicarboxylic acid component (A), a trihydric or higher polyhydric alcohol component (B) and a monovalent glycol ether component (C) in the number of moles shown in Table 1, the solid content was 75 as in Synthesis Example 1. % Polyester resin solution was obtained.

In addition, although all the description of each component in Table 1 was shown with the compound name, the brand name used for one part is as follows.
Polyethylene glycol monobutyl ether (EO21) (manufactured by NOF Corporation: UNIOX B-1000)
Polypropylene glycol monobutyl ether (PO20) (Nippon Yushi Co., Ltd .: Unilube MB-14)
Polyethylene glycol monomethyl ether (EO22) (manufactured by NOF Corporation: UNIOX M-1000)
Polyoxypropylene polyoxyethylene monobutyl ether (PO10, EO9) (manufactured by NOF Corporation: Unilube 50MB-11)
Biosuccinic acid (manufactured by Bioamber: succinic acid)

[Example 1]
As shown in Table 2, 24 parts of the polyester resin solution 1 having a solid content of 75% obtained in Synthesis Example 1 (18 parts of solid content), 38 parts of cuprous oxide, 10 parts of talc, A coating material was prepared by mixing and dispersing 3 parts, 1 part of an organic derivative of bentonite clay, 1 part of polyethylene oxide, and 25 parts of o-xylene using a sand mill. About the obtained antifouling paint, it used for the following various tests.

In addition, although description of each component in Table 2 was shown by the compound name, the brand name used for one part is as follows.
Bentonite Clay Organic Derivatives (Made by Elementis: Benton 52)
Polyethylene oxide (Ito Oil Co., Ltd .: ASA DS-525, 20% alkylcyclohexane paste)
Polyvinyl methyl ether (BASF Corporation: Lutnar M-40)
2,4,6-trichlorophenylmaleimide (manufactured by K.I. Kasei Co., Ltd .: IT354)
75% rosin resin (Arakawa Chemical Industries, Ltd .: China rosin WW, adjusted to 75% solids using o-xylene as solvent)

[Examples 2-31 and Comparative Examples 1-3]
Each antifouling paint was obtained in the same manner as in Example 1 except that the formulation shown in Table 2 was used. About the obtained antifouling paint, it used for the following various tests.

[Synthesis Example S-1 of Organosilyl Group-Containing (Meth) acrylic Acid Ester Copolymer]
A reaction vessel equipped with a stirrer, a condenser, a thermometer, a dripping device, a nitrogen introduction tube, and a heating / cooling jacket was charged with 492.5 parts of o-xylene, and heated and stirred under a temperature of 85 ° C. in a nitrogen stream. While maintaining the same temperature, a mixture of 250 parts of triisopropylsilyl acrylate, 250 parts of methyl methacrylate, and 5 parts of 2,2′-azobisisobutyronitrile as a polymerization initiator was put into the reactor from the dropping device for 3 hours. It was dripped over. Then, after stirring at the same temperature for 3 hours, 2.5 parts of 2,2′-azobisisobutyronitrile was added, and further stirred at the same temperature for 2 hours, the number average molecular weight was 5700, the weight A copolymer solution S-1 adjusted with o-xylene so that the average molecular weight was 13500 and the solid content was 50% was obtained.

[Synthesis example S-2 of organosilyl group-containing (meth) acrylic acid ester copolymer]
A reaction vessel equipped with a stirrer, a condenser, a thermometer, a dripping device, a nitrogen introduction tube, and a heating / cooling jacket was charged with 492.5 parts of o-xylene, and heated and stirred under a temperature of 85 ° C. in a nitrogen stream. While maintaining the same temperature, a mixture of 350 parts of triisopropylsilyl acrylate, 150 parts of methyl methacrylate, and 5 parts of 2,2′-azobisisobutyronitrile of the polymerization initiator was added to the reactor from the dropping apparatus over 3 hours. And dripped. Then, after stirring at the same temperature for 3 hours, 2.5 parts of 2,2′-azobisisobutyronitrile was added, and further stirred at the same temperature for 2 hours, the number average molecular weight was 5500, the weight A copolymer solution S-2 adjusted with o-xylene so that the average molecular weight was 14700 and the solid content was 50% was obtained.

[Example 32]
As shown in Table 3, 2.4 parts of the polyester resin solution 1 having a solid content of 75% obtained in Synthesis Example 1 (1.8 parts of solid content) and the solid resin obtained in Synthesis Example S-1 32.4 parts (solid content 16.2) of an organosilyl group-containing (meth) acrylic acid ester copolymer resin solution with a content of 50%, 36 parts of cuprous oxide, 9 parts of talc, 3 parts of valvule, A paint was prepared by mixing and dispersing 1 part of molecular sieve 4A, 1 part of an organic derivative of bentonite clay, 1 part of polyethylene oxide and 14.2 parts of o-xylene with a sand mill. About the obtained antifouling paint, it used for the following various tests.

In addition, although all the description of each component in Table 3 was shown with the compound name, the brand name used for one part is as follows.
Bentonite Clay Organic Derivatives (Made by Elementis: Benton 52)
Polyethylene oxide (Ito Oil Co., Ltd .: ASA DS-525, 20% alkylcyclohexane paste)
Polyvinyl methyl ether (BASF Corporation: Lutnar M-40)
2,4,6-trichlorophenylmaleimide (manufactured by K.I. Kasei Co., Ltd .: IT354)
75% rosin resin (Arakawa Chemical Industries, Ltd .: China rosin WW, adjusted to 75% solids using o-xylene as solvent)
Synthetic zeolite powder (Union Showa Co., Ltd .: Molecular sieve 4A)

[Examples 33 to 38 and Comparative Examples 4 to 5]
Each antifouling paint was obtained in the same manner as in Example 32 except that the formulation shown in Table 3 was used. About the obtained antifouling paint, it used for the following various tests.

[Short-term storage stability]
Each antifouling paint obtained in Examples 1 to 38 and Comparative Examples 1 to 5 was observed in accordance with JIS K5600-2-7, and the paint state after one month storage at room temperature was evaluated according to the following criteria. The results are shown in Tables 4 and 5.
○: The paint is suitable for use.
X: The paint does not become suitable for use.

[Long-term storage stability]
Each antifouling paint obtained in Examples 1 to 38 and Comparative Examples 1 to 5 was observed in accordance with JIS K5600-2-7, and the paint state after 6 months storage at room temperature was evaluated according to the following criteria. The results are shown in Tables 4 and 5.
○: The paint is suitable for use.
X: The paint does not become suitable for use.

[Anti-fouling performance test]
Each of the antifouling paints obtained in Examples 1 to 38 and Comparative Examples 1 to 5 was subjected to a blasted steel plate having a size of 90 × 300 × 1.2 mm, which had been previously anticorrosive-coated with an epoxy paint, and the dry film thickness was The test plate was prepared by air spray coating to 200 μm and drying for one week. This test plate is immersed in a 1m deep sea in the bay (Seto Inland Sea) of Hatsukaichi City, Hiroshima Prefecture, and the state of the coating is observed every 6 months for 12 months. The results are evaluated according to the following criteria. The results are shown in Table 5.
A: Biofouling area is less than 5%.
○: Biofouling area is 5% or more and less than 10%.
Δ: The biofouling area is 10% or more and less than 30%.
X: Biofouling area is 30% or more.

[Crack resistance test]
Each of the antifouling paints obtained in Examples 1 to 38 and Comparative Examples 1 to 5 was subjected to a blasted steel plate having a size of 90 × 300 × 1.2 mm, which had been previously anticorrosive-coated with an epoxy paint, and the dry film thickness was The test plate was prepared by air spray coating to 200 μm and drying for one week. Immerse this test board on the surface of the bay (Seto Inland Sea) in Hatsukaichi City, Hiroshima Prefecture so that half of the test paint plate comes out, and check the state of the coating for 6 months every 12 months. The results were observed and evaluated according to the following criteria, and the results are shown in Tables 4 and 5.
○: No cracks are observed.
Δ: Slight cracks are observed.
X: A crack is recognized.

[Seawater resistance test]
Each of the antifouling paints obtained in Examples 1 to 38 and Comparative Examples 1 to 5 was subjected to a blasted steel plate having a size of 90 × 300 × 1.2 mm, which had been previously anticorrosive-coated with an epoxy paint, and the dry film thickness was The test plate was prepared by air spray coating to 200 μm and drying for one week. This test plate was immersed in seawater at 25 ° C., and the state of the coating film was observed after 6 months and evaluated according to the following criteria. The results are shown in Tables 4 and 5.
○: Cracks, blisters, peeling, etc. are not observed in the coating film.
(Triangle | delta): A crack, a swelling, peeling, etc. are recognized slightly in a coating film.
X: Cracks, blisters, peeling, etc. are observed in the coating film.
During the above test, natural sea water having a water temperature of 23 ° C. ± 5 ° C., a pH of 8.1 ± 0.2, and a salinity of 32 ± 2 ‰ was used as the sea water, and the test was performed under flowing water for component adjustment during the period.

[Old paint adhesion test]
Each of the antifouling paints obtained in Examples 1 to 38 and Comparative Examples 1 to 5 was subjected to a blasted steel plate having a size of 90 × 300 × 1.2 mm, which had been previously anticorrosive-coated with an epoxy paint, and the dry film thickness was Air spray coating to 200μm, dried for 1 week, soaked in seawater for 3 months, washed the surface of the coating with clean water, dried for 1 week, old coating (old antifouling coating Film). Each of the antifouling paints obtained in Examples 1 to 38 and Comparative Examples 1 to 5 was applied by air spray to the old coating film so that the dry film thickness was 200 μm, and dried for one week to obtain a test plate. Created. This test plate was immersed in seawater for 3 months, dried for one week, and then evaluated according to the following criteria. The results are shown in Tables 4 and 5.

With a cutter on the coating film of the test plate, six vertical and horizontal scratches reaching the base were put in a grid pattern to prepare 25 squares of 4 mm square. A cellophane tape (24 mm width, manufactured by Nichiban Co., Ltd.) is applied to the 25 squares so that no air bubbles enter, and one end of this tape is held in your hand and quickly peeled off. Examined.
○: When the number of grids not peeled is 23 to 25 Δ: When the number of grids not peeled is 18 to 22
X: When the number of grids not peeled is 0 to 17 Natural seawater having a water temperature of 23 ° C. ± 5 ° C., a pH of 8.1 ± 0.2, and a salinity of 32 ± 2 ‰ is used as the sea water. The inside was performed under running water to adjust the ingredients.

[Self-polishing test]
Each antifouling paint obtained in Examples 1 to 38 and Comparative Examples 1 to 5 was subjected to a blasted steel plate having a size of 70 × 150 × 1.2 mm, which had been previously anticorrosive coated with an epoxy paint, and the dry film thickness was The test plate was prepared by air spray coating to 200 μm and drying for one week.
After fixing the above test piece to the outer surface of a cylindrical rotating body (drum-type rotor) installed in the test tank, the test plate has a water temperature of 23 ° C. ± 5 ° C., PH 8.1 ± 0. 2. Put natural seawater with a salinity of 32 ± 2 ‰, rotate with a motor so that the peripheral speed of the drum is 13 ± 3 knots, and run under running water so as not to affect self-polishing during the test. The self-polishing property was measured every 2000 hours for the amount of coating abrasion (μm) up to 6000 hours, and the results are shown in Tables 4 and 5.

As is clear from the results of Tables 4 and 5, in the paints of Comparative Examples 1 to 5, the storage stability of the paint, long-term antifouling properties, crack resistance, and any or all of the old paint film adhesion, Satisfactory results were not obtained.
On the other hand, the antifouling paint containing a polyester resin mainly composed of the dicarboxylic acid component of Examples 1 to 38, a trihydric or higher polyhydric alcohol component, and a monovalent glycol ether component is used over a long period of time. Self-polishing and flexible coating structure can be maintained, and it exhibits good antifouling performance over a long period of time without causing embrittlement and cracking of the coating. It was possible to obtain a coating film having excellent adhesion by overlaying the paints, and to maintain a good paint state even in a long-term storage state.
In particular, for Examples 22 to 38 in which polyvinyl methyl ether, rosin resin, 2,4,6-trichlorophenylmaleimide, and an organosilyl group-containing (meth) acrylic acid ester copolymer were combined, a better self Abrasiveness and long-term antifouling properties were observed.

  Antifouling paints that give good results in preventing pollution by organisms such as microorganisms and algae attached to the surface of various structures such as ships, marine structures, seawater introduction pipes, etc. Furthermore, it can be used for a polyester resin which is a component of a coating film of such a paint.

Claims (10)

An antifouling paint containing a polyester resin for an antifouling paint and an antifouling agent,
The polyester resin for antifouling paints is a polyester resin having a dicarboxylic acid component (A), a trihydric or higher polyhydric alcohol component (B), and a monovalent glycol ether component (C) as essential constituent components. Antifouling paint featuring. The antifouling paint according to claim 1, wherein the monovalent glycol ether component (C) is a glycol ether represented by the following formula (1).
[Chemical 1]
R ¹ O — [(EO) _m (PO) _n ] —H
(Wherein R ¹ is a linear or branched alkyl group having 1 to 5 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and m and n are averages of EO and PO, respectively. 0 or a positive integer representing the number of repetitions, and 2 ≦ m + n ≦ 50, and (EO) _m and (PO) _n are copolymer components added in a random or block form.) 3. The antifouling paint according to claim 2, wherein the glycol ether represented by the following formula 2 is used in place of the glycol ether represented by the formula 1 above.
[Chemical 2]
R ¹ O — [(EO) _m (PO) _n ] —H
(Wherein R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and m and n are averages of EO and PO, respectively. 0 or a positive integer representing the number of repetitions, 2 ≦ m + n ≦ 40, and (EO) _m and (PO) _n are copolymerization components added in a random or block form.)   The dicarboxylic acid component (A) is phthalic anhydride, phthalic acid, isophthalic acid, 1,2,3,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic acid, hexahydrophthalic anhydride, hexa One or more dicarboxylic acids selected from hydrophthalic acid, 3,4,5,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic acid, succinic anhydride, succinic acid and biosuccinic acid The antifouling paint according to any one of claims 1 to 3.   The trihydric or higher polyhydric alcohol component (B) is one or more selected from the group consisting of glycerin, diglycerin, trimethylolpropane, trimethylolethane, pentaerythritol and tris (2-hydroxyethyl) isocyanurate. The antifouling paint according to any one of claims 1 to 4, which is a monohydric alcohol.   The antifouling paint is an antifouling paint containing at least one rosin resin selected from the group consisting of tall rosin, gum rosin, wood rosin, hydrogenated rosin and polymerized rosin as an additive component. Antifouling paint as described in 1. The antifouling paint comprises, as an additive component, one or more polymers of the monomer (D) represented by the following general formula 3 and / or 1 of the monomer (D). An organosilyl group-containing (meth) acrylic acid ester copolymer comprising a polymer of one or more species or two or more polymerizable monomers (E) other than the monomer (D). The antifouling paint according to any one of claims 1 to 6, wherein the antifouling paint is contained.

  The antifouling paint according to any one of claims 1 to 7, wherein the antifouling paint is an antifouling paint containing polyvinyl alkyl ether as an additive component.   The antifouling agents are 2,4,6-trichlorophenylmaleimide, N-phenylmaleimide, N- (2-ethyl-6methylphenyl) -2,3dichloromaleimide and N- (2,6-diethylphenyl)- The antifouling paint according to any one of claims 1 to 8, which is an antifouling agent containing one or more maleimide compounds selected from the group consisting of 2,3 dichloromaleimide.   The antifouling paint according to any one of claims 1 to 9, wherein the antifouling paint is an antifouling paint containing at least one solvent selected from alkylcyclohexane, o-xylene, m-xylene and p-xylene. .