CN106905802A

CN106905802A - Antifouling paint compositions and the coated article with its film

Info

Publication number: CN106905802A
Application number: CN201610945373.5A
Authority: CN
Inventors: 川村力; 梅田穰; 北岛昌和
Original assignee: Kansai Paint Co Ltd; NKM Coatings Co Ltd
Current assignee: Kansai Paint Co Ltd; Kansai Paint Marine Co Ltd
Priority date: 2015-10-27
Filing date: 2016-10-26
Publication date: 2017-06-30
Anticipated expiration: 2036-10-26
Also published as: CN106905802B; KR20170049392A

Abstract

It is an object of the invention to, the coated articles such as the works of fishing net, ship, ocean or bay bank of antifouling paint compositions and the film with the antifouling paint compositions are provided, the antifouling paint compositions can form the antifouling coat for being not likely to produce the paint film defects such as film stripping, bubbling, cracking by maintaining excellent soil resistance for prolonged period of time.The present invention is the coated article of antifouling paint compositions and the film with said composition, and the antifouling paint compositions are included in resin matrix polyester resin, the resin of ester group containing silicyl and/or the resin and anti-fouling agent with metal carboxylate structure with specific Component units.

Description

Antifouling paint compositions and the coated article with its film

Technical field

The present invention relates to antifouling paint compositions and the coated article with its film, more specifically, shape is related to Into can pass through long-term maintain excellent soil resistance antifouling coat antifouling paint compositions and application with its film Article.

Background technology

In recent years, the antifouling paint resin of the copolymer containing organotin of marine pollution is worried as substitution, in sea Having water-disintegrable resin in water has carried out various researchs.Using the antifouling paint with water-disintegrable resin containing as Film and sea that composition (i.e. hydrolysis-type antifouling paint compositions) is formed in ship etc. with the surface of the works of contact with sea water Water contact when, described being lentamente hydrolyzed with water-disintegrable resin and film gradually dissolves in the seawater, film table Face is continuously updated, and thus maintains its antifouling property to be possibly realized.As having water-disintegrable resin in the seawater, so far Many hydrolysis-types containing the resin containing trialkylsilkl ester group or the resin with metal carboxylate structure are proposed to prevent Dirty coating composition.But, the alkyl that the resin containing trialkylsilkl ester group has by trialkylsilkl ester group The structure of species or the resin and hydrolysis rate is different, in addition, the resin with metal carboxylate structure because metal species or The structure of the resin and hydrolysis rate is different, therefore, use the antifouling paint compositions with these with water-disintegrable resin The control of the film for obtaining mostly dissolution velocity in the seawater becomes difficult.

Therefore, studying always as by and with have has water-disintegrable resin and rosin or rosin derivative Hydrolysis-type antifouling paint compositions control the method (with reference to patent document 1~6) of the dissolution velocity of film.By being so used in combination With water-disintegrable resin and rosin or rosin derivative, although the dissolution velocity of film can be controlled in a way, but, When the usage amount of rosin or rosin derivative is few, there is the dissolubility of the film that can not fully obtain in seawater, be difficult to continue The problem of the antifouling property of film.On the other hand, when the usage amount of rosin or rosin derivative is more, by the film in seawater Dissolution velocity become big and improve antifouling property, but the physical property or cementability of film can be reduced, therefore, it is possible to easily produce painting The paint film defect such as film stripping or bubbling, cracking, the long-term maintenance of antifouling property becomes difficult.

And, in order to solve these problems, it is proposed that contain polyester resin and containing three with the quality ratio in particular range The antifouling paint compositions (with reference to patent document 7) of aIkylsilyl groups ester base resin.According to described antifouling paint compositions, Although the antifouling coat of the paint film defects such as bubbling or cracking can be formed with excellent soil resistance and is not likely to produce, Constituted according to the exposed marine site of antifouling coat or coating, in terms of the long-term maintenance of antifouling property, film performance is not somewhat sometimes Foot, therefore, seeking further improvement.

Prior art literature

Patent document

Patent document 1：Unexamined Patent 10-30071 publications

Patent document 2：JP 2002-53797 publications

Patent document 3：JP 2011-26357 publications

Patent document 4：JP 2011-32489 publications

Patent document 5：International Publication No. 2011/046087

Patent document 6：Unexamined Patent 9-286933 publications

Patent document 7：International Publication No. 2015/156073

The content of the invention

Invent problem to be solved

It is an object of the present invention to provide the fishing of antifouling paint compositions and the film with the antifouling paint compositions The coated articles such as the works of net, ship, ocean or bay bank, the antifouling paint compositions can be by tieing up for prolonged period of time Excellent soil resistance is held, the antifouling coat for being not likely to produce the paint film defects such as film stripping, bubbling, cracking can be formed.

Means for solving the problems

The present inventor has made intensive studies to achieve these goals, as a result finds, by containing in resin matrix Polyester resin (A), the resin of ester group containing silicyl (B1) with specific Component units and/or with metal carboxylate structure Resin (B2) and anti-fouling agent (C) antifouling paint compositions obtained from film, control the dissolving speed of film in ocean Degree be it is possible, can be by maintaining excellent soil resistance for prolonged period of time, and the physical property of film is also excellent, therefore, will be upper In the case of stating the boat bottom that antifouling paint compositions are coated on ship, be not likely to produce under sail or in berthing film peel off or The paint film defects such as bubbling, cracking.The present invention is completed based on such opinion.

The present invention provides the antifouling paint compositions described in following items and the coated article with its film.

A kind of (item 1) antifouling paint compositions, its contain polyester resin (A), the resin of ester group containing silicyl (B1) and/or Resin (B2) and anti-fouling agent (C) with metal carboxylate structure, it is characterised in that the polyester resin (A) is in the resin With the Component units and total quality of the Component units shown in following formula (1) with the polyester resin (A) in skeleton Quality be polyester resin in the range of 2~50 mass % as benchmark, the polyester resin (A) and described containing silicyl Total mass ratio of ester base resin (B1) and the resin (B2) with metal carboxylate structure is 3/97~80/20 scope It is interior.

【Change 1】

(in formula, R₀Hydrogen atom or methyl are represented, m represents 1~100 integer.)

The antifouling paint compositions of (item 2) as described in item 1, it is characterised in that the resin of ester group containing silicyl (B1) 1 kind or 2 of monomer (b2) beyond the one kind or two or more and described monomer (b1) of the monomer (b1) shown in following formula (2) Plant the copolymer of the above.

【Change 2】

[in formula, R₄Represent hydrogen atom or methyl, R₁、R₂And R₃Separately represent alkyl, R₅Represent hydrogen atom or R₆- O-CO- (wherein, R₆Represent organic group or-SiR₇R₈R₉Shown silicyl, R₇、R₈And R₉Separately represent hydrocarbon Base.).]

The antifouling paint compositions of (item 3) as described in item 1 or 2, it is characterised in that described with metal carboxylate structure Resin (B2) has the characteristic group with metal carboxylate structure shown in following formula (3), described with metal carboxylate knot In the resin (B2) of structure the content of contained metallic atom using the solid constituent quality of the resin (B2) as benchmark be 0.04 In the range of~3.50 moles/kg.

【Change 3】

(in formula, M represents divalent metallic atom, and X is represented in the group for selecting free hydroxyl, organic acid residue and alcohol residue to constitute At least a kind group.)

The antifouling paint compositions of (item 4) as any one of item 1~3, it is characterised in that the polyester resin (A) Be using containing at least a kind raw mixture of composition in selected from the group being made up of lactic acid, the lactide of lactic acid and PLA, with And containing at least a kind raw mixture of composition in selected from the group being made up of glycolic, glycolide and polyglycolic acid at least A kind of raw mixture and the polyester resin that manufactures, and the polyester resin (A) acid number be 0.1~120KOHmg/g scope It is interior.

The antifouling paint compositions of (item 5) as any one of item 1~4, it is characterised in that the polyester resin (A) Weight average molecular weight in the range of 190~15000.

The antifouling paint compositions of (item 6) as any one of item 1~5, it is characterised in that the polyester resin (A) It is the polyester resin without metal carboxylate structure.

A kind of (item 7) coated article, it has the film of the antifouling paint compositions any one of item 1~6.

The effect of invention

Antifouling paint compositions of the invention can be by maintaining excellent soil resistance, and can be formed to be difficult for prolonged period of time Produce the film of the paint film defects such as film stripping, bubbling, cracking.

Specific embodiment

Antifouling paint compositions of the invention are to contain polyester resin (A), the resin of ester group containing silicyl (B1) and/or tool There are the resin (B2) of metal carboxylate structure and the antifouling paint compositions of anti-fouling agent (C), it is characterised in that the polyester resin (A) it is with institute in the resin matrix with the Component units and total quality of the Component units shown in following formula (1) It is polyester resin in the range of 2~50 mass % that the quality of polyester resin (A) is stated as benchmark, the polyester resin (A) and Total mass ratio of the resin of ester group containing silicyl (B1) and the resin (B2) with metal carboxylate structure is In the range of 3/97~80/20.

【Change 4】

Hereinafter, antifouling paint compositions of the invention are described in detail.

[polyester resin (A)]

There is the formula (1) institute in the resin matrix for the polyester resin (A) of antifouling paint compositions of the invention The Component units for showing.It is excellent in the manufacture of the resin in order to the Component units shown in the formula (1) are directed in into polyester resin Selecting will hand over selected from least a kind composition in the group being made up of lactic acid, the lactide of lactic acid and PLA and selected from by glycolic, second At least a kind composition of at least one of composition in the group that ester and polyglycolic acid are constituted is used as raw material.It is explained, this specification In glycolide alias be 1,4- bis-Alkane -2,5- diketone (1,4-Dioxane-2,5-dione).

In addition, R of the total quality of the Component units shown in the formula (1) in the formula (1)₀It is the situation of methyl Under, the quality using the polyester resin (A), as benchmark, is 2~50 mass %, preferably 5~40 mass %, more preferably In the range of 10~30 mass %, the R in the formula (1)₀In the case of for hydrogen atom, with the quality of the polyester resin (A) It is in the range of 2~50 mass %, preferably 4~40 mass %, further preferred 6~30 mass % as benchmark.In the composition Total quality of unit less than 2 mass % situation or more than 50 mass % in the case of, the film for obtaining chronically is maintained sometimes Soil resistance it is difficult.

Polyester resin (A) can be manufactured with known method, it is possible to use selected from by lactic acid, the lactide of lactic acid and poly- Lactic acid constitute group at least a kind composition and selected from the group being made up of glycolic, glycolide and polyglycolic acid at least 1 Plant the composition of at least one of composition；Beyond lactic acid, the lactide of lactic acid and PLA and glycolic, glycolide and polyglycolic acid Sour composition (a1)；With the alcohol composition beyond lactic acid, the lactide of lactic acid and PLA and glycolic, glycolide and polyglycolic acid (a2) these each compositions, are made reciprocally to react and manufacture.

It is explained, the above-mentioned reaction for manufacturing polyester resin (A) gathers comprising esterification, ester exchange reaction, open loop Close any one of the known reactions such as reaction, opening.In addition, in this specification, will be used to manufacture polyester tree sometimes The above-mentioned reaction of fat (A) is referred to as " polymerisation ".

The lactide and PLA of lactic acid, lactic acid

In the manufacture of polyester resin (A), lactic acid, the lactide of lactic acid and PLA can directly use commercially available product.These Compound is respectively present optical isomer, but in the present invention, it is possible to use contain the change of L- bodies and D- bodies with arbitrary ratio Compound.Can be by maintaining excellent soil resistance for prolonged period of time, being not likely to produce film stripping, drum/bubble, cracking etc. in order to be formed The antifouling coat of paint film defect, in the manufacture of polyester resin (A), among above-claimed cpd, particularly preferably uses the friendship of lactic acid Ester and/or PLA.

Glycolic, glycolide and polyglycolic acid

In the manufacture of polyester resin (A), glycolic, glycolide and polyglycolic acid can be used as it is commercially available product.In order to Formed can be by maintaining excellent soil resistance, being not likely to produce preventing for the paint film defects such as film strippings, bubbling, cracking for prolonged period of time Dirty film, in the manufacture of polyester resin (A), among above-claimed cpd, particularly preferably uses glycolic and/or glycolide.

In addition, in the manufacture of polyester resin (A), above-mentioned PLA and polyglycolic acid can respectively use Weight-average molecular Measure as the PLA in the range of 450~1000000 hands over polyglycolic acid.

Sour composition (a1)

In the present invention, sour composition (a1) can use the sour composition of the manufacture for being generally used for polyester resin.As so Sour composition, can enumerate for example：Alicyclic polyacid, aliphatic polybasic acids, aromatic polyvalent acid, aromatic monocarboxylate, fat Race's monocarboxylic acid, cycloaliphatic monocarboxylic and these sour carboxylate, acid anhydrides and halide.

In general alicyclic polyacid is with (predominantly 4~6 yuan of the ester ring type structure of more than 1 in 1 molecule Ring) and the carboxyl of more than 2 compound and the acid anhydrides of the compound, carboxylate and halide etc..It is alicyclic many as this First acid, can enumerate for example：1,2- cyclohexane dicarboxylic acids, 1,3- cyclohexane dicarboxylic acids, 1,4- cyclohexane dicarboxylic acids, 2- cyclohexene- 1,2- dicarboxylic acids, 3- cyclohexene -1,2- dicarboxylic acids, 4- cyclohexene -1,2- dicarboxylic acids, tetrahydrochysene methylphthalic acid class, 3- first Base -1,2- cyclohexane dicarboxylic acids, 4- methyl isophthalic acids, 2- cyclohexane dicarboxylic acids, 1,2,4- cyclohexanetricarboxylic acids, 1,3,5- hexamethylenes three The alicyclic polycarboxylic acids such as carboxylic acid；The acid anhydrides of these alicyclic polycarboxylic acids；The lower alkyl esters of these alicyclic polycarboxylic acids Compound etc., these can be used alone or are applied in combination two or more.

In general aliphatic polybasic acids are aliphatic compound, fat of the carboxyl in 1 molecule with more than 2 The acid anhydrides of compounds of group, the halide of the aliphatic compound.As the aliphatic polybasic acids, can enumerate for example：Butanedioic acid, third Diacid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, 12 The aliphatic polycarboxylic acids such as docosandioic acid, tridecandioic acid, octadecane diacid, citric acid；The acid anhydrides of these aliphatic polycarboxylic acids； Halide of these aliphatic polycarboxylic acids etc., these can be used alone or are applied in combination two or more.

In general aromatic polyvalent acid be the aromatic compound of the carboxyl in 1 molecule with more than 2 and be somebody's turn to do The halide of the acid anhydrides of aromatic compound, the carboxylate of the aromatic compound and aromatic compound.

As having 2 aromatic polyvalent acid of carboxyl in 1 molecule, can enumerate for example：Phthalic acid, isophthalic diformazan The aromatic polycarboxylic acids such as acid, terephthalic acid (TPA), naphthalene dicarboxylic acids, 4,4 '-diphenyldicarboxylic acid；These aromatic polycarboxylic acids Acid anhydride etc..

Used as the aromatic polyvalent acid with the carboxyl of more than 3 in 1 molecule, the aromatic series that can enumerate such as 3 yuan is more First carboxylic acid, 4 yuan aromatic polycarboxylic acid etc..As 3 yuan of aromatic polycarboxylic acid, can enumerate for example：Trimellitic acid, inclined benzene The trimellitic acid classes such as three acid anhydrides, trimellitic acid Arrcostab, trimellitic acid halide；Benzene-1,2,3-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid acid anhydride, benzene-1,2,3-tricarboxylic acid The benzene-1,2,3-tricarboxylic acid classes such as Arrcostab, benzene-1,2,3-tricarboxylic acid halide；Trimesic acid, trimesic acid Arrcostab, trimesic acid halide etc. are Benzenetricarboxylic acid class；The carboxyl various naphthalene tricarboxylic acids and its acid anhydrides different to the bonding position of aromatic rings；Bonding of the carboxyl to aromatic rings Position different various anthracene tricarboxylic acids and its acid anhydrides；The carboxyl various xenyl tricarboxylic acids different to the bonding position of aromatic rings and Its acid anhydrides；The carboxyl various benzophenone tricarboxylic acids and its acid anhydrides different to the bonding position of aromatic rings；The inclined benzene three of ethylenebis Acid and its acid anhydrides etc..In addition, as 4 yuan of aromatic polycarboxylic acid, can enumerate for example：PMA, pyromellitic acid dianhydride, The PMA classes such as benzenetetracarboxylic acid Arrcostab, PMA halide；Mellophanic acid, mellophanic acid dianhydride, mellophanic acid Arrcostab, The mellophanic acid class such as mellophanic acid halide；Prehnitic acid (prehnitic acid), prehnitic acid acid anhydride, prehnitic acid alkyl Prehnitic acid classes such as ester, prehnitic acid halide etc..Above-mentioned aromatic polyvalent acid can be used alone or be applied in combination 2 kinds with On.

In the present invention, the sour composition (a1) for the manufacture of polyester resin (A) can use aromatic monocarboxylate, fat The monocarboxylic acids such as race's monocarboxylic acid, cycloaliphatic monocarboxylic.As above-mentioned aromatic monocarboxylate, can enumerate for example：Benzoic acid, methylbenzene first Acid, ethyl benzoate, p-tert-butyl benzoic acid, naphthalene-carboxylic acid, salicylic acid, 4- methyl benzoic acids, 3- methyl benzoic acids, phenoxy group vinegar Acid, biphenyl carboxylic acid etc..In addition, as above-mentioned aliphatic monocarboxylic acid, can enumerate for example：Acetic acid, propionic acid, butyric acid, octanesulfonic acid, the last of the ten Heavenly stems Alkanoic acid, dodecylic acid, octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, laurate, tetradecanoic acid, palmitic acid, stearic acid, oleic acid, anti-oil Acid, brassidic acid, linoleic acid, leukotrienes, rosin acid, fatty acid distribution of coconut oil, cottonseed oil fatty acid, flaxseed oil aliphatic acid, rice bran oil Aliphatic acid, fish oil fatty acid, ready denier oil acid, soya fatty acid, linseed oil aliphatic acid, tung oil fatty acid, rapeseed oil The saturations such as aliphatic acid, Castor Oil Fatty Acid, dehydrated castor oil fatty acid, safflower oil fatty acid or undersaturated aliphatic list carboxylic Acid, these can be used alone or are applied in combination two or more.

As above-mentioned cycloaliphatic monocarboxylic, can enumerate for example：Cyclohexane-carboxylic acid, cyclopentane-carboxylic acid, Cycloheptanoic acid, 4- second Butylcyclohexane carboxylic acid, 4- hexyls cyclohexane-carboxylic acid, 4- lauryl cyclohexane-carboxylic acids etc., these can be used alone or are applied in combination Two or more.

In the present invention, the sour composition (a1) for the manufacture of polyester resin (A) can contain the glycerine of above-mentioned monocarboxylic acid The carboxylates such as ester.As the glyceride of monocarboxylic acid, can enumerate for example：It is cocounut oil, cottonseed oil, hemp-seed oil, rice bran oil, fish oil, appropriate Your oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, safflower oil etc..

In addition, in the present invention, from from the viewpoint of the long-term maintenance of soil resistance, for the manufacture of polyester resin (A) Sour composition (a1) preferably comprises aromatic polyvalent acid, and its content, using total molal quantity of sour composition (a1) as benchmark, is 30 to rub You are more than %, preferably 50 moles more than %, more preferably 70 moles more than %.

Alcohol composition (a2)

In the present invention, alcohol composition (a2) can use the alcohol composition of the manufacture for being generally used for polyester resin.As so Alcohol composition, preferably comprise 2 yuan of alcohol such as alicyclic diol, aliphatic diol, aromatic diol and/or more than 3 yuan of polyalcohol Material, can enumerate for example：Ethylene glycol, diethylene glycol, triethylene glycol, TEG, five ethylene glycol, 1,2- propane diols, two -1, 2- propane diols, three -1,2- propane diols, 1,2- butanediols, 2,3- butanediols, 1,2- hexylene glycols, 1,2- dihydroxies butylcyclohexane, 3- second Epoxide propane -1,2- glycol, 3- phenoxypropane -1,2- glycol, neopentyl glycol, 2- methyl-1,3-propanediols, 2- methyl -2, 4- pentanediols, 3- methyl isophthalic acids, 3- butanediols, 2- ethyl -1,3- hexylene glycols, 2,2- diethyl -1,3- propane diols, 2,2,4- front threes Base -1,3- pentanediols, 2-butyl-2-ethyl-1,3-propanediol, 2- phenoxypropane -1,3- glycol, 2- methyl -2- phenyl third Alkane -1,3- glycol, 1,3- propane diols, 1,3 butylene glycol, 2- ethyl -1,3- ethohexadiols, 1,3- dihydroxies butylcyclohexane, 1,4- fourths two Alcohol, 1,4- dihydroxies butylcyclohexane, 1,5- pentanediols, 1,6-HD, 2,5-HD, 3- methyl isophthalic acids, 5- pentanediols, 1,4- bis- Methylol hexamethylene, Tricyclodecane Dimethanol, 2,2- dimethyl -3- hydroxypropyl -2,2- dimethyl -3- hydroxy propionate (hydroxyls The carboxylate of base neopentanoic acid and neopentyl glycol), bisphenol-A, Bisphenol F, the alkylidene oxide addition product of bisphenol-A, it is double (4- hydroxyls oneself Base) -2,2- propane, double (4- hydroxyls hexyl) methane, double (1,1- dimethyl -2- hydroxyethyls) oxa-s of -2,4,8,10- four of 3,9- Esterdiol compound, glycerine, two glycerine, triglycerin, 1,2 such as spiral shell [5,5] hendecane, double (hydroxyethyl) terephthalates, 6- hexanes triol, pentaerythrite, dipentaerythritol, D-sorbite, mannitol, trimethylolethane, trimethylolpropane, two- Trimethylolpropane, three (2- hydroxyethyls) isocyanuric acid esters, make the lactone compounds such as 6-caprolactone and these polyalcohol additions Obtained from poly-lactone polyol compound etc., these can individually using or be applied in combination two or more.

Alternatively, it is also possible to make methyl alcohol, ethanol, propyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, n-hexyl alcohol, just pungent as needed Alcohol, lauryl alcohol, 2-Ethylhexyl Alcohol, decyl alcohol, cyclohexanol, benzylalcohol, stearyl alcohol, 2- phenoxetols, dodecyl alcohol etc. are single Alcohol；Oxirane, expoxy propane, epoxy butane, the ethylene oxidic ester (trade name " Cardura of synthesis chain is saturated aliphatic acid high E10 " HEXION Specialty Chemicals societies system) etc. mono-epoxy compounds with have Bronsted acid compound reaction and obtain To alcoholic compound etc. as manufacture polyester resin (A) when auxiliary material use.

In the present invention, the manufacture method of polyester resin (A) is not particularly limited, and can carry out according to known methods. Polyester resin (A) can for example make selected from least a kind composition in the group being made up of lactic acid, the lactide of lactic acid and PLA and At least a kind composition of at least one of composition in selected from the group being made up of glycolic, glycolide and polyglycolic acid, the acid into Divide the one kind or two or more and alcohol composition (a2) one kind or two or more in nitrogen stream, in 150~250 DEG C of temperature of (a1) Carry out polymerisation 2~10 hours and manufacture.In above-mentioned polymerisation, the reaction sequence of raw material can be adjusted arbitrarily, After the lactide of lactic acid is carried out ring-opening polymerization in advance and obtaining PLA or glycolide can be made pre- advanced Row ring-opening polymerization and after obtaining polyglycolic acid, make above-mentioned sour composition (a1) and alcohol composition (a2) in the ring-opening polymerization polymer In the presence of carry out polymerisation.Alternatively, it is also possible to by using the polymerisation of above-mentioned sour composition (a1) and alcohol composition (a2) Obtained from polyester resin and lactic acid lactide or glycolide polymerisation and/or ester exchange reaction, obtain polyester resin (A).These reactions can be carried out in the presence of known organic solvent.

In addition, in order to promote reaction, the polymerisation can be carried out using catalyst.As such catalyst, Can enumerate for example：Dibutyltin oxide, antimony trioxide, ferric acetate, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, Tetrabutyl titanate ester, tetra isopropyl titanate, Firebrake ZB, zinc chloride, zinc sulfate, zinc naphthenate, zinc oxide, lead borate, acetic acid The known catalyst such as aluminium, aluminium chloride.

In the present invention, the polyester resin (A) is by least a kind in selected from lactic acid, the lactide of lactic acid and PLA Composition and selected from the group being made up of glycolic, glycolide and polyglycolic acid at least a kind composition at least one into Point, the polymerisation of sour composition (a1) and alcohol composition (a2) and manufacture, above-mentioned sour composition (a1) and alcohol can be contained as needed Known organic compound and/or inorganic compound beyond composition (a2) is used as constituent, it is also possible to anti-with amidatioon Should, urethane reaction, imidization reaction, carbonation reaction, ureaization reaction etc. it is known chemically react and manufacture. For example, polyester resin (A) can be by make in the polymerization or after polymerisation reaction intermediate or reaction product with The metallic compounds such as organic acid zinc, copper organic acid, zinc chloride, copper chloride, zinc hydroxide, Kocide SD, zinc oxide, cupric oxide, Aliphatic acid, grease, single or multiple isocyanate compound, single or multiple amines, epoxidation with the nitrogen for being bonded hydrogen atom Modified polyester resin obtained from the reaction such as compound, acrylic resin, vinyl ester resin.In addition, with regard to polyester resin (A) Speech, in the case where raw material will be used as selected from least a kind composition in the group being made up of glycolic, glycolide and polyglycolic acid, Beyond the organic compounds such as lactic acid, the lactide of lactic acid and PLA can also be as above-mentioned sour composition (a1) and alcohol composition (a2) Constituent and comprising.

It is explained, the polyester resin (A) in the present invention there can be metal carboxylate structure, but in this case, with institute State solid constituent quality containing as metallic atom contained in benchmark, above-mentioned metal carboxylate structure of polyester resin (A) The content of the amount metallic atom more contained than in the resin (B2) with metal carboxylate structure described later is low, and preferably less than 0.04 Mole/kg, and then, more preferably described polyester resin (A) does not have above-mentioned metal carboxylate structure substantially.Polyester resin (A) When being with metal carboxylate structure, raised using the manufacturing cost of the antifouling paint compositions for having the resin sometimes.

In addition, antifouling paint compositions of the invention also containing comprising metallic compound composition (for example pigment composition or Anti-fouling agent composition etc.) in the case of, in the manufacture of such antifouling paint compositions or when preserving, sometimes comprising substantially not The composition of polyester resin (A) and above-mentioned metallic compound with metal carboxylate structure is reacted, through when generate gold Category carboxylate structure.From from the viewpoint of the storage-stable of antifouling paint compositions, the metal carboxylate structure for so generating In contained metallic atom content using the solid constituent quality of polyester resin (A) as benchmark, preferably less than 1.5 moles/ Kg, more preferably less than 0.04 mole/kg in the range of.

Polyester resin (A), from least a kind composition in selected from the group being made up of lactic acid, the lactide of lactic acid and PLA And selected from the group being made up of glycolic, glycolide and polyglycolic acid at least a kind composition of at least one of composition, described The constituent of sour composition (a1) and the alcohol composition (a2) is preferably 80 moles of more than % of total constituent of the resin, more Preferably 90 moles more than %.

In addition, from from the aspect of the soil resistance of the film by maintaining to obtain for prolonged period of time, the resin of polyester resin (A) Acid number is preferably in the range of 0.1~120mgKOH/g, in the range of more preferably 0.1~95mgKOH/g, particularly preferably In the range of 0.3~50mgKOH/g.

And then, in terms of the soil resistance by the film for maintaining to obtain for prolonged period of time and from the aspect of soil resistance, gather The weight average molecular weight of ester resin (A) is preferably in the range of 190~15000, in the range of more preferably 340~13000, especially In the range of preferably 600~8000.

In this specification, weight average molecular weight is will be using gel infiltration color as benchmark using the weight average molecular weight of polystyrene Spectrum (TOSOH Co., Ltd's system, " HLC8120GPC ") determine weight average molecular weight converted obtained by value.Weight average molecular weight can To use 4 post (trade names：" TSKgelG-4000H × L ", " TSKgelG-3000H × L ", " TSKgelG-2500H × L " and " TSKgelG-2000H × L " (being society of TOSOH Co., Ltd system)), mobile phase be tetrahydrofuran, temperature of the measurement be 40 DEG C, Flow velocity is 1ml/ minute, detector is to carry out under conditions of RI.

[resin of ester group containing silicyl (B1)]

Antifouling paint compositions of the invention also contain the resin of ester group containing silicyl in addition to above-mentioned polyester resin (A) And/or the resin with metal carboxylate structure (B2) (B1).The resin of ester group containing silicyl (B1) is following formula (2) institutes Monomer (b1) show, with polymerism unsaturated group and three Organosilyl ester groups (below, sometimes referred to as " monomer (b1) a kind of one kind or two or more and with the polymerism unsaturated group beyond above-mentioned monomer (b1) monomer (b2) ") or Copolymer of more than two kinds, preferable weight-average molecular weight (Mw) is the copolymer in the range of 1000~150000, more preferably Mw is the copolymer in the range of 3000~80000.

【Change 5】

[in formula (2), R₄Represent hydrogen atom or methyl, R₁、R₂And R₃Separately represent alkyl, R₅Represent hydrogen atom or R₆- O-CO- (wherein, R₆Represent organic group or-SiR₇R₈R₉Shown silicyl, R₇、R₈And R₉Separately represent hydrocarbon Base.).]

When Mw for the resin of the ester group containing silicyl (B1) of antifouling paint compositions of the invention is less than 1000, although The dissolution velocity of the film obtained by antifouling paint compositions becomes big, but, poor properties of film sometimes, easily produce bubbling or The paint film defects such as cracking.In addition, when the Mw of the resin of ester group containing silicyl (B1) is more than 150000, sometimes by antifouling paint The dissolution velocity of the film that composition is obtained is slack-off, soil resistance is poor.

In addition, the R in the formula (2)₅In the case of for hydrogen atom, the monomer (b1) is by following formulas (2-1) Represent.

【Change 6】

It is explained, the R in the formula (2-1)₄、R₁、R₂And R₃Respectively with the formula (2) in R₄、R₁、R₂And R₃It is identical.

R in the formula (2) or the formula (2-1)₁、R₂And R₃In alkyl be preferably the straight chain that carbon number is 1~10 Shape the alkyl with side chain or by arbitrarily substitution base substitution or unsubstituted phenyl, respective alkyl can with identical, Can also be different.Wherein, the alkyl is preferably the alkyl that carbon number is 1~5, particularly preferably methyl, ethyl, propyl group, The alkyl such as normal-butyl, sec-butyl, the tert-butyl group, isopropyl.

As the monomer (hereinafter referred to as " monomer (b1-1) ") shown in the formula (2-1), can enumerate for example：(methyl) third Olefin(e) acid trimethyl silyl ester, (methyl) acrylic acid triethylsilyl ester, (methyl) acrylic acid triisopropyl monosilane Base ester etc. (methyl) acrylic acid trialkylsilkl ester, wherein, dissolubility, antifouling property from the film for obtaining continue The generation of property, bubbling or cracking is difficult from the aspect of degree etc., preferably (methyl) acrylic acid triisopropylsilyl.

R in the formula (2)₅It is " R₆- O-CO- " (wherein, R₆Represent organic group or-SiR₇R₈R₉Shown monosilane Base, R₇、R₈And R₉Separately represent alkyl) when, the monomer (b1) is represented by following formulas (2-2).

【Change 7】

It is explained, the R in the formula (2-2)₄、R₁、R₂And R₃Respectively with the formula (2) in R₄、R₁、R₂And R₃It is identical.

As the R in the formula (2) or the formula (2-2)₆The organic group of expression, it is 1~10 that can enumerate carbon number Straight-chain or with side chain alkyl, cycloalkyl, unsaturated alkyl, aralkyl etc..

As straight-chain or with side chain the alkyl that above-mentioned carbon number is 1~10, can enumerate for example：Methyl, Ethyl, n-propyl, isopropyl, isobutyl group, normal-butyl, sec-butyl, the tert-butyl group, 2- methyl butyls, 2- ethyl-butyls, amyl group, 3- Methyl amyl, hexyl, heptyl, octyl group etc..

In addition, as above-mentioned cycloalkyl, can enumerate for example：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring Octyl group etc..

And then, as above-mentioned unsaturated alkyl, can enumerate：2- acrylic, 2- cyclobutenyls, 3- cyclobutenyls, 2- pentenyls, 3- Pentenyl, 4- pentenyls etc..

And, as above-mentioned aralkyl, such as benzyl, phenethyl, phenyl propyl etc. can be enumerated.

It is explained, above-mentioned alkyl, cycloalkyl, unsaturated alkyl and aralkyl there can be substitution base.As so Substitution base, such as alkoxy, acyl group etc. can be enumerated.In addition, on substitution radix, position of substitution etc., as long as without prejudice to sheet The effect of invention, is just not particularly limited.

As the monomer (hereinafter referred to as " monomer (b1-2) ") shown in the formula (2-2), can enumerate for example：Maleic acid two Ester compounds, the dimethyl ester compound (R in the formula (2-2)₄It is the compound of hydrogen atom) etc..

R in the formula (2) or the formula (2-2)₇、R₈And R₉In alkyl be preferably the straight chain that carbon number is 1~10 Shape the alkyl with side chain or by arbitrarily substitution base substitution or unsubstituted phenyl, respective alkyl can with identical, Can also be different.Wherein, the preferred carbon number of the alkyl is 1~5 alkyl, particularly preferred methyl, ethyl, propyl group, positive fourth The alkyl such as base, sec-butyl, the tert-butyl group, isopropyl.

The generation of the continuation, bubbling or cracking of dissolubility, antifouling property from the film for obtaining be difficult degree etc. side Face considers that the monomer (b1) preferably contains the unsaturated monomer of isopropyl silyl.As such monosilane containing isopropyl The unsaturated monomer of base, can enumerate for example：(methyl) acrylic acid triisopropylsilyl ester, 4- penetenoic acid triisopropyl first silicon Arrcostab, maleic acid double (triisopropylsilyl) ester, methyl triisopropylsilyl ester, maleic acid ethyls three Isopropyl silyl ester, maleic acid normal-butyl triisopropylsilyl ester, maleic acid isobutyl group triisopropylsilyl Ester, maleic acid tert-butyl group triisopropylsilyl ester, maleic acid n-pentyl triisopropylsilyl ester, maleic acid isopentyl Triisopropylsilyl ester, maleic acid 2- ethylhexyl triisopropylsilyls ester, maleic acid cyclohexyl triisopropyl first Silane base ester, fumaric acid double (triisopropylsilyl) ester, fumaric acid methyl triisopropyl monosilane ester, fumaric acid ethyls three Isopropyl monosilane ester, fumaric acid normal-butyl triisopropylsilyl ester, fumaric acid isobutyl group triisopropylsilyl ester, Fumaric acid n-pentyl triisopropylsilyl ester, fumaric acid isopentyl triisopropylsilyl ester, fumaric acid 2- ethyl hexyls Base triisopropylsilyl ester, fumaric acid cyclohexyl triisopropylsilyl ester etc., wherein, particularly preferred (methyl) propylene Sour triisopropylsilyl ester.In addition, these monomers containing triisopropylsilyl can be used alone or be applied in combination 2 More than kind.

The resin of ester group containing silicyl (B1) is preferably by monomer (b1) and monomer (b2) with the range of 20/80~70/30 Mass ratio (b1)/(b2) carry out resin obtained from copolymerization, further preferably by monomer (b1) and monomer (b2) with 30/70~ Mass ratio (b1)/(b2) in the range of 60/40 carries out resin obtained from copolymerization.

When mass ratio (b1)/(b2) of monomer (b1) and monomer (b2) is less than 20/80, the dissolving speed of the film for obtaining sometimes Degree is slow, and antifouling property is poor, when described mass ratio (b1)/(b2) is more than 70/30, although the dissolubility of the film for obtaining becomes big, But, sometimes by maintaining the anti-fouling effect to become difficult for prolonged period of time.

As be able to can be enumerated for example with the monomer (b2) of monomer (b1) (or monomer (b1-1) and/or (b1-2)) copolymerization： (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (first Base) (methyl) acrylic acid alkyl such as tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate Esters；(methyl) acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 2- methoxyl groups propyl ester, (methyl) acrylic acid 4- methoxyl group fourths (methyl) the alkoxyalkyl acrylate classes such as ester, (methyl) acrylic acid 2- ethoxy ethyl esters；(methyl) acrylic acid ethylene glycol list Methyl esters, molecular end are (methyl) acrylate with polyethylene oxide chain of alkoxy, a molecular end is alkane (methyl) acrylic acid such as (methyl) acrylate with PPOX chain, (methyl) propylene acid propylene glycol mono-methyl of epoxide Aklylene glycol mono-methyl class；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 6-caprolactone modified body, the allyl of the monoesters compound of 2 yuan of alcohol of 4- hydroxybutyls, (methyl) acrylic acid and carbon number 2~8 Alcohol, molecular end are (methyl) acrylic acid of the hydroxyl monomers such as (methyl) acrylate with polyethylene oxide chain of hydroxyl Hydroxy alkyl esters；(methyl) acrylonitrile, (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, (methyl) propylene Acyl group morpholine, N- isopropyls (methyl) acrylamide, N- hydroxymethyls (methyl) acrylamide, N- alkoxy methyls (methyl) third Acrylamide, (methyl) acrylic acid N, N- dimethyl aminoethyl ester, (methyl) acrylic acid N, N- diethylamino ethyl ester, N, N- The nitrogen containing monomers such as the addition product of dimethylaminopropyl (methyl) acrylamide, (methyl) glycidyl acrylate and amine； (methyl) esters of acrylic acids such as (methyl) benzyl acrylate, (methyl) phenyl acrylate；Vinyl chloride；Vinylidene chloride；(methyl) third Alkene nitrile；Vinylacetate；Butyl vinyl ether；Lauryl vinyl ether；NVP；Styrene；Vinyl first Benzene；AMS etc..

In addition, as the monomer (b2), it is also possible to using for example：The vinyl esters such as propionate, vinylacetate Compound；(methyl) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, butenoic acid, (methyl) propylene The carboxyl group-containing monomers such as sour β-carboxyethyl；(methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) acrylic acid 3,4- epoxycyclohexylmethyls ester, (methyl) acrylic acid 3,4- epoxy cyclohexylethyls ester, (methyl) Acrylic acid 3,4- expoxycyclohexyls propyl diester, allyl glycidyl ether etc. contain epoxy based monomers；2- (methyl) acryloyl Amine -2- methyl propane sulfonic acids, allyl sulphonic acid, styrene sulfonic acid, sulfoethvl (methyl) acrylate and their sodium salt or ammonium The monomers containing sulfonic group such as salt；The monomers with phosphate such as 2- (methyl) acryloyl-oxyethyl acid phosphoric acid ester；Methacrylaldehyde, two Acetone (methyl) acrylamide, (methyl) acrylic acid acetoacetoxyethyl ester, with 4~7 vinyl alkane of carbon atom Monomers containing carbonyl such as base ketone (such as ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) etc..

Foregoing illustrative monomer (b2) can be used alone or be applied in combination two or more.In addition, foregoing illustrative monomer (b2) among, particularly preferred (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 2- methoxyl group propyl ester etc..

It is explained, in this specification, " (methyl) acrylate " refers to acrylate or methacrylate, " (first Base) acrylic acid " refer to acrylic or methacrylic acid.In addition, " (methyl) acryloyl group " refers to acryloyl group or metering system Acyl group, " (methyl) acrylamide " refers to acrylamide or Methacrylamide.

In the present invention, the resin of ester group containing silicyl (B1) can be manufactured using known polymerization.Said It is bright, the resin of ester group containing silicyl (B1) as long as random copolymer, graft copolymer, bevelled junction configuration copolymer, block are common The known copolymer such as polymers, then can be the copolymer of any kind type.

The resin of ester group containing silicyl (B1) for example can by the presence of radical polymerization initiator, make the list Body (b1) and the monomer (b2) carry out copolymerization and obtain.

As the radical polymerization initiator in above-mentioned copolyreaction, can enumerate for example：2,2 '-azobis isobutyronitrile (AIBN), the double -2- methylbutyronitriles of 2,2 '-azo, dimethyl -2,2 ' the azo compounds species such as-azobisisobutylonitrile acid esters；Hexichol first Acyl peroxide, two (3- methyl benzoyls) peroxide, benzoyl (3- methyl benzoyls) peroxide, February The diacyl peroxide compounds such as osmanthus base peroxide；Di-tert-butyl peroxide, tert butyl peroxy benzoate, uncle The tert-butyl peroxide compounds such as butyl peroxy butylperoxyisopropyl carbonate, tert-butyl hydroperoxide caprylate；T-amyl peroxy Change -2 ethyl hexanoic acid ester, t-amyl peroxy acetic acid esters, t-amyl peroxy isononoate, t-amyl peroxy benzoic ether, The t-amyl peroxies such as t-amyl peroxy acetic acid esters, two (t-amyl peroxy compounds), 1,1- bis- (t-amyl peroxy) hexamethylene Compound compounds；Tertiary hexyl peroxidating -2 ethyl hexanoic acid ester, tertiary hexyl peroxide benzoate, tertiary hexyl peroxidating-isopropyl The tertiary hexyl peroxide compound classes such as base monocarbonate, tertiary hexyl peroxidating trimethylacetic acid ester, tertiary hexyl new decanoate ester peroxide Deng.These polymerization initiators can be used alone or two or more is applied in combination.

Usage amount by the such polymerization initiator of appropriate setting etc., can adjust the resin of ester group containing silicyl (B1) Molecular weight.

In addition, as the polymerization for obtaining the resin of ester group containing silicyl (B1), can enumerate for example：Polymerisation in solution Method, mass polymerization, emulsion polymerization, suspension polymerization etc..Among these, from can easily and precision synthesizes well described From the aspect of the resin of ester group containing silicyl (B1), particularly preferred solution polymerization process.

In above-mentioned copolyreaction, organic solvent can be as needed used.As such organic solvent, can enumerate For example：The aromatic hydrocarbon series solvents such as dimethylbenzene, toluene；The aliphatic hydrocarbon series solvent such as hexane, heptane；Ethyl acetate, butyl acetate, The ester series solvents such as isobutyl acetate, methoxypropyl acetate；The alcohol series solvents such as isopropanol, butanol；TwoAlkane, ether, dibutyl The ether series solvents such as ether；Ketone series solvents such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc..Among these, optimization aromatic hydrocarbon system solvent, Particularly preferred dimethylbenzene.In addition, these solvents can be used alone or be applied in combination two or more.

Reaction temperature in the copolyreaction is according to appropriate settings, usually 70 DEG C such as the species of polymerization initiator Temperature in the range of~160 DEG C, the temperature in the range of preferably 80 DEG C~140 DEG C.And then, it is anti-in the copolyreaction The appropriate setting such as species between seasonable according to reaction temperature or polymerization initiator, usually 4~8 hours or so.In addition, institute State copolyreaction is preferably carried out under the atmosphere of the non-active gas such as nitrogen, argon gas.

[there is the resin (B2) of metal carboxylate structure]

Antifouling paint compositions of the invention are in addition to the above-mentioned resin of ester group containing silicyl (B1), or contain instead of above-mentioned Silicyl ester group resin (B1), can contain the resin (B2) with metal carboxylate structure and (in this specification, sometimes should " having the resin (B2) of metal carboxylate structure " is referred to as " resin (B2) ").The resin (B2) as long as have metal carboxylic The resin of hydrochlorate structure, then be not restricted to species and composition of resin etc., it is possible to use known with metal carboxylate knot Paper mulberry fat.

The resin (B2) contains the characteristic group with metal carboxylate structure shown in following formulas (3).

【Change 8】

As the divalent metallic atom M in the formula (3), such as metal raw such as zinc, copper, magnesium, calcium, iron and tellurium can be enumerated Son, can preferably enumerate zinc or copper.

Resin (B2) containing the characteristic group (bb1) with the metal carboxylate structure that the X in the formula (3) is hydroxyl It can be for example 0.1~1.0 mole by making known resin with carboxyl and relative to 1 mole of carboxyl in the resin In the range of amount the, oxide of divalent metal or hydroxide etc. react in presence of water and obtain.Water in the reaction Usage amount is relative to 1 mole of amount being preferably in the range of 0.1~10.0 mole of above-mentioned carboxyl.The usage amount of the water is less than 0.1 Mole when, structural viscosity can become big sometimes, and the treatment of the resin (B2) with metal carboxylate structure of generation becomes difficult.Separately On the one hand, when the usage amount of the water is more than 10.0 moles, the lock out operation sometimes as excessive water turns into required.

Used as the specific manufacture method of the resin (B2) containing the characteristic group (bb1), can enumerate for example makes Resin, water and divalent metallic compound with carboxyl are put into reaction vessel, 50 DEG C~150 DEG C of temperature make its reaction 1~ 20 hours method etc..The reaction can add appropriate organic solvent and carry out in above-mentioned reaction vessel.As such Organic solvent, can enumerate such as alcohol system, ketone system, ester system, ether series solvent etc., these can using a kind or be applied in combination 2 kinds with On.

The divalent metallic compound for the manufacture of the resin (B2) containing the characteristic group (bb1) can be with Without particular limitation using known material, from from the aspect of cost, toxicity, reactivity etc., be preferably selected from by copper, zinc, calcium, At least a kind oxide of metal, salt or hydroxide in the group that magnesium, iron and tellurium are constituted, the oxidation of further preferred zinc or copper Thing, salt or hydroxide.

In addition, as the manufacture for the resin (B2) containing the characteristic group (bb1) with the carboxyl Resin, for example can be using the resin such as polyvinyl, polyester, polyurethane, natural resin, in the free degree of composition change Big aspect, it may be preferred to using by unsaturated monomers containing carboxyl such as (methyl) acrylic acid, maleic acid, fumaric acid, itaconic acids and Other unsaturated monomers such as (methyl) alkyl acrylate, styrene carry out polyvinyl obtained from copolymerization.

In addition, being the characteristic group of the metal carboxylate structure of organic acid residue as containing the X having in the formula (3) (bb2) resin (B2), can enumerate unsaturated monomer (bb2m) that for example will be containing characteristic group (bb2) polymer or 2 kinds The one kind or two or more and described unsaturated list of copolymer above, the unsaturated monomer (bb2m) containing characteristic group (bb2) The one kind or two or more copolymer of the unsaturated monomer (m1) beyond body (bb2m), above-mentioned copolymer are changed by arbitrary method Property resin or using above-mentioned copolymer-modified arbitrary resin etc..

As the unsaturated monomer (bb2m), for example following formulas (4) can be enumerated or the unsaturation shown in (5) is single Body.

【Change 9】

【Change 10】

In above-mentioned formula (4) or formula (5), R₁₀、R₁₁And R₁₂Hydrogen atom or methyl are represented, A represents organic acid residue, and M represents 2 Valency metallic atom.

Among the unsaturated monomer (bb2m), as the manufacture of the unsaturated monomer (bb2m-1) shown in above-mentioned formula (4) Method, can enumerate for example makes the polymerism unsaturated organic acids such as (methyl) acrylic acid, the oxide of divalent metal, hydroxide, salt Deng metallic compound and the method for the unitary organic acid reaction that can form organic acid residue；Make polymerism unsaturated organic acid and one Method of the reacting metal salt of first organic acid etc..These reactions can enter in the presence of organic solvent and/or water as needed OK.

Among the unsaturated monomer (bb2m), as the manufacture of the unsaturated monomer (bb2m-2) shown in above-mentioned formula (5) Method, can enumerate for example make the oxide of the polymerism unsaturated organic acids such as (methyl) acrylic acid and divalent metal, hydroxide, Method of the metallic compounds such as salt reaction etc..The reaction can also be carried out in the presence of organic solvent and/or water as needed.

In the case that X in above-mentioned formula (3) is organic acid residue, as the organic acid residue, can enumerate for example by vinegar Acid, monochloro acetic acid, single fluorine acetic acid, aphthenic acids, propionic acid, caproic acid, octanoic acid, 2 ethyl hexanoic acid, capric acid, neodecanoic acid, isostearic acid, palm fibre Palmitic acid acid, cresotinic acid, oleic acid, elaidic acid, linoleic acid, leukotrienes, stearic acid, castor oil acid, ricinelaidic acid, brassidic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5- Trichlorophenoxies acetic acid, 2,4 dichloro benzene epoxide acetic acid, quinoline carboxylic acid, nitrobenzene Formic acid, nitro naphthalene-carboxylic acid, pulvinic acid (pulvinic acid), rosin acid, neoabietic acid, dehydroabietic acid, hydroabietic acid, length Leaf pine acid, pimaric acid, isodextropimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid, resin acid, abietane, pimarane, The organic acid residues derived from organic acid such as isopimarane, the compound with Ladanum alkane skeleton.In addition, on above-mentioned formula (4) In A shown in organic acid residue, it is also possible to enumerate the organic acid residue as derived from above-mentioned organic acid.

As the concrete example of the unsaturated monomer (bb2m-1), can enumerate for example：(methyl) acrylic acid magnesium acetate, (methyl) acrylic acid zinc acetate, (methyl) acrylate acid zinc, (methyl) acrylic acid copper acetate, the acid of (methyl) acrylate Copper, list (methyl) acrylic acid chloroacetic acid magnesium, single (methyl) acrylic acid chloroacetic acid zinc, single (methyl) acrylic acid chloroacetic acid copper, single (first Base) acrylic acid fluorine magnesium acetate, singly (methyl) acrylic acid fluorine zinc acetate, single (methyl) acrylic acid fluorine copper acetate, (methyl) acrylic acid Propionic acid magnesium, (methyl) acrylic acid zinc propionate, (methyl) acrylic acid propionic acid copper, (methyl) acrylic acid caproic acid magnesium, (methyl) acrylic acid Caproic acid zinc, (methyl) acrylic acid caproic acid copper, (methyl) acrylic acid magnesium octoate, (methyl) acrylic acid zinc octoate, (methyl) acrylic acid Cupric octoate, (methyl) acrylic acid 2 ethyl hexanoic acid magnesium, (methyl) acrylic acid 2 ethyl hexanoic acid zinc, (methyl) acrylic acid 2- ethyl hexyls Base acid copper, (methyl) acrylic acid capric acid magnesium, (methyl) acrylic acid capric acid zinc, (methyl) acrylic acid capric acid copper, (methyl) acrylic acid Neodecanoic acid magnesium, (methyl) acrylic acid zinc neodecanoate, (methyl) acrylic acid neodecanoic acid copper, (methyl) acrylic acid isostearic acid magnesium, (first Base) acrylic acid isostearic acid zinc, (methyl) acrylic acid isostearic acid copper, (methyl) acrylic acid magnesium palmitate, (methyl) acrylic acid Zinc palmitate, (methyl) acrylic acid copper palmitate, (methyl) acrylic acid cresotinic acid magnesium, (methyl) acrylic acid cresotinic acid zinc, (first Base) acrylic acid cresotinic acid copper, (methyl) acrylic acid magnesium oleate, (methyl) acrylic acid zinc oleate, (methyl) acrylic acid copper oleate, (methyl) acrylic acid elaidic acid magnesium, (methyl) acrylic acid elaidic acid zinc, (methyl) acrylic acid elaidic acid copper, (methyl) acrylic acid are sub- Magnesium oleate, (methyl) acrylic acid zinc linoleate, (methyl) acrylic acid copper linoleate, (methyl) acrylic acid leukotrienes magnesium, (methyl) Acrylic acid leukotrienes zinc, (methyl) acrylic acid leukotrienes copper, (methyl) stearyl acrylate acetylenic acid magnesium, (methyl) stearyl acrylate alkynes Sour zinc, (methyl) stearyl acrylate acetylenic acid copper, (methyl) acrylic acid castor oil acid magnesium, (methyl) acrylic acid zinc ricinate, (first Base) acrylic acid castor oil acid copper, (methyl) acrylic acid ricinelaidic acid magnesium, (methyl) acrylic acid ricinelaidic acid zinc, (methyl) propylene Sour ricinelaidic acid copper, (methyl) acrylic acid brassidic acid magnesium, (methyl) acrylic acid brassidic acid zinc, (methyl) acrylic acid Brazil alkene Sour copper, (methyl) acrylic acid erucic acid magnesium, (methyl) acrylic acid erucic acid zinc, (methyl) acrylic acid erucic acid copper, (methyl) acrylic acid α- Naphthoic acid magnesium, (methyl) acrylic acid α-naphthalene acid zinc, (methyl) acrylic acid α-naphthoic acid copper, (methyl) propenoic acid beta-naphthoic acid magnesium, (methyl) Propenoic acid beta-naphthalene acid zinc, (methyl) propenoic acid beta-naphthoic acid copper, (methyl) acrylic acid magnesium benzoate, (methyl) propylene acid+benzoic acid Zinc, (methyl) acrylic acid copper benzoate, (methyl) acrylic acid 2,4,5- Trichlorophenoxies magnesium acetate, (methyl) acrylic acid 2,4,5- Trichlorophenoxy zinc acetate, (methyl) acrylic acid 2,4,5- Trichlorophenoxies copper acetate, (methyl) acrylic acid 2,4 dichloro benzene oxygen Base magnesium acetate, (methyl) acrylic acid 2,4 dichloro benzene epoxide zinc acetate, (methyl) acrylic acid 2,4 dichloro benzene epoxide copper acetate, (methyl) acrylic acid quinoline carboxylic acid magnesium, (methyl) acrylic acid quinoline carboxylic acid zinc, (methyl) acrylic acid quinoline carboxylic acid copper, (methyl) third Olefin(e) acid nitrobenzoic acid magnesium, (methyl) acrylic nitrocellulose zinc benzoate, (methyl) acrylic nitrocellulose copper benzoate, (methyl) propylene Aci-nitro naphthalene-carboxylic acid magnesium, (methyl) acrylic nitrocellulose naphthalene-carboxylic acid zinc, (methyl) acrylic nitrocellulose naphthalene-carboxylic acid copper, (methyl) acrylic acid Pulvinic acid magnesium, (methyl) acrylic acid pulvinic acid zinc, (methyl) acrylic acid pulvinic acid copper etc..These unsaturated monomers (bb2m-1) can basis Need suitably to select one kind or two or more and use.

As the unsaturated monomer (bb2m-2) shown in above-mentioned formula (5), can enumerate for example：Magnesium Acrylate Prepared ((CH₂= CHCOO)₂Mg), magnesinm methacrylate ((CH₂=C (CH₃)COO)₂Mg), zinc acrylate resin ((CH₂=CHCOO)₂Zn), metering system Sour zinc ((CH₂=C (CH₃)COO)₂Zn), acrylic acid copper ((CH₂=CHCOO)₂Cu), methacrylic acid copper ((CH₂=C (CH₃) COO)₂Cu) etc..These unsaturated monomers (b2m-2) suitably can be selected one kind or two or more and used as needed, at these In unsaturated monomer, from from the viewpoint of the antifouling property of the film for maintaining to obtain for a long time, (methyl) zinc acrylate resin is preferably used.

From from the viewpoint of the antifouling property of the film for maintaining to obtain for a long time, for obtaining described containing characteristic group (bb2) usage amount of the unsaturated monomer (bb2m-1) of resin (B2) is using the solid constituent quality of resin (B2) as base In the range of standard, preferably 0.5~30.0 mass %, in the range of more preferably 1.0~20.0 mass %.

In addition, from from the viewpoint of the antifouling property of the film for maintaining to obtain for a long time, it is described containing characteristic base for obtaining Group (bb2) resin (B2) the unsaturated monomer (bb2m-2) usage amount using the solid constituent quality of resin (B2) as In the range of benchmark, preferably 0.5~50.0 mass %, in the range of more preferably 1.0~30.0 mass %.

It is the tree of the characteristic group (b3) with metal carboxylate structure of alcohol residue as containing the X in above-mentioned formula (3) Fat (B2), can enumerate for example：The polymer or copolymer of more than two kinds of the unsaturated monomer (b3m) containing characteristic group (b3), Beyond the one kind or two or more and described unsaturated monomer (b3m) of the unsaturated monomer (b3m) containing characteristic group (b3) not The one kind or two or more copolymer of saturation monomer (m2), the resin that above-mentioned copolymer has been modified by arbitrary method or profit With above-mentioned copolymer-modified arbitrary resin etc..

As the manufacture method of the unsaturated monomer (b3m), can enumerate for example：Make the polymerisms such as (methyl) acrylic acid not The metallic compounds such as unsaturated organic acid, the oxide of divalent metal, hydroxide, salt and can be formed alcohol residue alcohols reaction Method；Make polymerism unsaturated organic acid and the method for metallic alkoxide compound reaction etc..These reaction can as needed, Carried out in the presence of organic solvent and/or water.

In addition, the resin (B2) can also by make be selected from by the unsaturated monomer (bb2m-1), (bb2m-2) and (b3m) a kind of at least a kind unsaturated monomer in the group for constituting and the unsaturated monomer (m3) beyond as needed they or Two or more carries out copolymerization and obtains.

The unsaturated monomer (m1), (m2) and (m3) can be identical respectively, it is also possible to different.As described unsaturated single Body (m1), (m2) and (m3), can enumerate the monomer as the manufacture that can be used in the resin of ester group containing silicyl (B1) (b2) unsaturated monomer for illustrating.

The copolyreaction containing unsaturated monomer (bb2m) and/or (b3m) can for example trigger in radical polymerization Carried out in the presence of agent.Radical polymerization initiator can be used and can be used in the resin of ester group containing silicyl (B1) The same initiator of the initiator of the copolyreaction of monomer (b1) and monomer (b2) in manufacture.

In addition, the resin (B2) for example can be by making the known resin with carboxyl, relative in the resin 1 mole of carboxyl be the metallic compounds such as amount the, oxide of divalent metal or hydroxide in the range of 0.1~1.0 mole and Organic acid as needed, alcoholic compound or water etc. are manufactured in 50 DEG C~200 DEG C of thermotonus 1~20 hour.By this The X in the characteristic group with metal carboxylate structure in the resin (B2) of reaction generation shown in contained, described formula (3) is only It is at least a kind group in the group for selecting free hydroxyl, organic acid residue and alcohol residue to constitute, its component ratio is without spy Do not limit.In addition, the reaction can be carried out in the presence of appropriate organic solvent, and as organic solvent in this case, can Such as alcohol system, ketone system, ester system, ether series solvent etc. are enumerated, these using a kind or can be applied in combination two or more.

Above-mentioned divalent metallic compound for the manufacture of the resin (B2) can without particular limitation using known Divalent metallic compound, from from the aspect of cost, toxicity, reactivity etc., is preferably selected from what is be made up of zinc, copper, magnesium, calcium, iron and tellurium The oxide of at least a kind oxide of metal, salt or hydroxide in group, further preferred zinc or copper, salt or hydroxide.

The above-mentioned resin with carboxyl for the manufacture of the resin (B2) for example can be using polyvinyl, poly- The resins such as ester, polyurethane, natural resin, at the big aspect of the free degree of composition change, it may be preferred to use (methyl) propylene The unsaturated monomers containing carboxyl such as acid, maleic acid, fumaric acid, itaconic acid and (methyl) alkyl acrylate, styrene etc. other not Saturation monomer carries out the polyvinyl of copolymerization.

In addition, the resin (B2) containing characteristic group (bb2) can be by making known resin and unitary with carboxyl The divalent reacting metal salt of organic acid and manufacture.

In the present invention, having shown in the contained formula (3) in the resin (B2) with metal carboxylate structure As long as the X in the characteristic group of metal carboxylate structure is in the group for selecting free hydroxyl, organic acid residue and alcohol residue composition At least a kind group, and then, the content of contained metallic atom is with the resin (B2) in the metal carboxylate structure Solid constituent quality is the preferably scope of 0.07~3.00 mole/kg in the range of 0.04~3.50 mole/kg as benchmark It is interior, in the range of more preferably 0.10~2.50 mole/kg.When the content of above-mentioned metallic atom is more than 3.50 moles/kg, sometimes Shortened during the holding of the soil resistance of the film for obtaining, when it is less than 0.04 mole/kg, there is the soil resistance drop of the film for obtaining Low tendency.

As the manufacture method other than the above of the resin (B2) with metal carboxylate structure, can enumerate for example at 1 point There is the condensation reaction of the compound and metallic compound of more than 2 carboxyls in son, using having with metal carboxylate structure Sudden reaction or condensation reaction of polyol compound etc..

[anti-fouling agent (C)]

Antifouling paint compositions of the invention except the polyester resin (A) and the resin of ester group containing silicyl (B1) and/or Outside resin (B2) with metal carboxylate structure, also contain anti-fouling agent (C).As described anti-fouling agent (C), it is possible to use Known anti-fouling agent, can enumerate such as inorganic compound, the organic compound containing metal and metal-free organic compound Thing etc..

As above-mentioned inorganic compound, can enumerate for example：Cuprous oxide, copper powder, cupric thiocyanate, copper carbonate, copper chloride, sulphur The copper compounds such as sour copper；The zinc compounds such as zinc sulfate, zinc oxide；Nickel compounds such as nickel sulfate, copper-nickel alloy etc..

As the organic compound containing above-mentioned metal, for example, can use organic copper based compound, organic nickel system chemical combination Thing, organic zinc based compound etc., in addition it is also possible to use maneb, Mancozeb, propineb etc..And then, as described Organic copper based compound, can enumerate for example：Oxine copper, copper pyrithione, nonyl benzene copper phenolsulfonate, double (ethylenediamine) copper-bis- (ten Dialkyl benzene sulfonic acids ester), copper acetate, copper naphthenate, double (pentachlorobenzene phenolic acid) copper etc..In addition, as organic nickel system chemical combination Thing, can enumerate for example：Nickel acetate, nickel dimethyldithiocarbamate etc..And, as the organic zinc based compound, can Enumerate：Zinc acetate, carbaminate, PZ, ZPT, ethylenebis dithiocarbamates first Sour zinc etc..

As the organic compound for not containing above-mentioned metal, can enumerate for example：The thio phthalyl of N- trihalomethyls is sub- Amine, aminodithioformic acid, N- aryl maleimides, 3- substitutionization amino -1,3- thiazolidines, dithiocyanogen Base system compound, triazine based compound etc..

As above-mentioned N- trihalomethyls thiophthalimide, can enumerate for example：N- trichloromethylthios neighbour's benzene two Carboximide, N- fluorine dichloromethyl thiophthalimides etc..

As above-mentioned aminodithioformic acid, can enumerate for example：Double (dimethylthiocarbamoyl) disulfides, N- first Base ammonium dithiocarbamate, ethylenebis (aminodithioformic acid) ammonium, milneb etc..

As above-mentioned N- aryl maleimides, can enumerate for example：N- (2,4,6- trichlorophenyls) maleimide, N-4- Tolylmaleimide, N-3- chlorophenylmaleimides, N- (4- n-butylphenyls) maleimide, N- (anilino- benzene Base) maleimide, N- (2,3 xylidine base) maleimide, 2,3- bis- chloro- N- (2 ', 6 '-diethyl phenyl) Malaysia acyl Imines, the chloro- N- of 2,3- bis- (2 '-ethyl -6 '-aminomethyl phenyl) maleimide etc..

Used as above-mentioned 3- substitutionizations amino -1,3-thiazoles alkane -2,4- diketone can be enumerated for example：3- benzylideneaminos -1,3- Thiazolidine, 3- (4- methylbenzylideneaminos) -1,3- thiazolidines, 3- (2- hydroxyl benzal ammonia Base) -1,3- thiazolidines, 3- (4- dimethylaminos benzylideneamino) -1,3- thiazoline -2,4- diketone, 3- (2, 4- dichlorin benzylidenes amino) -1,3- thiazolidines etc..

As above-mentioned dithiocyanogen base system compound, can enumerate for example：Dithiocyanogen methylmethane, dithiocyanogen base ethane, 2,5- dithiocyanogen base thiophene etc..

As above-mentioned triazine based compound, can enumerate for example：2- methyl mercapto -4- tert-butylamino -6- cyclopropylaminos-s- Triazine etc..

In addition, as the organic compound for not containing above-mentioned metal, in addition to foregoing illustrative organic compound, can arrange Citing is such as：2,4,5,6- termils, N, the chloro- 2-N- octyl groups -3- (2H) of N- dimethyl dichlorophenyls urea, 4,5- bis- are different Thiazolinone, N, N- dimethyl-N '-phenyl-(N- fluorine dichloros methyl mercapto) sulphamide, tetra methylthiuram disulfide, the iodo- 2- of 3- Propynyl butylcarbamate, 2- (methyloxycarbonylamino) benzimidazole, 2,3,5,6- tetra- chloro- 4- (methyl sulphonyl) pyrrole Pyridine, AMICAL 48, double DMDSs are for the double dithiocarbamates capronates of carbamoyl zinc ethene, phenyl (double pyridines) bismuth dichloride, 2- (4- thiazolyls) benzimidazole, pyridinium triphenylboron amine complex, Medetomidine (system Name：(±) 4- [1- (2,3- 3,5-dimethylphenyls) ethyl] -1H- imidazoles), the two fluoro- N- of chloro- N- ((dimethylamino) sulfonyl) (p-methylphenyl) NSC-249992, the bromo- 5- trifluoromethyl pyrpoles of 2- (rubigan) -3- cyano group -4-, chloromethyl-n-octyl two Thioether etc..

Foregoing illustrative each compound can be used singly or in combination two or more by the anti-fouling agent (C).In addition, The anti-fouling agent (C) from from the viewpoint of the antifouling property played stably, preferably uses oxygen in foregoing illustrative each compound Change it is cuprous, particularly preferably and with cuprous oxide and copper pyrithione.

[antifouling paint compositions and the coated article with its film]

Antifouling paint compositions of the invention are to contain polyester resin (A), the resin of ester group containing silicyl (B1) and/or tool There are the resin (B2) of metal carboxylate structure and the antifouling paint compositions of anti-fouling agent (C), it is characterised in that the polyester resin (A) there is the Component units shown in the formula (1), the polyester resin (A) and ester group containing silicyl in the resin matrix Total mass ratio of resin (B1) and the resin (B2) with metal carboxylate structure is in the range of 3/97~80/20.

Above-mentioned polyester resin (A) and the resin of ester group containing silicyl (B1) and/or the resin with metal carboxylate structure (B2) mass ratio be 3/97~80/20 in the range of, in the range of preferably 7/93~60/40, more preferably 10/90~ In the range of 40/60.When above-mentioned mass ratio is in the range of 3/97~80/20, can be by maintaining for prolonged period of time by the present invention The excellent antifouling property of antifouling coat that obtains of antifouling paint compositions, in addition, in the antifouling coat, being not likely to produce The paint film defects such as film stripping, bubbling, cracking.When above-mentioned mass ratio is less than 3/97 or more than 80/20, sometimes by long-term The antifouling property of the film that ground maintenance is obtained becomes difficult.

The resin of ester group containing silicyl (B1) in coating composition of the invention and the tree with metal carboxylate structure The mass ratio of fat (B2) can be used in the range of 0/100~100/0.

In antifouling paint compositions of the invention, the content of the anti-fouling agent (C) is with above-mentioned polyester resin (A) and containing first Total quality of silylation ester base resin (B1) and the resin (B2) with metal carboxylate structure, as benchmark, is 50~500 In the range of quality %, in the range of preferably 250~400 mass %.When the content of anti-fouling agent (C) is less than 50 mass %, pass through sometimes Crossing the antifouling property of the film for maintaining to obtain for prolonged period of time becomes difficult, in addition, the content of the anti-fouling agent (C) is more than 500 matter During amount %, the physical property reduction of the film for obtaining sometimes is peeling or expands etc. and be bad.

In antifouling paint compositions of the invention, except polyester resin (A), the resin of ester group containing silicyl (B1) and/or Outside resin (B2) and anti-fouling agent (C) with metal carboxylate structure, can coordinate as needed：It is pigment, dyestuff, de- The additives such as aqua, plasticizer, thixotropic agent (anti-sagging agent), defoamer, antioxidant；Polyester resin (A), containing silyl ester Resin beyond base resin (B1) and the resin (B2) with metal carboxylate structure；Organic acid；Solvent etc. is for general painting The various composition of feed composition.These compositions can be used alone or be applied in combination two or more.

As above-mentioned pigment, can enumerate for example：Colcother, talcum, titanium oxide, yellow iron oxide, silica, calcium carbonate, The coloring pigments such as barium sulfate, calcium oxide, carbon black, naphthol reds, phthalocyanine blue；Talcum, silica, mica, clay, calcium carbonate, height The extender pigments such as ridge soil, white alumina, aluminium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, zinc sulphide.

The content of the pigment in antifouling paint compositions of the invention is with polyester resin (A) and ester group containing silicyl Total quality of resin (B1) and the resin (B2) with metal carboxylate structure is used as benchmark, preferably 0.05~1000 matter In the range of amount %, in the range of more preferably 1~500 mass %.

Above-mentioned dehydrating agent is the composition for contributing to the storage-stable of antifouling paint compositions to improve.As such dehydration Agent, for example, in inorganic system, anhydrous gypsum, semi-hydrated gypsum (plaster of paris), synthetic zeolite system adsorbent can be enumerated (for example " Molecular sieve " (trade name) etc.) etc., additionally, can enumerate ortho acid esters (such as original acid A ester, former methyl acetate, Ortho-boric acid ester etc.), silicate class, isocyanates etc..Among these, anhydrous gypsum preferably as the dehydrating agent of inorganic system, Semi-hydrated gypsum (plaster of paris).In addition, these dehydrating agents can be used alone or two or more kinds may be used.It is explained, prevents The content of the dehydrating agent in dirty coating composition can suitably be adjusted, but with polyester resin (A) and ester group containing silicyl Total quality of resin (B1) and the resin (B2) with metal carboxylate structure as benchmark, preferably 0~100 mass %'s In the range of, in the range of more preferably 0.5~25 mass %.

The plasticizer is the composition for contributing to the resistance to cracking of antifouling coat that obtains or water resistance to improve etc..As this The plasticizer of sample, can enumerate for example：Tricresyl phosphate, dioctyl phthalate, chlorinated paraffin, flowing alkane, just Paraffins, chlorinated paraffin, polybutene, terpene phenol, tricresyl phosphate (TCP), polyvinyl ethyl ether etc..These increase Modeling agent can be used alone or two or more kinds may be used.It is explained, coordinates in antifouling paint compositions of the invention In the case of plasticizer, the content of the plasticizer in the antifouling paint compositions is with polyester resin (A) and containing silyl ester Total quality of base resin (B1) and the resin (B2) with metal carboxylate structure is used as benchmark, preferably 0.5~10 mass % In the range of, in the range of more preferably 1~5 mass %.

As above-mentioned antioxidant, can enumerate for example：2,6- di-t-butyl -4- methylphenols etc..

As above-mentioned thixotropic agent, can enumerate for example：Organic system wax (such as Tissuemat E, OPE, polyamide Wax, amide waxe, rilanit special wax etc.), organic clay based compound (amine salt of such as Al, Ca, Zn, stearate salt, lecithin Fat salt, alkylsulfonate etc.), bentonite, synthesis fine particle silica etc..These thixotropic agent can be used alone, it is also possible to And use two or more.In the case of coordinating thixotropic agent in antifouling paint compositions of the invention, in the antifouling paint compositions The content of thixotropic agent can suitably be adjusted, for example, with polyester resin (A) and the resin of ester group containing silicyl (B1) and tool There is total quality of resin (B2) of metal carboxylate structure as benchmark, be in the range of 0.25~50 mass %.

Antifouling paint compositions of the invention are except polyester resin (A), the resin of ester group containing silicyl (B1) and with metal Beyond the resin (B2) of carboxylate structure, can as needed contain one kind or two or more other resinaes.As so Resinae, acrylic resin, the acrylic acid for for example being used extensively as the matrix resin of antifouling paint can be enumerated It is organic siliconresin, epoxy resin, fluororesin, polybutene resin, silicon rubber, polyurethane resin, polyamide, vinyl chloride Copolymer resins, chlorinated rubber, chlorinated alkenes resin, styrenebutadiene copolymer resin, ketone resin, ethylene-vinyl acetate Copolymer resins, chlorinated ethylene resin, alkyd resin, coumarone resin, terpene phenol resin, Petropols etc..

In addition, antifouling paint compositions of the invention can contain known rosin based compound.As such rosin Based compound, can enumerate for example：Rosin, rosin derivative, rosin metal salt etc..And then, as the rosin, example can be enumerated Such as：Appropriate your rosin, rubber rosin, wood rosin etc..In addition, used as the rosin derivative, can enumerate for example makes hydrogenated rosin, pine Maleinized rosin, formylated rosin, newtrex that the reaction of fragrant and maleic anhydride is obtained etc..And, as the rosin metal Salt, can enumerate for example：Resin acid zinc, resin acid calcium, copper rosinate, the reaction of resin acid magnesium and metallic compound and rosin Thing etc..These rosin based compounds can be used alone or be applied in combination two or more.

In the case of coordinating rosin based compound in antifouling paint compositions of the invention, the antifouling paint compositions In the content of rosin based compound be not particularly limited, for example, with polyester resin (A) and the resin of ester group containing silicyl (B1) And total quality of the resin (B2) with metal carboxylate structure is used as benchmark, preferably below 50 mass %, further preferred 30 Below quality %.

Antifouling paint compositions of the invention can coordinate aliphatic solvent, aromatic solvent (such as dimethylbenzene, toluene Deng), ketone series solvent (such as methyl iso-butyl ketone (MIBK), cyclohexanone etc.), ester series solvent, ether series solvent (such as propylene glycol monomethyl ether, third Glycol monomethylether acetate etc.), alcohol series solvent (such as isopropanol etc.) etc. is usually as having that the solvent of antifouling paint is used Machine solvent.It is explained, the use level of organic solvent can suitably be adjusted, for example, for the total of antifouling paint compositions consolidates Body composition rate turns into the use level in the range of 20~90 mass %, can also be added according to operability in application.

Antifouling paint compositions of the invention can be prepared by the method same with known antifouling paint compositions. For example, can be by by polyester resin (A), the resin of ester group containing silicyl (B1) and/or tree with metal carboxylate structure Fat (B2), anti-fouling agent (C) and the organic solvent as needed or additive etc. it is disposable or make an addition to successively tank diameter, It is stirred, mixes to manufacture.

In addition, coated article of the invention is the article of the film with antifouling paint compositions of the invention.Above-mentioned painting Dress article can by comprising making above-mentioned antifouling paint compositions 1 time~be repeatedly coated with or be impregnated in base material surface operation and Make the method for the operation that the above-mentioned antifouling paint compositions of the coating or impregnation are dried and obtain.

As above-mentioned base material, the base material for for example being contacted with seawater or fresh water (such as often or discontinuously) can be enumerated, specifically For, aouatic structure thing；Ship plank or hull bottom；Generate electricity aqueduct or cooling tube；Fishing net, the fishing of cultivation use or fixation Tool or the floating material for using in these；Attached tool of the fishing nets such as rope etc..It is explained, by antifouling paint compositions of the invention The thickness of the film for obtaining it is contemplated that depletion rate (dissolution velocity) of film etc. and be suitably adjusted, for example, as every The thickness (μm) that application is 1 time, be set to 30~250 μm/it is secondary, preferably 75~150 μm/secondary or so, can as needed recoat 2 60~500 μm or so are set to more than secondary.

When above-mentioned coated article is obtained, can the surface of the base material be coated with priming paint, anticorrosive coating and The surface of adhesive coating as needed is by hairbrush coating, spraying, roller coat, impregnating method application antifouling painting of the invention Feed composition.In addition, antifouling paint compositions of the invention can carry out repeating painting on existing antifouling coat surface.Film Drying can be carried out in room temperature, it is also possible to be thermally dried to about 100 DEG C of temperature as needed.

【Embodiment】

Hereinafter, embodiment and comparative example are enumerated, the present invention is further specifically described, but the present invention is not limited to reality Apply example.It is explained, " part " and " % " in following embodiments refers respectively to " mass parts " and " quality % ".

The manufacture of polyester resin (A)

The manufacture of (Production Example 1) polyester resin (A1)

Load in the reaction unit of the 2L for possessing thermometer, agitator and rectifying column 415.3 parts of PA, 235.7 parts of NPG, The lactide of 237.9 parts of DEG, 161.6 parts of lactic acid, 160 DEG C are warming up to by the contents temperature of reaction unit.Then, reaction is filled The contents temperature put was warming up to 230 DEG C with 3 hours from 160 DEG C, after keeping contents temperature 2 hours at 230 DEG C, by rectifying column Separator is changed to, about 50.0 parts of dimethylbenzene are loaded in reaction unit, while make water and xylenes and remove condensation water, While carrying out polycondensation.The acid number of polyester resin of generation is confirmed for after below 3.0mgKOH/g, stopping is heated and begun to cool down, Addition dimethylbenzene is diluted, and thus obtains polyester resin (A1) solution of solid constituent 70%.It is explained, by toluene and different The mixed liquor (mass ratio 1/1) of propyl alcohol determines sample as solvent dissolving, by the alcohol system solution of the potassium hydroxide of 1/10 equivalent The above-mentioned resin of titration determination acid number.

Here, the relation of the suitable compound of the shorthand notation of the polyester raw material with this specification described below.

PA；Phthalic anhydride, iPA；M-phthalic acid, AD；Adipic acid, HHPA；Hexahydrophthalic anhydride, EG；Second Glycol, PG；Propane diols, NPG；Neopentyl glycol, 1,6-HD；1,6-HD, BEPG；2-butyl-2-ethyl-1,3-propanediol, CHDM；1,4 cyclohexane dimethanol, DEG；Diethylene glycol, TEG；Triethylene glycol, Tetra EG；TEG, DPG；Dipropyl two Alcohol, TMP；Trimethylolpropane, G；Glycerine, PE；Pentaerythrite, LA；The lactide of lactic acid, GL；Glycolide

(Production Example 2~8,13~17) polyester resin (A2)~(A8), the manufacture of (A13)~(A17)

Except by the sour composition in Production Example 1 and alcohol into addition to the cooperation being divided into shown in table 1-1, in the same manner as Production Example 1 Operation, obtains each polyester resin (A2)~(A8), the resin solution of (A13)~(A17) of solid constituent 70%.

The manufacture of (Production Example 9) polyester resin (A9)

Load in the reaction unit of the 2L for possessing thermometer, agitator and rectifying column 340.9 parts of iPA, 215.6 parts of NPG, The lactide of 217.7 parts of DEG, 147.8 parts of lactic acid, 160 DEG C are warming up to by the contents temperature of reaction unit.Then, reaction is filled The contents temperature put was warming up to 230 DEG C with 3 hours from 160 DEG C, after keeping contents temperature 2 hours at 230 DEG C, by rectifying column Separator is changed to, about 45 parts of dimethylbenzene are loaded in reaction unit, while make water and xylenes and remove condensation water, one While carrying out polycondensation.Confirm the acid number of polyester resin of generation after below 3.0mgKOH/g, contents temperature to be cooled into 160 ℃.Further 152.0 parts of PA of addition, are kept for 1 hour at 160 DEG C and after carrying out addition reaction (half-esterification), begun to cool down.It is cold But to 130 DEG C afterwards, addition dimethylbenzene is diluted, and thus obtains the resin solution of the polyester resin (A9) of solid constituent 70%.

The manufacture of (Production Example 10) polyester resin (A10)

The 2L for possessing thermometer, agitator and rectifying column load in reaction unit 292.8 parts of iPA, 185.2 parts NPG, 186.9 parts of DEG, the lactide of 127.0 parts of lactic acid, 160 DEG C are warming up to by the contents temperature of reaction unit.Then, will be anti- The contents temperature of device is answered to be warming up to 230 DEG C with 3 hours from 160 DEG C, after keeping contents temperature 2 hours at 230 DEG C, by essence Evaporate tower and be changed to separator, about 45 parts of dimethylbenzene are loaded in reaction unit, while making water and xylenes and removing condensation Water, while carrying out polycondensation.Confirm the acid number of polyester resin of generation after below 3.0mgKOH/g, contents temperature to be cooled down To 160 DEG C.Further 276.1 parts of HHPA of addition, are kept for 1 hour at 160 DEG C and after carrying out addition reaction (half-esterification), started Cooling.It is cooled to 130 DEG C afterwards, addition dimethylbenzene is diluted, and thus obtains the polyester resin (A10) of solid constituent 70% Resin solution.

The manufacture of (Production Example 11) polyester resin (A11)

The 2L for possessing thermometer, agitator and rectifying column load in reaction unit 415.3 parts of PA, 235.7 parts NPG, 237.9 parts of DEG, the lactic acid aqueous solution of 229.5 part of 88 mass %, 130 DEG C are warming up to by the contents temperature of reaction unit. Then, the contents temperature of reaction unit is warming up to 160 DEG C with 3 hours from 130 DEG C, keeps contents temperature 2 small at 230 DEG C Shi Hou, separator is changed to by rectifying column, about 50.0 parts of dimethylbenzene is loaded in reaction unit, while making water and xylenes And condensation water is removed, while carrying out polycondensation.Confirm the acid number of polyester resin of generation after below 3.0mgKOH/g, to stop adding Heat simultaneously begins to cool down, and addition dimethylbenzene is diluted, and thus obtains the resin solution of the polyester resin (A11) of solid constituent 70%.

The manufacture of (Production Example 12) polyester resin (A12)

The 2L for possessing thermometer, agitator and water separator load in reaction unit 217.4 parts of PA, 18.2 parts EG, 205.7 parts of PE, 625.3 parts of soya fatty acids, lactide, 50.0 parts of dimethylbenzene of 28.2 parts of lactic acid, by reaction unit Tolerant temperature is warming up to 160 DEG C, is kept for 1 hour.Then, the contents temperature of reaction unit was warming up to 4 hours from 160 DEG C 240 DEG C, while the condensation water of generation is removed at 240 DEG C, while carrying out polycondensation.Confirm that resinous acid value is for about below 3.0mgKOH/g Afterwards, stop heating and beginning to cool down, addition dimethylbenzene is diluted, and thus obtains the polyester resin (A12) of solid constituent 70% Resin solution.

The resinous acid value and weight average molecular weight of polyester resin (A1)~(A17) that will be obtained in above-mentioned each Production Example with it is each The use level of Production Example is shown in table 1-1 together.

【Table 1】

The manufacture of (Production Example 1 ') polyester resin (A1 ')

The 2L for possessing thermometer, agitator and rectifying column load in reaction unit 428.7 parts of PA, 243.3 parts NPG, 245.7 parts of DEG, 134.4 parts of glycolides (GL), 160 DEG C are warming up to by the contents temperature of reaction unit.Then, will be anti- The contents temperature of device is answered to be warming up to 230 DEG C with 3 hours from 160 DEG C, after keeping contents temperature 2 hours at 230 DEG C, by essence Evaporate tower and be changed to separator, about 50.0 parts of dimethylbenzene are loaded in reaction unit, while making water and xylenes and removing contracting Heshui, while carrying out polycondensation.Confirm the acid number of polyester resin of generation for after below 3.0mgKOH/g, stopping is heated and started Cooling, addition dimethylbenzene is diluted, and thus obtains polyester resin (A1 ') solution of solid constituent 70%.

(Production Example 2 '~8 ', 13 '~18 ') polyester resin (A2 ')~(A8 '), the manufacture of (A13 ')~(A18 ')

Except by the sour composition in Production Example 1 ' and alcohol into addition to the cooperation being divided into shown in table 1-2, it is same with Production Example 1 ' Ground operation, obtains each polyester resin (A2 ')~(A8 '), the resin solution of (A13 ')~(A18 ') of solid constituent 70%.

The manufacture of (Production Example 9 ') polyester resin (A9 ')

The 2L for possessing thermometer, agitator and rectifying column load in reaction unit 351.0 parts of iPA, 222.0 parts NPG, 224.1 parts of DEG, 122.6 parts of glycolides, 160 DEG C are warming up to by the contents temperature of reaction unit.Then, reaction is filled The contents temperature put was warming up to 230 DEG C with 3 hours from 160 DEG C, after keeping contents temperature 2 hours at 230 DEG C, by rectifying column Separator is changed to, about 45 parts of dimethylbenzene are loaded in reaction unit, while make water and xylenes and remove condensation water, one While carrying out polycondensation.Confirm the acid number of polyester resin of generation after below 3.0mgKOH/g, contents temperature to be cooled into 160 ℃.Further 156.4 parts of PA of addition, are kept for 1 hour at 160 DEG C and after carrying out addition reaction (half-esterification), begun to cool down.It is cold But to 130 DEG C afterwards, addition dimethylbenzene is diluted, and the resin for thus obtaining the polyester resin (A9 ') of solid constituent 70% is molten Liquid.

The manufacture of (Production Example 10 ') polyester resin (A10 ')

The 2L for possessing thermometer, agitator and rectifying column load in reaction unit 300.2 parts of iPA, 189.9 parts NPG, 191.7 parts of DEG, 104.9 parts of glycolides, 160 DEG C are warming up to by the contents temperature of reaction unit.Then, reaction is filled The contents temperature put was warming up to 230 DEG C with 3 hours from 160 DEG C, after keeping contents temperature 2 hours at 230 DEG C, by rectifying column Separator is changed to, about 45 parts of dimethylbenzene are loaded in reaction unit, while make water and xylenes and remove condensation water, one While carrying out polycondensation.Confirm the acid number of polyester resin of generation after below 3.0mgKOH/g, contents temperature to be cooled into 160 ℃.Further 278.5 parts of HHPA of addition, are kept for 1 hour at 160 DEG C and after carrying out addition reaction (half-esterification), begun to cool down. It is cooled to 130 DEG C afterwards, addition dimethylbenzene is diluted, and thus obtains the resin of the polyester resin (A10 ') of solid constituent 70% Solution.

The manufacture of (Production Example 11 ') polyester resin (A11 ')

The 2L for possessing thermometer, agitator and rectifying column load in reaction unit 428.7 parts of PA, 243.3 parts NPG, 245.7 parts of DEG, 176.1 parts of glycolics, 130 DEG C are warming up to by the contents temperature of reaction unit.Then, reaction is filled The contents temperature put was warming up to 160 DEG C with 3 hours from 130 DEG C, after keeping contents temperature 2 hours at 230 DEG C, by rectifying column Separator is changed to, about 50.0 parts of dimethylbenzene are loaded in reaction unit, while make water and xylenes and remove condensation water, While carrying out polycondensation.The acid number of polyester resin of generation is confirmed for after below 3.0mgKOH/g, stopping is heated and begun to cool down, Addition dimethylbenzene is diluted, and thus obtains the resin solution of the polyester resin (A11 ') of solid constituent 70%.

The manufacture of (Production Example 12 ') polyester resin (A12 ')

The 2L for possessing thermometer, agitator and water separator load in reaction unit 217.4 parts of PA, 18.2 parts EG, 205.7 parts of PE, 625.3 parts of soya fatty acids, 22.7 parts of glycolides, 50.0 parts of dimethylbenzene, by the content of reaction unit Temperature is warming up to 160 DEG C, is kept for 1 hour.Then, the contents temperature of reaction unit was warming up to 240 with 4 hours from 160 DEG C DEG C, while the condensation water of generation is removed at 240 DEG C, while carrying out polycondensation.Confirm resinous acid value be for about below 3.0mgKOH/g it Afterwards, stop heating and beginning to cool down, addition dimethylbenzene is diluted, and thus obtains the polyester resin (A12 ') of solid constituent 70% Resin solution.

The resinous acid value and weight average molecular weight of polyester resin (A1 ')~(A18 ') that will be obtained in above-mentioned each Production Example with The use level of each Production Example is shown in table 1-2 simultaneously.

【Table 2】

The manufacture of the resin of ester group containing silicyl (B1)

The manufacture of (Production Example 18) ester group containing silicyl resin (B1-1)

Load 40 parts of dimethylbenzene in the beaker with mixer, liquidus temperature is maintained 140 DEG C, to small with 3 in beaker When be added dropwise table 2 shown in each unsaturated monomer and day oil (strain) system peroxide system polymerization initiator " Perbutyl I " (business The name of an article) 1 part of mixture, after completion of dropwise addition, kept for 30 minutes in the temperature.Then, be added dropwise within 20 minutes 10 parts of dimethylbenzene and The mixture that 1 part of " PerbutylI " (trade name), after the temperature continuously stirs 2 hours, starts the cooling of liquid phase.And then, Dimethylbenzene is added among beaker, the solution of the resin of generation is prepared in the way of as the mass % of solid component concentration 50, contained The resin solution of silicyl ester group resin (B1-1).

(the Production Example 19,20) resin of ester group containing silicyl (B1-2), the manufacture of (B1-3)

In addition to the cooperation of the unsaturated monomer being set to shown in table 2, operated in the same manner as Production Example 18, obtained containing monosilane The resin solution (the mass % of solid component concentration 50) of base ester base resin (B1-2), (B1-3).

【Table 3】

Table 2

The numerical value of the monomer in each Production Examples of ※ represents mass parts.

The manufacture of the resin (B2) with metal carboxylate structure

The manufacture of the resin (B2-1) of (Production Example 21) with metal carboxylate structure

241.7 parts of the loading in possessing thermometer, thermostat, agitator, reflux cooler and the reaction vessel of pump is added dropwise Dimethylbenzene, 197.5 parts of butyl acetates, 241.7 parts of n-butanols, while the content in reaction vessel is stirred, while will The temperature of the content is warming up to 105 DEG C.Thereafter, will containing 104.2 parts of methacrylic acids, 304.4 parts of ethyl acrylates, 272.4 parts of methoxyethyl acrylates, the mixed solution of 54.5 parts of 2,2- azos double (2- methylbutyronitriles), using pump is added dropwise with one Constant speed degree was added dropwise in the reaction vessel for being maintained at 105 DEG C and being equably stirred with 4 hours.The dropwise addition of the mixed solution After end, the temperature of the content in reaction vessel is maintained at 105 DEG C 1 hour by continuation, thus obtains acrylic resin soln.

And then, 49.7 parts of zinc oxide, 34.0 parts of deionized waters are added in the resin solution for obtaining, continuously stirred at 100 DEG C Mix 20 hours, thus obtain the resin solution of the resin (B2-1) with metal carboxylate structure that is non-volatile or dividing about 50%.Should The content (hreinafter referred to as " tenor ") of contained metallic atom is 0.79mol/kg in resin (B2-1).

The manufacture of the resin (B2-2) of (Production Example 22) with metal carboxylate structure

563.0 parts of the addition in possessing thermometer, thermostat, agitator, reflux cooler and the reaction vessel of pump is added dropwise Dimethylbenzene, 140.7 parts of n-butanols, 110 DEG C to 120 DEG C are maintained at by the temperature of the mixed solution in reaction vessel.In the solution In with certain speed be added dropwise within 3 hours containing 281.5 parts of ethyl acrylates, 117.3 parts of 2-EHAs, 70.4 part third The mixed solution of olefin(e) acid, 37.5 parts of 2,2- azos double (2- methylbutyronitriles).After the completion of dropwise addition of the mixed solution, continuing will be mixed The temperature for closing solution is maintained at 2 hours from 110 DEG C to 120 DEG C, thus obtains acrylic resin soln.

And then, 236.4 parts of aphthenic acids, 82.8 parts of Kocide SDs are added in the resin solution for obtaining, 120 DEG C are warming up to, Kept for 2 hours.During this period, remove generation water (about 30 parts of dehydrating amount), obtain nonvolatile component about 50% with metal carboxylic The resin solution of the resin (B2-2) of hydrochlorate structure.Contained tenor is 1.08mol/kg in the resin (B2-2).

It is explained, the tenor such as zinc, copper in above-mentioned resin is quantified using fluorescent X-ray method.

【Table 4】

Table 3

(note 1) (CH₂=CHCOO)₂Zn

(note 2) 2,2- azos are double (2- methylbutyronitriles)

The preparation of antifouling paint compositions and various experiments

(embodiment 1~28) and (comparative example 1~8) and (embodiment 29~57) and (comparative example 9~16)

Evaluate

By the resin solution of polyester resin (A1)~(A17) and (A1')~(A18'), the resin of ester group containing silicyl (B1- 1) resin solution, anti-fouling agent, pigment of~(B1-3), the resin (B2-1) with metal carboxylate structure and (B2-2) etc. are with table Being coordinated with being combined into shown in 4-1~table 4-4, mixing dispersion is carried out with the mixing speed of about 2000rpm using homogenizer. After dispersion, DISPARLON A630-20XN (this chemical conversion of nanmu society system, anti-sagging agent) and solvent are added, carry out dispersion stirring, prepared Coating composition (E1)~(E73).The coating composition that will be prepared tests (table 5-1~table 5-4 tables for following antifouling properties Show result of the test), adhesive test (table 6-1~table 6-4 represents result of the test) and resistance to cracking experiment (table 7-1~table 7-4 Represent result of the test).

＜ antifouling properties test ＞

Sprayed in the way of as 200 μm of dry film thickness on the two sides of blasting treatment steel plate (100mm × 300mm × 2mm) Mist application epoxy antirusting paint, and then, the application epoxy adhesive coating in the way of dry film thickness turns into 100 μm.At this The two sides of coated plate passes through 4 each coating compositions of atomized spray painting application in the way of dry film thickness turns into 480 μm of one side, in temperature 20 DEG C of degree, the thermostatic constant wet chamber of humidity 75% dry 1 week, make test film.Using the test film, triple county Du Hui prefectures south she Gesture raised path between farm fields gravel Pu carries out the Seawater immersion of 60 months, through when ground determination test film on aufwuch occupied area ratio (bond area).

◎：(qualified) is not observed aufwuch

○：The occupied area of (qualified) aufwuch is less than 5%

△：The occupied area of (unqualified) aufwuch is 5% less than 30%

×：The occupied area of (unqualified) aufwuch is more than 30%

＜ adhesive tests ＞

Have at the sandblasting of bendability in the way of to be mountable to columnar drum (diameter 500mm × height 240mm) In reason steel plate (120mm × 120mm × 1mm), atomized spray painting epoxy antirust is applied in the way of as 200 μm of dry film thickness Material, and then, the application epoxy adhesive coating in the way of dry film thickness turns into 100 μm.The one side of the steel plate after the application In the way of dry film thickness turns into 480 μm by 4 each coating compositions of atomized spray painting application, in 20 DEG C of temperature, humidity 75% Thermostatic constant wet chamber dries 1 week, makes test film.The test film is installed on above-mentioned cylindrical drum, makes the cylindrical drum in soldier Storehouse county is rotated 24 months by 500mm under the sea in good gulf with 16 nautical miles.From it is marine through when ground recovery test piece, make 5mm × 5mm Gridiron pattern, implement paper tape and peel off the evaluation of cementability for causing.Evaluation is set to ISO 2409：1992 commenting as benchmark Valency.

◎：(qualified) Table1Classification 01

○：(qualified) Table1Classification 2

△：(unqualified) Table1Classification 3

×：(unqualified) Table1Classification 45

＜ resistance to crackings test ＞

Its film is visually observed with the test film for above-mentioned adhesive test, the presence or absence of generation of cracking is have studied.

◎：(qualified) is not observed cracking

○：(qualified) somewhat observes fine cracking in film coated surface

△：(unqualified) although being not reaching to substrate, in film coated surface it was observed that many fine and clear and definite cracking

×：It is (unqualified) to observe the cracking for reaching substrate

【Table 5】

【Table 6】

【Table 7】

【Table 8】

【Table 9】

Table 5-1 antifouling properties are tested

【Table 10】

Table 5-2 antifouling properties are tested

【Table 11】

Table 5-3 antifouling properties are tested

【Table 12】

Table 5-4 antifouling properties are tested

【Table 13】

Table 6-1 adhesive tests

【Table 14】

Table 6-2 adhesive tests

【Table 15】

Table 6-3 adhesive tests

【Table 16】

Table 6-4 adhesive tests

【Table 17】

Table 7-1 resistance to crackings are tested

【Table 18】

Table 7-2 resistance to crackings are tested

【Table 19】

Table 7-3 resistance to crackings are tested

【Table 20】

Table 7-4 resistance to crackings are tested

Claims

1. a kind of antifouling paint compositions, it contains polyester resin (A), the resin of ester group containing silicyl (B1) and/or with gold Belong to the resin (B2) and anti-fouling agent (C) of carboxylate structure, it is characterised in that

The polyester resin (A) is have the Component units and following formula (1) shown in following formula (1) in the resin matrix Total quality of shown Component units using the quality of the polyester resin (A) as benchmark as 2~50 mass % in the range of Polyester resin,

The polyester resin (A) and the ester group containing silicyl resin (B1) and the resin with metal carboxylate structure (B2) total mass ratio be 3/97~80/20 in the range of,

【Change 1】

In formula, R₀Hydrogen atom or methyl are represented, m represents 1~100 integer.

2. antifouling paint compositions according to claim 1, it is characterised in that the resin of ester group containing silicyl (B1) 1 kind or 2 of monomer (b2) beyond the one kind or two or more and described monomer (b1) of the monomer (b1) shown in following formula (2) The copolymer of the above is planted,

【Change 2】

In formula, R₄Represent hydrogen atom or methyl, R₁、R₂And R₃Separately represent alkyl, R₅Represent hydrogen atom or R₆- O-CO-, In formula, R₆Represent organic group or-SiR₇R₈R₉Shown silicyl, R₇、R₈And R₉Separately represent alkyl.

3. antifouling paint compositions according to claim 1 and 2, it is characterised in that described with metal carboxylate structure Resin (B2) have following formula (3) shown in the characteristic group with metal carboxylate structure, it is described with metal carboxylate The content of contained metallic atom is as benchmark using the solid constituent quality work of the resin (B2) in the resin (B2) of structure In the range of 0.04~3.50 mole/kg,

【Change 3】

In formula, M represents the metallic atom of divalent, and X is represented in the group for selecting free hydroxyl, organic acid residue and alcohol residue to constitute extremely Few a kind of group.

4. antifouling paint compositions according to any one of claims 1 to 3, it is characterised in that the polyester resin (A) Be using containing at least a kind raw mixture of composition in selected from the group being made up of lactic acid, the lactide of lactic acid and PLA, with And containing at least a kind raw mixture of composition in selected from the group being made up of glycolic, glycolide and polyglycolic acid at least A kind of raw mixture and the polyester resin that manufactures, and the polyester resin (A) acid number be 0.1~120KOHmg/g scope It is interior.

5. antifouling paint compositions according to any one of Claims 1 to 4, it is characterised in that the polyester resin (A) Weight average molecular weight in the range of 190~15000.

6. antifouling paint compositions according to any one of Claims 1 to 5, it is characterised in that the polyester resin (A) It is the polyester resin without metal carboxylate structure.

7. a kind of coated article, it has the film of the antifouling paint compositions any one of claim 1~6.