CN101809102A

CN101809102A - Antifouling coating composition, process for producing the composition, antifouling coating film formed from the composition, coated object having the coating film on surface, and method of antifouling treatment by forming the coating film

Info

Publication number: CN101809102A
Application number: CN200880109720A
Authority: CN
Inventors: 毛利喜代美; 和久英典; 藤本贵义
Original assignee: Nitto Kasei Co Ltd
Current assignee: Nitto Kasei Co Ltd
Priority date: 2007-11-21
Filing date: 2008-11-17
Publication date: 2010-08-18
Also published as: JP2011026357A; WO2009066632A1; TW200932852A

Abstract

An antifouling coating composition is provided which can form in seawater a coating film which stably dissolves away from the beginning to show a satisfactory antifouling effect, has excellent water resistance, and can effectively produce the antifouling effect over long. The composition is reduced in the content of volatile organic compounds (VOCs) vaporizing off into the air and is highly safe environmentally. The antifouling coating composition comprises (A) a polymer which is obtained by polymerizing a polymerizable unsaturated triorganosilyl carboxylate and has a number-average molecular weight of 1,000-20,000 and (B) at least one zinc salt selected among zinc salts of rosins and zinc salts of rosin derivatives. In the composition, (1) the weight ratio of the content of the polymer (A) to the content of the zinc salt (B), (A)/(B), is from 45/55 to 10/90, (2) the composition has a nonvolatile content of 75 wt.% or higher, and (3) the composition substantially contains neither a rosin nor a rosin derivative each having a free carboxyl group.

Description

Antifouling paint compositions, the method for preparing said composition, antifouling coat, the surface that is formed by said composition have the coated article body that this is filmed, and carry out the method for antifouling processing by forming described filming

Technical field

The present invention relates to a kind of antifouling paint compositions, a kind of method for preparing said composition, a kind of antifouling coat, a kind of its surface of using said composition to form and have this coated article body of filming, and a kind ofly film and carry out the method for antifouling processing by forming this.

Background technology

Aquatic fouling organism, for example barnacle (barnacle), pipe worm (Tubeworm), Mytilus edulis (common mussel), bugula neritina (Bugula neritina), Ascidian (sea squirt), sea lettuce (green laver), sea lettuce (sea lettuce), and foundry loam etc., be attached to boats and ships (especially bottom of ship), fish for instrument for example fishing net and fishing net accessory, and be immersed in works in the seawater for example on the power station aqueduct, cause functional lesion, appearance damage and other problems of boats and ships etc.

So far, all be to prevent adhering to of aquatic fouling organism by the surface that applies boats and ships with the antifouling paint that comprises the multipolymer that contains organotin, fishes for instrument and be submerged works.For example, contain filming that the antifouling paint of the polymkeric substance of band tributyl tin group forms, make this polymeric constituent be dissolved in gradually in the seawater, cause film coated surface constantly to be replaced, thereby can prevent that aquatic fouling organism from investing on described the filming by coating.After the dissolving, can apply this again and film to show persistent antifouling property.But, because marine pollution matter has now abandoned using described antifouling paint.

The have three Organosilyl groups multipolymer that contains three Organosilyl esters of---it compares toxicity with the organotin group littler and the environment hazardous property is littler---, be developed recently and as the hydrolyzable multipolymer to replace containing the multipolymer (document 1-12) of organotin.

But, comprise the filming of multipolymer of containing three Organosilyl esters and have following shortcoming.During---it has three normal-butyl silyl-group or similar linear alkyl chain group---obtains when using a kind of monomer that contains three Organosilyl esters by copolymerization multipolymer, gained is filmed and is had higher hydrolysis rate.This dissolution rate that causes filming increases gradually, and becomes too high after through longer for some time.In addition, gained is filmed and is had relatively poor water tolerance, and is easy to expand or cracking, makes to be difficult to use this to film for a long time.

For addressing this problem, consider that all organic groups wherein all have the multipolymer that contains three Organosilyl esters (patent documentation 6-12) of branched alkyl group.But though only the multipolymer that contains three Organosilyl esters of containg branched alkyl radical group has good water tolerance, filming of obtaining had low hydrolysis rate.Therefore, need the cost certain hour just can make to film and begin dissolving, cause the anti-fouling effect of starting stage bad.Thus, the inherent aquatic fouling organism of initial time section has in activity or the relative colder zone of seawater, and aquatic fouling organism is attached to coated surface.

For addressing these problems, once attempted containing the multipolymer of three Organosilyl esters and regulating the dissolution rate (patent documentation 2-10) of filming in conjunction with rosin (or rosin derivative) by use.

But, when using rosin (or rosin derivative), though contained metallic compound reaction forms metal-salt in a part of rosin and this coating composition during the coating preparation, but reactive not enough, this rosin (or rosin derivative) that causes having the free carboxy acid remains in this coating composition.Particularly, when using a large amount of rosin, the rosin of high per-cent (or rosin derivative) tends to remain in this coating composition.Rosin (or rosin derivative) has high-hydrophilic, therefore can reduce the water tolerance of filming.As a result, be easy in filming to occur for example bubbling, defectives such as cracking.

Therefore, proposed a kind of wherein with excessive metallic compound and the premixed method of rosin (patent documentation 9 and 10).But in the method, even use excessive metallic compound, this metallic compound and rosin still can not fully react, and make to be difficult to remove fully the rosin (or rosin derivative) that contains the free carboxy acid.

In addition,, worldwide limit solvent based coating in recent years, because solvent based coating is dispersed in the air a large amount of organic solvents in view of environmental problem.Therefore, attempt reducing the content (patent documentation 11 and 12) of organic solvent in the coating.Be difficult to by using these methods to provide to have the antifouling paint of good coating property and antifouling property.

When building new boats and ships, for effectively utilizing dock, in dock, build hull sometimes, then, after hull bottom is applied, make hull float in the seawater outside the dock and the inside for preparing hull., make boats and ships return dock, and apply setting coat thereafter.But because hull is floated in the seawater inner about three months of cost that need of preparation simultaneously, therefore at this section in the period, organism is attached to the surface of filming.Perhaps, even can prevent adhering to of organism, foundry loam still may be attached on this films.These organisms and foundry loam can't be removed satisfactorily by washing with water.If under the situation of not removing described organism and foundry loam satisfactorily, apply setting coat, then the time film and to ftracture, come off etc. when navigation.

[patent documentation 1] Japanese uncensored patent disclosure text No.1998-30071

[patent documentation 2] Japanese uncensored patent disclosure text No.1999-116857

[patent documentation 3] Japanese uncensored patent disclosure text No.1999-116858

[patent documentation 4] Japanese uncensored patent disclosure text No.2000-248228

[patent documentation 5] Japanese uncensored patent disclosure text No.2000-265107

[patent documentation 6] Japanese uncensored patent disclosure text No.2000-265107

[patent documentation 7] Japanese uncensored patent disclosure text No.2002-53796

[patent documentation 8] Japanese uncensored patent disclosure text No.2002-53797

[patent documentation 9] Japanese uncensored patent disclosure text No.2002-97406

[patent documentation 10] Japanese uncensored patent disclosure text No.2003-261816

[patent documentation 11] WO 2005/005516 A1

[patent documentation 12] Japanese uncensored patent disclosure text No.2005-082725

Summary of the invention

Technical problem

An object of the present invention is to provide a kind of antifouling paint compositions of filming that forms, this is filmed in seawater since the starting stage and promptly demonstrates stable solubility and good anti-fouling effect and enough water tolerance, and can demonstrate anti-fouling effect long-term effectively; This antifouling paint compositions is also because of only being dispersed in the air a spot of volatile organic compounds (VOC) to the environment high close friend simultaneously.

Technical scheme

The inventor has carried out extensive studies for addressing the above problem, and finds that above-mentioned purpose can realize by the composition that use has a specific composition.On the basis of this discovery finished the present invention.

Particularly, the invention provides following antifouling paint compositions, prepare said composition method, have the coated article body that this is filmed by antifouling coat, its surface of using said composition to form, and film and carry out the method for antifouling processing by forming this.

The 1st. a kind of antifouling paint compositions, it contains:

Polymkeric substance (A), it is 1 for a kind of number-average molecular weight that obtains by a kind of polymerisable unsaturated carboxylic acid three organic silicomethane esters of polymerization, 000-20,000 polymkeric substance; With

Zinc salt (B), it is at least a zinc salt that is selected from rosin zinc salt and the rosin derivative zinc salt;

This antifouling paint compositions (1) has 45/55 to 10/90 polymkeric substance (A) content and the weight ratio ((A)/(B)) of zinc salt (B) content;

(2) has the non-volatile substance content that is not less than 75 weight %; And

(3) do not contain the rosin or the rosin derivative of free carboxy substantially.

The 2nd. the 1st antifouling paint compositions, wherein the number-average molecular weight of polymkeric substance (A) is 2,000-15,000, and molecular weight dispersity (degree of dispersion of molecularweight) is less than 2.5.

The 3rd. the 1st or 2 antifouling paint compositions, wherein the second-order transition temperature of polymkeric substance (A) is 20-70 ℃.

The 4th. the 1st antifouling paint compositions, wherein polymkeric substance (A) is (methyl) vinylformic acid triisopropyl silicomethane ester copolymer.

The 5th. the methyl methacrylate of (methyl) vinylformic acid triisopropyl silicomethane ester by copolymerization (a) 30-60 weight % of the 3rd antifouling paint compositions, wherein said (methyl) vinylformic acid triisopropyl silicomethane ester copolymer, (b) 10-50 weight % and (c) the removing of 0-60 weight % (a) and (b) (methyl) acrylate middle the definition obtain.

The 6th. the 1st antifouling paint compositions, wherein said rosin zinc salt is at least a zinc salt that is selected from gum resin zinc salt, wood rosin zinc salt and starex zinc salt, and described rosin derivative zinc salt is at least a zinc salt that is selected from staybelite zinc salt and nilox resin zinc salt.

The 7th. the 1st antifouling paint compositions, wherein said non-volatile substance content are not less than 80 weight % and use stormer viscosity meter (Stormer viscometer) to be 80-100KU 25 ℃ of viscosity that record.

The 8th. the 1st antifouling paint compositions, wherein content of volatile organic compound is less than 400g/L.

The 9th. the 1st antifouling paint compositions, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains the 10-100 part by weight of zinc oxide.

The 10th. the 1st antifouling paint compositions, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains 100-400 weight part Red copper oxide.

The 11st. the 10th antifouling paint compositions, the median size of wherein said Red copper oxide are 8-20 μ m.

The 12nd. the 1st antifouling paint compositions, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains the organic stain control agent of 1-100 weight part.

The 13rd. the 1st antifouling paint compositions, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains 1-50 weight part softening agent.

The 14th. the 13rd antifouling paint compositions, wherein said softening agent are a kind of epoxidized oil lipid.

The 15th. the 1st antifouling paint compositions, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains 1-50 weight part dewatering agent.

The 16th. the 15th antifouling paint compositions, wherein said dewatering agent are at least a waterbinding agent that is selected from alkoxyl silicone alkanes and alkyl orthoformate.

The 17th. the 1st antifouling paint compositions, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains 1-50 weight part fatty acid acyl amine dispersion agent.

The 18th. the anti-fouling treatment method that each antifouling paint compositions is implemented in a kind of use 1-17 item, this method are included in the step that the surface of waiting to be coated with thing forms antifouling coat.

The 19th. the antifouling coat that each antifouling paint compositions forms in a kind of use 1-17 item.

The 20th. a kind of its surface has the coated thing of the 19th antifouling coat.

The 21st. a kind of method for preparing antifouling paint compositions, the method includes the steps of:

With polymkeric substance (A)---it is 1 for a kind of number-average molecular weight that obtains by a kind of polymerisable unsaturated carboxylic acid three organic silicomethane esters of polymerization, 000-20,000 polymkeric substance---mixes with zinc salt (B)---it is at least a zinc salt that is selected from rosin zinc salt and rosin derivative zinc salt---;

Described antifouling paint compositions (1) has the weight ratio ((A)/(B)) of the content of 45/55 to 10/90 polymkeric substance (A) content and zinc salt (B);

The 22nd. the 21st the method for preparing antifouling paint compositions, the method includes the steps of:

Polymkeric substance (A) is mixed with zinc salt (B);

Adding median size in the mixture of polymkeric substance (A) and zinc salt (B) is the Red copper oxide of 3-10 μ m; With

The use decollator mixes the mixture that obtains and disperses.

The 23rd. the 21st the method for preparing antifouling paint compositions, the method includes the steps of:

Polymkeric substance (A) is mixed with zinc salt (B);

Use decollator that this mixture is disperseed simultaneously at blended; With

Adding median size is the Red copper oxide of 10-20 μ m and mixes.

Antifouling paint compositions

Antifouling paint compositions of the present invention contains:

(A) a kind of number-average molecular weight that obtains by a kind of polymerisable unsaturated carboxylic acid three organic silicomethane esters of polymerization is 1,000-20,000 polymkeric substance (polymkeric substance (A)); With

(B) at least a zinc salt (zinc salt (B)) that is selected from rosin zinc salt and rosin derivative zinc salt; Wherein

(1) weight ratio ((A)/(B)) of the content of the content of polymkeric substance (A) and zinc salt (B) is 45/55 to 10/90;

(2) non-volatile substance content is not less than 75 weight %; And

(3) this antifouling paint compositions does not contain the rosin or the rosin derivative of free carboxy substantially.

Polymkeric substance (A)

It is 1 that antifouling paint compositions of the present invention contains a kind of number-average molecular weight (Mn) that obtains by a kind of polymerisable unsaturated carboxylic acid three organic silicomethane esters of polymerization, 000-20,000 and be preferably 2,000-15,000 polymkeric substance (being a kind of polymkeric substance that contains polymerisable unsaturated carboxylic acid three organic silicomethane ester units).

The containing of polymkeric substance (A) makes and can form a kind of filming of can demonstrating anti-fouling effect effectively and can prevent well that aquatic fouling organism from adhering to.

If the Mn of polymkeric substance (A) is 1,000-20,000, filming of then obtaining will have gratifying physicals (hardness and intensity).This has prevented cracking and/or the generation that comes off, and makes to keep anti-fouling effect for a long time.If Mn is less than 1,000, though the meltage of filming increases, this is filmed and becomes too crisp and easy and ftracture.If Mn surpasses 20,000, then can't keep the anti-fouling effect of filming for a long time.Particularly, if Mn surpasses 20,000, filming of then obtaining becomes extremely firm, but has lower solubility; Therefore, anti-fouling effect variation gradually.If Mn surpasses 20,000, then the viscosity of polymkeric substance (A) becomes too high.The viscosity that contains the coating composition of polymkeric substance (A) also becomes high.Therefore, when using this class coating composition, need a large amount of organic solvents (thinner) as coating; This influences cost benefit and environment unfriendly.

An example measuring the method for Mn is gel permeation chromatography (GPC).When by gpc measurement Mn, Mn does to represent by the value (use polystyrene standards) that measures behind the reference substance drawing standard curve to use polystyrene.

Preferred polymers (A) has the molecular weight dispersity less than 3.0.If molecular weight dispersity is less than 3.0, then the viscosity of coating composition can significantly reduce.This effectively reduces the consumption of solvent when using this class coating composition as coating.This also makes and can obtain a kind ofly providing the antifouling paint of filming with good physical and desirable long-term anti-fouling effect.

Particularly, preferred Mn is 2,000-15,000 and molecular weight dispersity less than 2.5 polymkeric substance as polymkeric substance (A).More preferably Mn is 5,000-10,000 and molecular weight dispersity be that the polymkeric substance of 2.0-1.0 is as polymkeric substance (A).

Polymkeric substance (A) preferably has 20-70 ℃ and more preferably 30-60 ℃ second-order transition temperature (Tg).When Tg was in 20-70 ℃ scope, hardness of filming and intensity were subjected to the influence of water temperature and free air temperature hardly, made to keep the hardness and the intensity that suit for a long time.If Tg is lower than 20 ℃, filming of then obtaining is soft.When water temperature and free air temperature rising, filming becomes too soft, and defectives such as cold flow easily take place.If Tg surpasses 60 ℃, filming of then obtaining becomes too hard; This can cause filming and take place to ftracture or come off.

Polymkeric substance (A) can obtain by polymerization or at least a monomer that contains three Organosilyls by following general formula (I) expression of copolymerization.

R in the mutual-through type (I) ¹Do not limit especially, as long as it is the alkyl that contains a polymerisable unsaturated double-bond.But a preferred embodiment is as follows.

CH ₂＝C(CH ₃)-，CH ₂＝CH-，CH ₂＝CH-CH ₂-CH ₂-，

More preferably CH ₂=C (CH ₃)-or CH ₂=CH-.

R ⁵Example comprise C ₁-C ₈The alkyl of straight or branched, cycloalkyl, unsaturated alkyl, aralkyl etc.

C ₁-C ₈The example of the alkyl of straight or branched comprises methyl, ethyl, n-propyl, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, 2-methyl butyl, 2-ethyl-butyl, amyl group, 3-methyl amyl, hexyl, heptyl, octyl group etc.

The example of cycloalkyl comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group etc.

The example of unsaturated alkyl comprises 2-propenyl, crotyl, 3-butenyl, pentenyl, 3-pentenyl, 4-pentenyl etc.

The example of aralkyl comprises benzyl, styroyl, hydrocinnamyl etc.

Described alkyl, cycloalkyl, unsaturated alkyl, aralkyl etc. can have a substituting group.Substituent example comprises alkoxyl group, acyl group etc.Substituent number and the position of substitution are not limited, as long as can influence effect of the present invention sharply.

R ⁶To R ⁸Example can be identical or different, and represent C ₃-C ₈Branched-chain alkyl or phenyl.C ₃-C ₈The example of branched-chain alkyl comprises sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, 2-methyl butyl, isopentyl, 2-ethyl-butyl, 3-methyl amyl etc.R ⁶To R ⁸Preferred embodiment comprise sec.-propyl, sec-butyl, the tertiary butyl and phenyl.Wherein, preferred especially sec.-propyl.

In general formula (I), R ²To R ⁴Can be identical or different, and preferably represent C separately ₃-C ₈Branched-chain alkyl or phenyl.C ₃-C ₈The example of branched-chain alkyl with as R ⁶To R ⁸The listed alkyl of example identical.More specifically, R ²To R ⁴Preferred sec.-propyl, sec-butyl, the tertiary butyl and phenyl, and more preferably sec.-propyl.

The monomeric example that contains three Organosilyls by general formula (I) expression comprises the monomer that contains the triisopropyl silyl, the monomer that contains tri-iso-butylsilyl, the monomer that contains three sec-butyl silyls, the monomer that contains the triisopentyl silyl, the monomer that contains the triphenyl silyl, the monomer that contains di-isopropyl isobutyl-silyl, the monomer that contains di-isopropyl sec-butyl silyl, the monomer that contains di-isopropyl isopentyl silyl, the monomer that contains the diisopropyl phenyl silyl, the monomer that contains sec.-propyl diisobutyl silyl, the monomer that contains sec.-propyl two sec-butyl silyls, the monomer that contains tertiary butyl diisobutyl silyl, the monomer that contains tertiary butyl diisoamyl silyl, contain the monomer of t-butyldiphenylsilyl etc.These monomers that contain three Organosilyls can use separately or be used in combination.Wherein, preferably contain the triisopropyl silyl monomer, contain the monomer of three sec-butyl silyls and contain the monomer of t-butyldiphenylsilyl, and more preferably contain the monomer of triisopropyl silyl.In view of production method, production cost, raw material availability and environmental safety, preferably incite somebody to action wherein R ²To R ⁴The monomer that contains the triisopropyl silyl that is sec.-propyl is as the monomer that contains three Organosilyls.

The monomeric example that contains the triisopropyl silyl comprises (methyl) vinylformic acid triisopropyl silicomethane ester, 4-pentenoic acid triisopropyl silicomethane ester, two (triisopropyl silyl) esters of toxilic acid, toxilic acid methyl triisopropyl silicomethane ester, toxilic acid ethyl triisopropyl silicomethane ester, toxilic acid normal-butyl triisopropyl silicomethane ester, toxilic acid isobutyl-triisopropyl silicomethane ester, toxilic acid tertiary butyl triisopropyl silicomethane ester, toxilic acid n-pentyl triisopropyl silicomethane ester, toxilic acid isopentyl triisopropyl silicomethane ester, toxilic acid 2-ethylhexyl triisopropyl silicomethane ester, toxilic acid cyclohexyl triisopropyl silicomethane ester, two (triisopropyl silyl) esters of fumaric acid, fumaric acid methyl triisopropyl silicomethane ester, fumaric acid ethyl triisopropyl silicomethane ester, fumaric acid normal-butyl triisopropyl silicomethane ester, fumaric acid isobutyl-triisopropyl silicomethane ester, fumaric acid n-pentyl triisopropyl silicomethane ester, fumaric acid isopentyl triisopropyl silicomethane ester, fumaric acid 2-ethylhexyl triisopropyl silicomethane ester, fumaric acid cyclohexyl triisopropyl silicomethane ester etc.These monomers can use separately or be used in combination.Especially, the monomer that preferably conduct of (methyl) vinylformic acid triisopropyl silicomethane ester is contained the triisopropyl silyl.

Herein, (methyl) vinylformic acid triisopropyl silicomethane ester means vinylformic acid triisopropyl silicomethane ester or methacrylic acid triisopropyl silicomethane ester.

Preferably with (methyl) vinylformic acid triisopropyl silicomethane ester copolymer (multipolymer (A)) as polymkeric substance (A).Especially, preferably will by copolymerization (a) usually 30-60 weight % and preferred 30-50 weight % (methyl) vinylformic acid triisopropyl silicomethane ester, (b) usually 10-50 weight % and preferred 10-40 weight % methyl methacrylate and (c) usually the multipolymer that obtains of (methyl) acrylate except that (a) and (b) of 0-60 weight % and preferred 0-50 weight % as multipolymer (A).

Unit " weight % " expression each monomeric per-cent when the total amount that will treat comonomer is defined as 100 weight %.

If the content of monomer (a) drops in the scope of 30-60 weight %, filming of then obtaining will demonstrate required anti-fouling effect effectively.In addition, can suitably control the hydrolysis rate of filming, keep desirable anti-fouling effect for a long time.This has also improved water tolerance and intensity that gained is filmed.

If the content of monomer (a) is less than 30 weight %, filming of then obtaining will have relatively poor solubility, make this film and be difficult to demonstrate long-term anti-fouling effect.If the content of monomer (a) surpasses 60 weight %, filming of then obtaining will have too high solubility, make that being difficult to design this films.In addition, this will make to film and can not have gratifying water tolerance and intensity.

When the content of monomer (b) in the scope of 10-50 weight %, filming of then obtaining can keep the hardness and the intensity that suit for a long time.If filming that the content of monomer (b) less than 10 weight %, then obtains will become too soft and be prone to defectives such as cold flow.If the content of monomer (b) surpasses 50 weight %, though the intensity of filming that obtains will improve, this is filmed and will become too hard, causes the risk that has cracking or come off.

Term " other (methyl) acrylate " (monomer (c)) means acrylate or methacrylic ester except that methyl methacrylate.Its specific examples comprises (methyl) alkyl acrylates such as methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate; (methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-methoxyl group propyl ester, (methyl) vinylformic acid 4-methoxyl group butyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester; (methyl) vinylformic acid alkylene glycol mono-methyls such as (methyl) vinylformic acid glycol monomethyl methyl esters, (methyl) vinylformic acid propylene glycol mono-methyl; (methyl) acrylic acid hydroxy alkyl esters such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate; (methyl) vinylformic acid dialkylamino ethyl esters such as (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester; And (methyl) vinylformic acid three organic silicomethane esters such as the three normal-butyl silicomethane esters of (methyl) vinylformic acid outside the demonomerization (a), (methyl) vinylformic acid triisobutyl silicomethane ester, (methyl) vinylformic acid three sec-butyl silicomethane esters, (methyl) vinylformic acid triphenyl silicomethane ester, (methyl) vinylformic acid tert-butyl diphenyl silicomethane ester.In addition, also can use (methyl) benzyl acrylate, (methyl) phenyl acrylate etc.The example of above-mentioned monomer (c) can be used alone as or in conjunction with as the monomer component of multipolymer (A).Wherein, especially preferably with (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-methoxyl group propyl ester etc. as monomer (c).

In multipolymer (A) synthetic, remove above-mentioned monomer (a) and (b) and (c) any monomer all can influence the water tolerance of filming and the amount interpolation of solubility sharply.

The example of monomer available comprises vinyl compound, aromatic substance, vinylformic acid and the methacrylic acid with a functional group.Described example with vinyl compound of a functional group comprises vinylchlorid, vinylidene chloride, (methyl) vinyl cyanide, vinyl-acetic ester, butyl vinyl ether, lauryl vinyl ether, N-vinyl pyrrolidone etc.The example of aromatic substance comprises vinylbenzene, Vinyl toluene, alpha-methyl styrene etc.

Especially, multipolymer (A) is preferably the multipolymer of the monomer (monomer (c)) of (methyl) vinylformic acid triisopropyl silicomethane ester (monomer (a)), methyl methacrylate (monomer (b)) and at least a being selected from (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid 2-methoxyl group ethyl ester and (methyl) vinylformic acid 2-methoxyl group propyl ester.

Polymkeric substance (A) can be random copolymers, alternating copolymer, periodic copolymer or segmented copolymer.

Polymkeric substance (A) can by for example in the presence of polymerization starter polymerization single polymerization monomer (a), monomer (b) and monomer (c) obtain.

The example of the polymerization starter that uses in described polyreaction comprises 2,2 '-Diisopropyl azodicarboxylate (AIBN), 2,2 '-azo two-2-methylbutyronitrile, dimethyl-2,2 '-azo-compounds such as azo-bis-isobutyrate; Diacyl peroxides such as dibenzoyl peroxide, peroxidation two (3-toluyl), benzoyl peroxide (3-toluyl), dilauroyl peroxide; Tert-butyl peroxides such as di-t-butyl peroxide, t-butyl per(oxy)benzoate, the peroxy isopropyl base carbonic acid tert-butyl ester, the Peroxycaprylic acid tert-butyl ester; Peroxidation-2 ethyl hexanoic acid tert-pentyl ester, Peracetic Acid tert-pentyl ester, the different n-nonanoic acid tert-pentyl ester of peroxide, benzoyl hydroperoxide tert-pentyl ester, Peracetic Acid tert-pentyl ester, Peroxycaprylic acid tert-pentyl ester, two (peroxidation tert-pentyl), 1, t-amyl peroxy things such as 1-two (peroxidation tert-pentyl) hexanaphthene; And uncle's hexyl superoxide such as peroxidation-own ester of 2 ethyl hexanoic acid uncle, the own ester of benzoyl hydroperoxide uncle, the own ester of peroxy isopropyl base list carbonic acid uncle, the own ester of peroxide PIVALIC ACID CRUDE (25) uncle, the own ester of Peroxycaprylic acid uncle, the own ester of peroxide neodecanoic acid uncle.These polymerization starters can use separately or be used in combination.The preferred embodiment of described polymerization starter comprises diacyl peroxide, tert-butyl peroxide, t-amyl peroxy thing and uncle's hexyl superoxide.Wherein, more preferably t-amyl peroxy thing and uncle's hexyl superoxide.Compare with the situation of using other polymerization starter, can obtain having more narrow molecular weight distributions and more low viscous polymkeric substance as polymerization starter by using t-amyl peroxy thing or uncle's hexyl superoxide.

By the amount of the used polymerization starter of suitable selection, the suitable molecular weight of telomerized polymer (A).

The example of polymerization process comprises solution polymerization, mass polymerization, letex polymerization, suspension polymerization etc.Wherein, the preferred solution polymerization is because it can be easily and accurately prepares multipolymer (A).

In polyreaction, if necessary, can add a kind of organic solvent.The example of organic solvent comprises aromatic hydrocarbon solvents such as dimethylbenzene, toluene; Aliphatic hydrocarbon such as hexane, heptane solvent; Esters solvents such as ethyl acetate, butylacetate, isobutyl acetate, acetate methoxyl group propyl ester; Alcoholic solvent such as Virahol, butanols; Ether solvents such as diox, ether, dibutyl ether; Ketones solvent such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Deng.Preferred aromatic hydrocarbons kind solvent wherein, and more preferably dimethylbenzene.These solvents can use separately or be used in combination.

Temperature of reaction in the described polyreaction can suit to select according to the type of polymerization starter etc., but is generally 70-140 ℃, and preferred 80-120 ℃.This polyreaction required time can suit to select according to temperature of reaction etc., but is generally about 4-8 hour.

Described polyreaction is preferably for example carried out in nitrogen and the argon gas at inert atmosphere.

Zinc salt (B)

Antifouling paint compositions of the present invention contains at least a zinc salt (zinc salt (B)) that is selected from rosin zinc salt and rosin derivative zinc salt.Because above-mentioned zinc salt has the higher consistency of polymkeric substance (A), so they can stably be present in and film.Therefore, the present composition has good long storage.

When using sodium salt except that above-mentioned zinc salt, calcium salt, magnesium salts etc. as rosin (or rosin derivative) metal-salt, because sodium salt etc. has too high wetting ability (though high unlike the wetting ability of the rosin with free carboxy acid (or rosin derivative)), the risk that therefore exists the water tolerance of filming to reduce.

The example of rosin zinc salt comprises gum resin zinc salt, wood rosin zinc salt, starex zinc salt etc.These salt can use separately or be used in combination.

The example of rosin derivative zinc salt comprises maleic acid anhydridization rosin zinc salt, formylation rosin zinc salt, polymerized rosin zinc salt, staybelite zinc salt, nilox resin zinc salt etc.These salt can use separately or be used in combination.

In the present invention, the rosin zinc salt is preferably and is selected from least a in gum resin zinc salt, wood rosin zinc salt and the starex zinc salt; And the rosin derivative zinc salt is to be selected from least a in staybelite zinc salt and the nilox resin zinc salt.

Abietate and rosin derivative salt are available commercially.Perhaps, abietate and rosin derivative salt can be by currently known methods productions.For example, rosin (or rosin derivative) zinc salt can have free carboxy (COO by making ^-Group) reacts under the situation that rosin (or rosin derivative) and zinc oxide heat in solution and make.

One of principal character of the present composition is that it contains the zinc salt (B) of relatively large amount.The weight ratio of the content of the content of polymkeric substance in the said composition (A) and zinc salt (B) ((A)/(B)) is preferred 45/55 to 10/90, and more preferably 40/60 to 20/80.When this weight ratio drops in 45/55 to 10/90 the scope, filming of obtaining will have good hardness and intensity, make to control the meltage of filming on demand, and this be filmed and demonstrates long-term anti-fouling effect.

In addition, rosin zinc salt and rosin derivative zinc salt have lower viscosity than polymkeric substance (A) and the metal-salts such as mantoquita except that rosin zinc salt and rosin derivative zinc salt.Therefore, by rosin zinc salt and the rosin derivative zinc salt that uses relatively large amount, promptly in above-mentioned weight ratio scope, can reduce the viscosity of coating composition.In the case, because the gained coating composition has lower viscosity, therefore when using said composition to make coating, can reduce the amount of solvent.This causes obtaining the antifouling paint of the volatile organic compounds (VOC) of a kind of required non-volatile substance that contains comparatively large vol content and less per-cent, and is promptly low-the VOC antifouling paint.

The present composition does not contain the rosin and the rosin derivative of free carboxy substantially.Particularly, the content of rosin described in the present composition and rosin derivative preferably is not higher than 1 weight %, and more preferably 0-0.1 weight %.The rosin and the rosin derivative that contain free carboxy have high-hydrophilic.Therefore, when containing this class rosin and rosin derivative when filming, the water tolerance of filming will reduce, and this can cause filming and defectives such as foaming, cracking upward occur.

Red copper oxide

Antifouling paint compositions of the present invention preferably also contains Red copper oxide.Red copper oxide can play stain control agent.By containing Red copper oxide, filming of obtaining can demonstrate anti-fouling effect effectively.

It the form of Red copper oxide is not had special restriction, as long as can influence effect of the present invention sharply.For example, Red copper oxide can adopt the particulate form.

The median size of particulate state Red copper oxide is preferably 3-20 μ m, and more preferably 8-20 μ m.When the present composition contains median size and is the Red copper oxide of 3-20 μ m, can control the dissolution rate of filming as required, thereby can show long-term anti-fouling effect.When the median size of Red copper oxide drops in the 8-20 mu m range, can further reduce the viscosity of coating composition of the present invention, produce low VOC antifouling paint as required.

A preferred embodiment of the form of Red copper oxide is the Red copper oxide that its surface applies with the coating agent.When using particulate state Red copper oxide, preferably each particulate surface is applied with the coating agent.By applying, can advantageously prevent the oxidation of Red copper oxide with the coating agent.

The example of available coating agent comprises stearic acid, lauric acid, glycerol, sucrose, Yelkin TTS etc.These coating agents can use separately or be used in combination.

With respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the present composition preferably contains 100-400 weight part, more preferably 200-300 weight part Red copper oxide.When the total amount with respect to per 100 parts by weight polymer (A) and zinc salt (B), when the content of Red copper oxide was the 100-400 weight part, filming to demonstrate good anti-fouling effect.

Wish that Red copper oxide contained in the described composition is aggregated thing (A), zinc salt (B), a kind of following coverings such as organic solvent.When Red copper oxide was aggregated thing (A) etc. unsatisfactorily and covers, Red copper oxide can't be scattered in the composition satisfactorily and may occur assembling.When Red copper oxide is assembled, gained film be prone to the cracking or come off.

Except that oxidation was cuprous, the present composition also can contain any other inorganic stain control agents of the amount that can influence anti-fouling effect sharply.Copper rhodanide), cupronickel, copper powder etc. the example of available inorganic stain control agent comprises cupric thiocyanide (common name:.These inorganic stain control agents can use separately or be used in combination.

Pigment

Antifouling paint compositions of the present invention can contain multiple pigment.By adding one or more pigment, can improve intensity, weathering resistance, water tolerance and the solubility of filming.

Particularly, the preferred present composition also contains zinc oxide.By adding zinc oxide, can quicken film dissolving in seawater of gained, and can show anti-fouling effect effectively.The form of zinc oxide there is not special restriction.For example, can use particulate state zinc oxide.

When using particulate state zinc oxide, its particle diameter is not had special restriction, and can in the scope that can influence effect of the present invention, select sharply.

With respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the content of zinc oxide is preferably 10-100 weight part and more preferably 20-50 weight part in the present composition.When total amount, when the content of zinc oxide drops in the scope of 10-100 weight part, can suitably control the dissolution rate of filming with respect to per 100 parts by weight polymer (A) and zinc salt (B).When the total amount with respect to per 100 parts by weight polymer (A) and zinc salt (B), the content of zinc oxide is during less than 10 weight parts, the dissolving in seawater of can't quickening satisfactorily to film.When the total amount with respect to per 100 parts by weight polymer (A) and zinc salt (B), when the content of zinc oxide surpassed 100 weight parts, the solubleness of filming excessively increased.This makes restive dissolution rate of filming.

Except that above-mentioned zinc oxide, also can use known water-soluble pigment and water-insoluble pigment as described pigment.

The example of water-soluble pigment comprises Red copper oxide, cupric oxide, cupric thiocyanide, zinc carbonate, zinc sulphide, secondary calcium phosphate, calcium phosphate, Calucium Silicate powder, iron carbonate, iron carbonyl, magnesium hydroxide, magnesiumcarbonate etc.These water-soluble pigment can use separately or be used in combination.Particularly, preferably use at least a in Red copper oxide and the cuprous thiocyanate as water-soluble pigment.

As an example of water-soluble pigment and the Red copper oxide of mentioning can be identical or different with above-mentioned those listed Red copper oxide.

The example of water-insoluble pigment comprises titanium dioxide, ferric oxide, talcum, lime carbonate, silicon-dioxide, kaolin, perlite, mica, barium sulfate, graphite, carbon black etc.They can use separately or be used in combination.Particularly, preferably use at least a in titanium dioxide, ferric oxide, talcum, lime carbonate, silicon-dioxide, kaolin and the barium sulfate as water-insoluble pigment.

Water-soluble pigment has the effect that improves in the seawater solubleness of filming.Zinc oxide is a kind of compound that belongs to water-soluble pigment class.Water-insoluble pigment has the effect that reduces in the seawater solubleness of filming.Therefore, by the type and the consumption of water-soluble pigment of suitable selection and water-insoluble pigment, can suitably control the physicals and the solvability of filming.

To the content of pigment in the present composition without limits.But, advantageously the content of pigment is selected that gained is filmed and has 20-50% and the more preferably pigment volume concentration (PVC) of 25-45% (PVC).

PVC is less than 20% film too soft, and the undercapacity that has.PVC will be fragility and easy to crack above 50% film.

Described PVC can obtain by following calculating formula.

The cumulative volume (ml) * 100 of PVC (%)=pigment cumulative volume (ml) (comprising the pigment that is not dissolved in the solvent) ÷ solid ingredient

In this calculating formula, statement " cumulative volume of solid ingredient (ml) " is meant the volume summation of pigment, polymkeric substance (A), zinc salt (B) etc.When the present composition contains above-mentioned listed Red copper oxide and following organic stain control agent, softening agent, dewatering agent, dispersion agent etc., during the volume of these components is included in described " cumulative volume of solid ingredient (ml) ".

With Red copper oxide similarly, wish that pigment contained in the described composition is with polymkeric substance coverings such as (A).When pigment is aggregated thing (A) etc. and covers satisfactorily, can effectively prevent the cracking that gained is filmed or come off.

Organic stain control agent

Antifouling paint compositions of the present invention also can contain any organic stain control agent.

To described organic stain control agent without limits, as long as they have aquatic fouling organism and kill or walk quickly and keep away effect.Copper pyrithione (copper pyrithione)) example of described organic stain control agent comprises 2-mercaptopyridine-N-cupric oxide (popular name: organocopper compound such as; Zinc Pyrithione (zinc pyrithione)), zineb (popular name: zineb (zineb)), two (dimethyl dithiocarbamic acid) zinc (popular name: ziram (ziram)), two (Methyl disulfide is for formamyl) ethylenebis (dithiocarbamic acid) zinc (popular name: organic zinc compound such as polycarbamate (polycarbamate)) 2-mercaptopyridine-N-zinc oxide (popular name:; Organoboron compounds such as pyridine-triphenylborane, 4-isopropyl pyridine base-diphenyl methyl borine, 4-phenylpyridyl-phenylbenzene borine, triphenyl-boron-just-octadecylamine, triphenyl [3-(2-ethyl hexyl oxy) propyl group amine] boron; And 2,4,6-trichlorine maleimide, N-(2,6-diethyl phenyl)-2, maleimide compounds such as 3-dichloro maleimide.Other examples of organic stain control agent comprise 4,5-two chloro-2-n-octyl-3-isothiazoloness (popular name: Sea-Nine 211), 3,4-dichlorophenyl-N-N-dimethyl urea (popular name: Diuron Tech (diuron)), 2-methylthio group-4-tertiary butyl amino-6-cyclopropyl amino-s-triazine (popular name: Irgarol 1051), 2,4,5,6-daconil M (popular name: m-tetrachlorophthalodinitrile (chlorothalonil)), N-dichloro fluorine methylthio group-N ', N '-dimethyl-N-p-methylphenyl sulphonamide (popular name: Tolylfluanid (tolylfluanid)), N-dichloromethane sulfenyl-N ', N '-dimethyl-N-phenyl-sulfamide (popular name: dichlofluanid (dichlofluanid)), 2-(4-thiazolyl) benzoglyoxaline (popular name: thiabendazole (thiabendazole)), 3-(benzo [b] thiophene-2-yl)-5,6-dihydro-1,4,2-Evil thiazine-4-oxide compound (popular name: bethoxazine), 2-(rubigan)-3-cyano group-4-bromo-5-trifluoromethyl pyrpole (popular name: Econea 028) etc.Wherein, preferred Zinc Pyrithione, copper pyrithione, pyridine-triphenylborane, 4-isopropyl pyridine base-diphenyl methyl borine, bethoxazine, zineb, Sea-Nine 211 and Irgarol 1051.More preferably copper pyrithione, Zinc Pyrithione, pyridine-triphenylborane and bethoxazine.These organic stain control agents can use separately or be used in combination.

With respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the content of organic stain control agent is preferably the 1-50 weight part in the present composition, and more preferably 10-30 weight part.If with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the content of organic stain control agent then can't demonstrate the anti-fouling effect of organic stain control agent satisfactorily less than 1 weight part.If with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), described content surpasses 50 weight parts, does not then observe with the proportional anti-fouling effect of the increase of organic antifouling dosage to improve; Therefore this is uneconomic.

Softening agent

Antifouling paint compositions of the present invention also can contain a kind of softening agent.By containing described softening agent, can improve the plasticity-of composition, obtain a kind of preferred firm filming.This has also improved to film treats the adhesivity of coated object.

The example of accessible plasticizer comprises phosphoric acid ester such as Tritolyl Phosphate, trioctyl phosphate, triphenylphosphate; Phthalic ester such as dibutyl phthalate, dioctyl phthalate (DOP); Adipic acid ester such as Polycizer W 260, Octyl adipate; Sebate such as Uniflex DBS, dioctyl sebacate; Epoxidized oil such as epoxidised soybean oil, epoxy linseed oil lipid; Alkyl vinyl ether polymers such as methyl ethylene ether polymer, ethyl vinyl ether polymer; And polyalkylene glycol such as polyoxyethylene glycol, polypropylene glycol.Other examples of softening agent comprise that the Tg of five sulfuration uncle nonyls, Vaseline, polybutene, tri trimellitate (2-ethylhexyl) ester, silicone oil, whiteruss, clorafin, ethylenically-unsaturated carboxylic acid ester's polymer formation is not higher than-20 ℃ polymeric plasticiser etc.These softening agent can use separately or be used in combination.

In the present invention, preferred described softening agent be selected from phosphoric acid ester, epoxidized oil lipid, and Tg be not higher than at least a in ethylenically-unsaturated carboxylic acid ester's polymkeric substance of-20 ℃.Wherein, more preferably epoxidized oil lipid.

The content of softening agent depends on the content of rosin zinc salt in the said composition and/or rosin derivative zinc salt in the present composition, but, be preferably 1-50 weight part and more preferably 5-30 weight part with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B).If with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the content of softening agent then can't obtain the improvement of gratifying physicals (intensity and adhesivity) less than 1 weight part.If with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), described content surpasses 50 weight parts, and then filming becomes too soft, and in fact unavailable.

Dewatering agent

Preferred antifouling paint compositions of the present invention also contains a kind of dewatering agent.Described dewatering agent is a kind of reagent of removing water in the composition.The example of available dewatering agent comprises waterbinding agent and siccative (dehydrating agent).Described waterbinding agent and siccative all can use separately, and perhaps described waterbinding agent and siccative can be used in combination.

Described waterbinding agent be a kind of can be by removing the compound of the water in the coating composition with water reaction.The example of waterbinding agent comprises alkyl orthoformates such as original acid A ester, ethyl orthoformate; Alkoxyl silicone alkanes such as tetraethoxysilane, four butoxy silanes, tetraphenoxy-silicane alkane, four (2-oxyethyl group butoxy) silane, methyltrimethoxy silane, Union carbide A-162, dimethyldiethoxysilane, trimethylethoxysilane, phenylbenzene diethoxy silane; Reach acid anhydrides such as maleic anhydride, Tetra hydro Phthalic anhydride.

Described siccative be a kind of can be by water be incorporated into the compound of removing water in the said composition in this siccative with the form of crystal water.The example of siccative comprises dehydrated gyp-, molecular sieve, sal epsom, sodium sulfate etc.

The preferred waterbinding agent that uses is as dewatering agent.Preferred waterbinding agent is to be selected from least a in alkoxyl silicone alkanes and the alkyl orthoformate, and particularly preferred waterbinding agent is a tetraethoxysilane.

To the dewatering agent content in the present composition without limits, but with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), this content is preferably 1-50 weight part and more preferably 2-30 weight part.If with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the content of dewatering agent is less than 1 weight part, then the present composition can not reach gratifying package stability.If with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the content of dewatering agent surpasses 50 weight parts, and then filming to become too crisp.Particularly, waterbinding agent is volatile in air.Therefore, when using waterbinding agent as dewatering agent, for reducing the disadvantageous effect to environment, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the amount of waterbinding agent preferably is not higher than 30 weight parts.

Dispersion agent

The present composition preferably also contains a kind of dispersion agent (a kind of antisettling agent).By containing dispersion agent, can prevent in the present composition storage process sedimentation of present composition component (for example pigment, Red copper oxide, zinc oxide, titanium dioxide, ferric oxide, talcum etc.), and the formation of lump (hard-caked sediment).This has also solved the use present composition forms composition (coating) drip when filming on treating the coated object surface problem effectively.

The example of dispersion agent comprises oxidic polyethylene class dispersion agent, fatty acid acyl amine dispersion agent, the fatty acid ester dispersion agent, hydrogenated castor oils dispersion agent, plant polymerization oils dispersion agent, the polyether ester type tensio-active agent, the sulfuric acid ester type anion surfactant, poly carboxylic acid amine salt class dispersion agent, the polycarboxylic acid dispersion agent, high-molecular-weight poly ethers dispersion agent, acrylate copolymer class dispersion agent, extraordinary silicon class dispersion agent, the talcs dispersion agent, swelling great soil group dispersion agent, the kaolin families dispersion agent, silica type dispersion agent etc.These dispersion agents can use separately or be used in combination.The present composition preferably contains fatty acid acyl amine dispersion agent as dispersion agent.The present composition can contain the mixing solutions of polymkeric substance (A) and other components, mix then and disperse this mixing solutions to be prepared by for example preparation.When described mixing solutions contains fatty acid acyl amine dispersion agent, can improve the package stability of this mixing solutions, and can obtain the present composition easier and reliably.

In the present invention, can use the commercially available dispersion agent that gets.The example of fatty acid acyl amine dispersion agent comprises Dispalon A603-10X (or 20X), Dispalon 6900-10X (or 20X) and Dispalon 6810-10X (or 20X) (all being Kusumoto Chemicals, the product of Ltd.); Talen 7500-20 and Flownon SP-1000 (both are Kyoeisha Chemical Co., the product of Ltd.); Deng.

Dispersion agent can use after for example in the dimethylbenzene being dispersed to organic solvent.Content to dispersion agent in the present composition is unrestricted; But with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), its content is preferably the 1-50 weight part, and more preferably 2-30 weight part.If with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the content of dispersion agent then can not show the effect (promptly preventing to form lump) of dispersion agent less than 1 weight part.Particularly, the package stability of the present composition may become not enough.If with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), the content of dispersion agent surpasses 50 weight parts, and then the viscosity of composition becomes too high, and this may make coating become difficult.In addition, can't obtain in the improvement that prevents aspect the lump formation by the content that improves dispersion agent, therefore, this is uneconomic.

Other additives etc.

The present composition also can contain dyestuff, antisettling agent, defoamer etc.

Usually with present composition dissolving or be dispersed in the organic solvent.This can make coating use as required.The example of available organic solvent comprises dimethylbenzene, toluene, mineral solvent oil (mineralspirit), MIBK, butylacetate etc.Wherein, preferred especially dimethylbenzene and MIBK.These organic solvents can use separately or be used in combination.

Particularly, when using the present composition, can reduce the amount of used organic solvent.This viscosity owing to the present composition is lower.Sometimes will use the coating of described composition to be called in the art " high solid coating ".

More particularly, the present composition can be used as low VOC antifouling paint compositions.The coating that the application of the invention composition obtains discharges more a spot of volatile organic compounds in air, thereby has reduced the disadvantageous effect to environment.

VOC content in the present composition is preferably less than 400g/L, and more preferably in the scope of 300-350g/L.

The content of non-volatile substance is not less than 75 weight % usually in the present composition, preferably is not less than 80 weight %, and more preferably is not less than 85 weight %.

Use the viscosity of the present composition that the stormer viscosity meter records under 25 ℃ to be preferably 70-100KU, and more preferably 80-100KU.In the time of in using viscosity the scope at 70-100KU of stormer viscosity meter, use coating composition of the present invention can easily obtain enough thick filming with a small amount of solvent at the composition that records under 25 ℃.In addition, when composition viscosity is in this scope, can effectively prevents the sedimentation of present composition component (for example pigment, Red copper oxide, zinc oxide, titanium dioxide, ferric oxide, talcum etc.) and make long storage become possibility.

Described viscosity can be measured according to JIS-5400 (or ASTM D562-01).Can use the commercially available stormer viscosity meter that gets.

The present composition demonstrates good storing stability, even gelation or curing also take place after long storage hardly.

The preparation method of antifouling paint compositions

The method for preparing antifouling paint compositions of the present invention may further comprise the steps:

With (A)---a kind of number-average molecular weight that obtains by a kind of polymerisable unsaturated carboxylic acid three organic silicomethane esters of polymerization is 1,000-20,------at least a zinc salt (zinc salt (B)) that is selected from rosin zinc salt and rosin derivative zinc salt---mixes 000 polymkeric substance (polymkeric substance (A)) with (B).

The antifouling paint compositions that obtains by this preparation method has following feature.

(1) weight ratio ((A)/(B)) of the content of the content of polymkeric substance (A) and zinc salt (B) is 45/55 to 10/90.

(2) non-volatile substance content is not less than 75 weight %.

Above-mentioned preparation method of the present invention can effectively obtain antifouling paint compositions of the present invention.

Can use above polymkeric substance listed under the title of polymkeric substance (A) and zinc salt (B) and zinc salt as polymkeric substance (A) and zinc salt (B).If necessary, can add above listed pigment, Red copper oxide, organic stain control agent, dewatering agent, dispersion agent and other additives.

Can suit to the amount of polymkeric substance (A), zinc salt (B) and other components to select, thereby make the gained antifouling paint compositions contain the interior polymkeric substance (A) of above-mentioned acceptable content range, zinc salt (B) etc.

The hybrid mode of preferred these components is, with polymkeric substance multiple material dissolves such as (A) or be scattered in the solvent.For example, at first polymkeric substance (A) and zinc salt (B) can be dissolved or dispersed in the solvent, mix with other material (for example, organic stain control agent) then.The example of useable solvents comprises dimethylbenzene, toluene, mineral solvent oil, MIBK, butylacetate etc.Wherein, preferred especially dimethylbenzene.They can use separately or be used in combination.

When using Red copper oxide to prepare antifouling paint compositions of the present invention, preferably suitably select preparation method 1 or preparation method 2 according to the median size of used Red copper oxide.

Particularly, when using median size, preferably select preparation method 1 as the Red copper oxide of 3-10 μ m, preferred 3-8 μ m.

The preparation method 1

Antifouling paint compositions can be the Red copper oxide of 3-10 μ m and preferred 3-8 μ m and use the decollator mixing and disperse the gained mixture to be prepared by interpolation median size in the mixture of polymkeric substance (A) and zinc salt (B).

Median size is that the Red copper oxide of 3-10 μ m easily produces secondary aggregation.Therefore, when only interpolation contained the material of Red copper oxide, the composition that obtains may have caking.This can cause cracking that gained films etc.In preparation method 1, use decollator will contain compounding substances mixing and the dispersion of median size, thereby can alleviate the secondary aggregation of Red copper oxide as the Red copper oxide of 3-10 μ m.This makes and can obtain wherein Red copper oxide by wishing the dispersive antifouling paint compositions.

Preparation method 1 can make antifouling paint compositions as the compounding substances of the Red copper oxide of 3-10 μ m by using decollator to mix and disperseing to contain polymkeric substance (A), zinc salt (B) and median size.

If necessary, described compounding substances also can contain multiple additives such as pigment mentioned above, organic stain control agent, dewatering agent, dispersion agent.

Can suit to the content of polymkeric substance (A), zinc salt (B), Red copper oxide etc. in the described compounding substances to select, thereby make the gained antifouling paint compositions contain the above-mentioned interior polymkeric substance (A) of content range, zinc salt (B), the Red copper oxide etc. accepted.

Preferred described compounding substances is by with polymkeric substance multiple material dissolves such as (A) or be scattered in the solvent and be prepared.An example for preparing the method for described compounding substances is, polymkeric substance (A) and zinc salt (B) are dissolved or dispersed in the solvent, mixes with other materials (for example above-mentioned organic stain control agent etc.) then.The example of useable solvents is identical with above-mentioned examples of solvents.

Decollator can be selected from the decollator that can be used as micropulverizer on demand.Its specific examples comprises runner milling and dissolver.

The example of spendable runner milling comprises that ball mill, sand mill, ball mill (bead mill, pearl mill), Dyno runner milling, Cowle runner milling, basket runner milling, attritor etc. are generally used for mixing and the runner milling of dispersion paints.

Dissolver is a kind of decollator with rotating paddle type shredder.Mixing solutions can mix and disperses by rotating this shredder.When using dissolver as decollator, the preferred shredder high speed rotating of this dissolver.By making the shredder high speed rotating, can advantageously alleviate the secondary aggregation of Red copper oxide.

Dissolver also can be described as decollator.

During as described Red copper oxide, preferably select following preparation method 2 as the Red copper oxide of 10-20 μ m, preferred 13-20 μ m when using median size.

The preparation method 2

Antifouling paint compositions can be prepared by the mixture that uses decollator to mix and to disperse to obtain in the following manner: polymkeric substance (A) is mixed with zinc salt (B), also mixes to wherein adding the Red copper oxide of median size as 10-20 μ m and preferred 13-20 μ m then.

Median size is that secondary aggregation takes place the Red copper oxide of 10-20 μ m hardly.Therefore, the present composition can prepare in the following way: use decollator to mix and disperse to contain the compounding substances of polymkeric substance (A) and zinc salt (B), in the blending dispersion system that obtains, add Red copper oxide, use mixing device to mix described mixture then to grind Red copper oxide particulate mode as few as possible.In the method, Red copper oxide is ground hardly, so the surface-area of Red copper oxide is limited in the relatively little scope in the resulting composition.For example, the surface-area of Red copper oxide can be not more than 1.3 * 10 ^-3Mm ², and preferably 3.0 * 10 ^-4To 1.3 * 10 ^-3Mm ²Scope in.

As mentioned above, wish that Red copper oxide contained in the composition is aggregated thing coverings such as (A) satisfactorily.

When Red copper oxide has small surface area, can reduce the amount of the used polymkeric substance (A) in the cuprous surface of capping oxidation, zinc salt (B), organic solvent etc.As a result, can obtain low VOC antifouling paint as required.

For antifouling coat, when the surface-area of Red copper oxide hour, even seawater temperature higher (particularly being not less than 30 ℃) still can be controlled the dissolution rate of filming effectively.Preparation method 2 can shorten the time of using decollator to implement this method, thereby reduces the production cost of the present composition.

Used identical among described compounding substances and the preparation method 1, except this compounding substances oxygen-freeization cuprous.

Can suitably select the amount of the Red copper oxide that added, thereby the antifouling paint compositions that obtains be contained to accept Red copper oxide in the content range.

Decollator can be identical with used decollator among the preparation method 1.

Unrestricted to mixing device, can use any known mixing device.For example, can use above-mentioned dissolver.When using described dissolver, preferably the rotating speed of shredder is set to middling speed or low speed.Rotating speed by shredder is set to middling speed or low speed, can effectively prevent the fragmentation of Red copper oxide.

Anti-fouling treatment method, antifouling coat and coated article body

Anti-fouling treatment method of the present invention is characterised in that, uses above-mentioned antifouling paint compositions treating to form antifouling coat on the surface of coated object.Thereby anti-fouling treatment method of the present invention can be brought in constant renewal in described film coated surface by the dissolving gradually on antifouling coat surface and prevent adhering to of aquatic fouling organism.Film after the dissolving, can continue to show anti-fouling effect by applying said composition again.

The example that can form the object of filming thereon comprises boats and ships (particularly bottom of ship), fishes for instrument, is immersed in works in the seawater etc.The example of fishing for instrument is included in the aquaculture or fixedly establishes the fishing net that uses in the net, and the fishing net accessory for example is connected in buoy on the fishing net, rope etc.The example that is immersed in the works in the seawater comprises power station aqueduct, bridge, port facilities etc.

Antifouling coat of the present invention can form by antifouling paint compositions being applied to the object surfaces that formation thereon films (entirely or partly).

The example of coating method comprises brushing, spraying, dipping, flow coat, spin coating etc.These coating methods can use separately or be used in combination.

Coating composition carries out drying after applying.Drying temperature can be room temperature.Can suitably select time of drying according to thickness of filming etc.The thickness of antifouling coat can suitably be selected according to the route speed of the type that forms the object film thereon, boats and ships, seawater temperature etc.For example, when forming the object film thereon and be bottom of ship, the thickness of antifouling coat is generally 50-500 μ m, and preferred 100-400 μ m.

Antifouling coat of the present invention has the following advantages.

1) this is filmed and is dissolved in the seawater with stable manner for a long time, thereby constantly changes film coated surface, and this can realize good anti-fouling effect and prevent aquatic fouling organism adhering to film coated surface.

2) this is filmed and has good water tolerance, even be arranged in seawater for a long time, can prevent that also foaming, expansion, cracking or other defect from appearring in film coated surface.

3) this is filmed and has required hardness, can resist cold flow and other defect.

4) this is filmed and adheres to securely on the object that formation is filmed thereon, makes to be easier to apply on this object.

Has described antifouling coat on the surface of coated article body of the present invention.Coated article body of the present invention can have described antifouling coat on its whole surface or its part.

The antifouling coat that coated article body and function of the present invention has above-mentioned 1-4 item feature applies.Therefore, can on demand it be coated to boats and ships (particularly bottom of ship), fish for instrument, be immersed in works in the seawater etc.

For example, when antifouling coat was formed on the surface of bottom of ship, this antifouling coat dissolved gradually from this surface, thereby film coated surface always is updated.This has prevented the adhesion of aquatic fouling organism.

In addition, control the hydrolysis rate of antifouling coat in seawater on demand.Thus, but this anti-fouling effect of boats and ships long term maintenance; In addition,, for example during berthing, assemble rigging etc., almost do not observe the adhesion and the fouling of aquatic fouling organism even when boats and ships are not mobile yet, but and long-term performance go out this anti-fouling effect.

Even the surface of described antifouling coat does not still have cracking substantially or comes off after the long period.Therefore, do not need to form again new filming existing filming after removing fully.Therefore, by thereon directly recoat can effectively form this antifouling coat with described antifouling coat composition.This makes can be easily and continue to keep anti-fouling effect at low cost.

Beneficial effect

Antifouling paint compositions of the present invention can reduce the content of volatile organic compounds in the gained coating (organic solvent etc.).This has reduced when forming the antifouling coat with adequate thickness may be dispersed into airborne organic compound, and has therefore reduced the disadvantageous effect to environment.

The present composition has good storage property for a long time.Particularly, even the present composition also multiviscosisty hardly, gelation or curing after long storage.In addition, antifouling paint compositions of the present invention has very high environmental safety, even and also do not cause pollution of the sea substantially after being dissolved in seawater.

The antifouling coat that uses antifouling paint compositions of the present invention to form has the following advantages.

4) this is filmed and adheres to securely on the object that formation is filmed thereon, makes to be easier to apply on this object.The antifouling coat that coated article body and function of the present invention has above-mentioned 1-4 item feature covers.Therefore, can be on demand to boats and ships (particularly bottom of ship), fish for instrument, be immersed in works in the seawater etc. and apply.For example, when antifouling coat was formed on the surface of bottom of ship, this antifouling coat dissolved gradually from this surface, thereby film coated surface always is updated.This has prevented the adhesion of aquatic fouling organism.

In addition, described antifouling coat has suitable solubility.Therefore, when boats and ships are not mobile, for example in berthing, assemble processes such as rigging, almost do not observe the adhesion and the fouling of aquatic fouling organism yet, but and long-term performance go out this anti-fouling effect.This has reduced the friction resistance of boats and ships, and has correspondingly reduced the fuel cost when navigating by water.

In addition, even also there is paint film defect hardly in the surface of described antifouling coat after the long period.Therefore, the coated article body can be by with the direct recoat of antifouling coat composition on it and form new antifouling coat on demand after using predetermined period.This makes and can a kind of easy and cheap mode continue to keep described anti-fouling effect.

Embodiment

Feature of the present invention is by further illustrating with reference to embodiment shown below etc.But the present invention is not subject to described embodiment etc.

In each preparation embodiment, contrast preparation embodiment, embodiment and comparative examples, " % " expression " weight % ".

The viscosity of multipolymer (A) solution uses Brookfield (Brookfield) viscometer to measure down at 25 ℃.

Non-volatile residue by 125 ℃ down heating 1 hour measure according to JIS K5601-1-2 (or ISO 3251) standard.

Number-average molecular weight (Mn) is measured by gel permeation chromatography (GPC) (use polystyrene standards).

The GPC condition is as follows:

Equipment: HLC-8220GPC; Tosoh Corporation

Post: TSK-gel Super HZM-M, two

Flow velocity: 0.35mL/min

Detector: RI

Post thermostat temperature: 40 ℃

Elutriant: THF

The weight-average molecular weight (Mw) that will record subject to the foregoing by GPC records molecular weight dispersity divided by Mn.

The second-order transition temperature of described multipolymer (Tg) records according to JIS K 7121 standards, use SeikoInstruments SSC/5200 differential scanning calorimeter.

The viscosity of coating composition records under 25 ℃ according to JIS K 5400 standards, use stormer viscosity meter.Measuring condition is as follows:

The stormer viscosity meter: stormer viscosity meter NO.453, by Coating Tester Co., Ltd. makes

Measure temperature: 25 ± 0.5 ℃

Sample size: 500ml (the 500ml sample carrier is filled to graticule with sample)

Weight: 75-1,000g

Measuring method: measure rotor and produce the required time of 100 commentaries on classics.Under the situation that changes weight, measure.In the value in producing required 27-33 scope second of 100 commentaries on classics, select the most close 30 seconds value, and change into KU unit and measure the KU value by the quality of used weight with in required time of generation 100 commentaries on classics of second, use chart.

The amount of each composition shown in the table 1 is represented with g.

Preparation embodiment 1 (preparation of multipolymer (A) solution)

330g dimethylbenzene packed into one is equipped with 1 of thermometer, reflux exchanger, agitator and dropping funnel, in the 000ml flask; Subsequently, the mixing solutions of 150g vinylformic acid triisopropyl silicomethane ester, 150g methyl methacrylate, 50g n-butyl acrylate, 150g methacrylic acid 2-methoxyl group ethyl ester and the 5g Peroxycaprylic acid tert-butyl ester was dropwise added in 3 hours in this flask, stir under nitrogen atmosphere at 115-120 ℃ simultaneously.After dropwise adding, under 115-120 ℃, carried out polyreaction 2 hours.Subsequently the 2g Peroxycaprylic acid tert-butyl ester (other) is added in the gained reaction soln, thereby under 115-120 ℃, makes this polyreaction proceed 2 hours again, make multipolymer (A) solution S-1 thus.Table 1 shows viscosity, non-volatile residue, number-average molecular weight (Mn), molecular weight dispersity (Mw/Mn) and the second-order transition temperature (Tg) of copolymer solution S-1.

Preparation embodiment 2-6 (preparation of multipolymer (A) solution)

Use solvent, monomer and the polymerization starter shown in the table 1, with preparation embodiment 1 in identical step implement polyreaction, thereby make multipolymer (A) solution S-2 to S-6.Table 1 shows viscosity, non-volatile residue, number-average molecular weight (Mn), molecular weight dispersity (Mw/Mn) and the second-order transition temperature (Tg) of each gained copolymer solution.

Contrast preparation embodiment 1 (preparation of copolymer solution H-1)

Use organic solvent, monomer, polymerization starter and the temperature of reaction shown in the table 1, with preparation embodiment 1 in identical step implement polyreaction, thereby make copolymer solution H-1.Table 1 shows viscosity, non-volatile residue, number-average molecular weight (Mn), molecular weight dispersity (Mw/Mn) and the second-order transition temperature (Tg) of gained copolymer solution.

Contrast preparation embodiment 2 (preparation of copolymer solution H-2)

330g dimethylbenzene packed into one is equipped with 1 of thermometer, reflux exchanger, agitator and dropping funnel, in the 000ml flask; Subsequently, the mixing solutions of 150g methacrylic acid triisopropyl silicomethane ester, 150g methyl methacrylate, 50g n-butyl acrylate, 100g n-BMA, 50g methacrylic acid 2-methoxyl group ethyl ester and the 1g Peroxycaprylic acid tert-butyl ester was dropwise added in 2 hours in this flask, stir under nitrogen atmosphere at 90-100 ℃ simultaneously.After dropwise adding, under 90-100 ℃, carried out polyreaction 2 hours.Subsequently the 2g Peroxycaprylic acid tert-butyl ester (other) is added in the gained reaction soln, thereby under 90-100 ℃, makes this polyreaction proceed 2 hours again, make copolymer solution H-2 thus.Table 1 shows viscosity, non-volatile residue, number-average molecular weight (Mn), molecular weight dispersity (Mw/Mn) and the second-order transition temperature (Tg) of copolymer solution H-2.

Table 1-2

Embodiment 1 and 2 and comparative examples 1-5 (preparation of coating composition)

With multipolymer (A) solution S-1 that obtains among the preparation embodiment 1-6 to S-6 (solids content: each about 60%) or the copolymer solution H-1 and the H-2 (solids content: each about 60%) that in contrast preparation embodiment 1 and 2, obtain, as multipolymer, mix with ratio shown in the table 2 (weight %) with following material: as the rosin zinc salt, about 60%) or the xylene solution of staybelite zinc salt (solids content: about 60%) xylene solution of gum resin zinc salt (solids content:; As rosiny, about 60%) or the xylene solution of staybelite (solids content: about 60%) xylene solution of gum resin (solids content:; As Red copper oxide, median size is the Red copper oxide of 3 or 6 μ m; And additionally, listed any organic stain control agent, pigment, additive and solvent in the table 2.Above-mentioned each composition is mixed with small desk laboratory sand mill (using the granulated glass sphere of diameter as 1.5-2.5mm) and disperse, thereby make coating composition.Non-volatile substance content, VOC content, PVC and the dope viscosity of each gained coating composition have been shown in the table 2.

Embodiment 3-8 (preparation of coating composition)

With multipolymer (A) solution S-3 that obtains among the preparation embodiment 3-6 each to S-6, as multipolymer, mix with ratio shown in the table 2 (weight %) with following material: as the rosin zinc salt, about 60%) or the xylene solution of staybelite zinc salt (solids content: about 60%) xylene solution of gum resin zinc salt (solids content:; And additionally, listed any stain control agent, pigment, additive and solvent in the table 2.Above-mentioned each composition is mixed with small desk laboratory sand mill (using the granulated glass sphere of diameter as 1.5-2.5mm) and disperse, and the gained mixture is shifted out.In this mixture, add median size subsequently and be the Red copper oxide of 13 or 19 μ m and slowly stir, thereby make coating composition with stirring rake.Non-volatile substance content, VOC content, PVC and the dope viscosity of each gained coating composition have been shown in the table 2.

Table 2-1

Table 2-2

Experimental example 1 (but sprayability)

Each coating composition that obtains among embodiment 1-8 and the comparative examples 1-5 is sprayed into through on (blast-finished) sheet tin (75x150mm) of ash propel polish, makes the thickness of dry coating can be about 100 μ m.The coating composition that can spray is assessed as " A ", and the coating composition that can not spray is assessed as " B ".

Experimental example 2 (stability test of coating composition)

Each coating composition that obtains among embodiment 1-8 and the comparative examples 1-5 is sealed in the wide-mouth tin can of 100ml and in thermostat container and stored 1 month down, afterwards, measure the viscosity of coating composition with brookfield's viscometer in 40 ℃.

The following assessment of the viscosity of coating composition:

A: the change amount of viscosity is less than 500mPas/25 ℃ (the basic no change of coating composition)

B: the change amount of viscosity is 500-5,000mPas/25 ℃ (viscosity increases slightly)

C: the change amount of viscosity is 5,000-100,000mPas/25 ℃ (viscosity significantly increases)

D: the change of viscosity is too significantly so that can't measure (coating composition changes gel or curing into)

The results are shown in the table 3.

Can see that from table 3 coating composition (comparative examples 2 and 3) that contains the rosin (or rosin derivative) with free carboxy lacks permanent stability.

Experimental example 3 (hardness of film)

Each antifouling paint compositions that obtains among embodiment 1-8 and the comparative examples 1-5 is applied to the thickness that makes dry coating on the transparency glass plate (75x150x1mm) can be about 100 μ m, and following dry 1 day at 40 ℃.Use the pendulum testing machine at 25 ℃ of hardness of film of measuring the gained dry coating.Result's (counts) is shown in Table 3.Be practical purpose, preferred counts is 20-50.

From table 3, can see, use filming of coating composition of the present invention (embodiment 1-8) formation to have suitable hardness.

Experimental example 4 (adhesiveness test of filming)

According to JIS K-5600-5-6 standard, test the adhesivity that each is filmed.Particularly, test according to following method.At first each coating composition that obtains among embodiment 1-8 and the comparative examples 1-5 is applied to (75x150x2mm) and make the thickness of dry coating can be about 100 μ m on the sheet tin (75x150x2mm) through the fiber-reinforced plastic plate (FRP plate) of ash propel polish.Then with the coating that applies 40 ℃ of dryings 1 day, thereby make the dry coating of the about 100 μ m of thickness.On this dry coating (2x2mm, grid number=100 in the cross hatch), carry out adhesiveness test.

To the following assessment of adhesivity:

A: the grid number that does not come off is 70-100

B: the grid number that does not come off is 40-69

C: the grid number that does not come off is 20-39

D: the grid number that does not come off is 0-19

The results are shown in the table 3.

From table 3, can see, use filming of coating composition of the present invention (embodiment 1-8) formation to adhere to securely on described FRP plate and the sheet tin.

Experimental example 5 (flexibility test of filming)

Each coating composition that obtains among embodiment 1-8 and the comparative examples 1-5 is applied to through making the thickness of dry coating can be about 100 μ m on the sheet tin (75x150mm) of ash propel polish.Then with coated coating 40 ℃ of dryings 1 day, thereby make the dry coating of the about 100 μ m of thickness.This is scribbled crooked 90 ° of the sheet tin of dry coating, and the state of filming that visual inspection should bending.

Flexible following assessment:

A: basic flawless

B: contain minute crack

C: contain big crackle

D: a part is filmed and is easily come off

The results are shown in the table 3.

From table 3, can see the firm and anti-embrittlement of filming of using coating composition of the present invention (embodiment 1-8) to form.

Experimental example 6 (water tolerance test of filming)

By a kind of protective system (a kind of A/C based on vinyl) is applied on the mat glass plate (75x150x1mm), make its dried thickness can be about 50 μ m, then it is carried out drying, thereby form a kind of anticorrosive coating film.Subsequently each coating composition that obtains among embodiment 1-8 and the comparative examples 1-5 is applied on the described anticorrosive coating film, thereby makes the thickness of dry coating can be about 100 μ m.With the coating of this coating 40 ℃ of dryings 1 day, thereby make the sample that dry coating thickness is about 100 μ m.With this sample dipping 3 months under 35 ℃, in the natural sea-water, this situation of filming afterwards by visual inspection.

The following assessment of water tolerance:

A: filming does not change

B: the color of filming changes a little

C: the slight foaming of filming

D: in filming, observe defective for example crackle, expand and come off

The results are shown in the table 3.

From table 3, can see, use filming of coating composition of the present invention (embodiment 1-8) formation to have good water tolerance.

Table 3

Experimental example 7 (the solubility test (whirl test) of filming)

Be 515mm and highly be the rotary drum of 440mm at diameter of the center of jar assembling, this rotary drum is rotated by engine.This jar also has one and keeps seawater temperature constant refrigerating unit and a maintenance seawater pH constant pH two-position controller.

According to two test boards of following method preparation.

By a kind of protective system (a kind of A/C based on vinyl) is applied on the hard vinyl chloride sheet (75x150x1mm), make its dried thickness can be about 50 μ m, then carry out drying, thereby form a kind of anticorrosive coating film.Each antifouling paint compositions that obtains among embodiment 1-8 and the comparative examples 1-5 is applied on the described anticorrosive coating film, makes its dried thickness can be about 300 μ m.With the coating of this coating 40 ℃ of dryings 3 days, thereby make the test board of dry coating with about 300 μ m thickness.

One of the test board of preparation thus is fixed on the rotary drum of swivel arrangement in aforesaid device so that this test board contact seawater, and makes the speed rotation of rotary drum with 20 joints.In the process of the test, seawater temperature remains on 25 ℃, and pH remains on 8.0-8.2; Seawater is changed once weekly.

Use laser focusing displacement gauge (laser focus displacement gauge) that the initial coating thickness and the residue coating thickness after 1 month, 3 months and 6 months of each test board are measured; And by initial coating thickness and residue the difference between the coating thickness is calculated the thickness that institute's dissolved is filmed, thereby record in initial 6 amounts that the middle of the month, institute's dissolved was filmed.

The meltage of filming is according to total meltage (μ m) expression of filming during this period.The results are shown in the table 4.

Can see that from table 4 use filming of coating composition of the present invention (embodiment 1-8) formation to begin promptly to dissolve with enough big amount from the initial stage, this shows, the initial stage anti-fouling effect that these are filmed and can provide good.

Can see, use the initial stage of filming of the coating composition formation of comparative examples 1-5 not to be soluble in seawater and not demonstrate effective anti-fouling effect.Think that the filming of coating composition formation of using comparative examples 2 and 3 has lower water tolerance, thereby take place to ftracture and/or come off at test period.

Table 4

Experimental example 8 (foundry loam adhiesion test)

Each coating composition that obtains among embodiment 1-8 and the comparative examples 1-5 is applied on two surfaces of hard vinyl chloride sheet (100x200x2mm), makes the thickness of dry coating can be about 100 μ m.The coating of this coating is descended dry 3 days in room temperature (25 ℃), thereby make the test board that dry coating thickness is about 100 μ m.This test board is immersed in the place of 1.5m below sea level of Wakayama Prefecture, Japan string this city.Behind dipping 1 month, 2 months and 3 months, the visual inspection foundry loam is to the adhesion of test board.

The results are shown in the table 5.

The degree of adhesion of the digitized representation foundry loam in the table 5.The following assessment of the degree of adhesion of foundry loam:

0: do not observe foundry loam substantially.

1: a small amount of foundry loam adheres on the test board.

2: foundry loam adheres to the whole surface of test board than heavy back, but is easy to remove with brush.

3: foundry loam adheres to the whole surface of test board than heavy back, and is difficult for removing with brush.

From table 5, can see, compare, use filming of coating composition of the present invention (embodiment 1-8) formation not have foundry loam substantially and adhere to the filming of coating composition formation of using comparative examples 1-5.This is because filming of using that coating composition of the present invention forms can fully be dissolved since the initial stage.

Experimental example 9 (recoating test)

Each test board that will carry out the foundry loam adherence test of experimental example 8 washs by pouring into a mould ion exchanged water thereon, and descends dry 1 day in room temperature (25 ℃).Each coating composition that obtains among embodiment 1-8 and the comparative examples 1-5 is applied on the surface of test board subsequently, makes the thickness of dry coating can be about 100 μ m.The coating of this coating is descended dry 3 days in room temperature (25 ℃), and formation thickness is the test board of newly filming of about 100 μ m on its old coating film thereby make.On this test board, measure the adhering test of filming (2x2mm, grid number=100 in the cross hatch) according to JIS K-5600-5-6.

To the following assessment of adhesivity:

A: the grid number that does not come off is 70-100.

B: the grid number that does not come off is 40-69.

C: the grid number that does not come off is 20-39.

D: the grid number that does not come off is 0-19.

The results are shown in the table 5.

From table 5, can see, compare, the demonstration of filming of using coating composition of the present invention (embodiment 1-8) to form the enough adhesivityes of filming that make new advances old coating film with filming of forming of the coating composition that uses comparative examples 1-5.This is because use the filming of coating composition formation of comparative examples 1-5 to have the relatively poor solubility of initially filming, and causes taking place in the short period of time foundry loam to these adhesions of filming.Comparatively speaking, use filming of coating composition formation of the present invention to demonstrate the sufficiently high solubility of initially filming, make film coated surface be updated, cause foundry loam to adhere to hardly.

Table 5

Experimental example 10 (antifouling test)

Each coating composition that obtains among embodiment 1-8 and the comparative examples 1-5 is applied to hard vinyl chloride sheet (100x200x2mm) thus two surfaces on make the thickness of dry coating can be about 200 μ m.The coating of this coating is descended dry 3 days in room temperature (25 ℃), thereby make the test board that dry coating thickness is about 200 μ m.This test board is immersed in the place of 1.5m below sea level in owase city, Mie Prefecture, Japan, and the stained situation to this test board detects in 24 months.

The results are shown in the table 6.

Digitized representation fouling organism adherent area (%) in the table 6.

Can see from table 6, compare that the substantially anhydrous living fouling organism of filming that uses coating composition of the present invention (embodiment 1-8) to form adheres to the filming of coating composition formation of using comparative examples 1-5.This is because use filming of coating composition formation of the present invention to demonstrate the hydrolysis rate that reduces a little, makes them stablize dissolving with constant rate of speed in the long term.

Table 6

Claims

1. antifouling paint compositions, it contains:

This antifouling paint compositions

(1) has 45/55 to 10/90 polymkeric substance (A) content and the weight ratio ((A)/(B)) of zinc salt (B) content;

2. the antifouling paint compositions of claim 1, wherein the number-average molecular weight of polymkeric substance (A) is 2,000-15,000 and molecular weight dispersity less than 2.5.

3. claim 1 or 2 antifouling paint compositions, wherein the second-order transition temperature of polymkeric substance (A) is 20-70 ℃.

4. the antifouling paint compositions of claim 1, wherein polymkeric substance (A) is (methyl) vinylformic acid triisopropyl silicomethane ester copolymer.

5. the methyl methacrylate of (methyl) vinylformic acid triisopropyl silicomethane ester by copolymerization (a) 30-60 weight % of the antifouling paint compositions of claim 3, wherein said (methyl) vinylformic acid triisopropyl silicomethane ester copolymer, (b) 10-50 weight % and (c) the removing of 0-60 weight % (a) and (b) (methyl) acrylate middle the definition obtain.

6. the antifouling paint compositions of claim 1, wherein said rosin zinc salt is at least a zinc salt that is selected from gum resin zinc salt, wood rosin zinc salt and starex zinc salt, and described rosin derivative zinc salt is at least a zinc salt that is selected from staybelite zinc salt and nilox resin zinc salt.

7. the antifouling paint compositions of claim 1, wherein said non-volatile substance content is not less than 80 weight % and uses the stormer viscosity meter to be 80-100KU 25 ℃ of viscosity that record.

8. the antifouling paint compositions of claim 1, wherein said content of volatile organic compound is less than 400g/L.

9. the antifouling paint compositions of claim 1, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains the 10-100 part by weight of zinc oxide.

10. the antifouling paint compositions of claim 1, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains 100-400 weight part Red copper oxide.

11. the antifouling paint compositions of claim 10, the median size of wherein said Red copper oxide are 8-20 μ m.

12. the antifouling paint compositions of claim 1, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains the organic stain control agent of 1-100 weight part.

13. the antifouling paint compositions of claim 1, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains 1-50 weight part softening agent.

14. the antifouling paint compositions of claim 13, wherein said softening agent are a kind of epoxidized oil lipid.

15. the antifouling paint compositions of claim 1, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains 1-50 weight part dewatering agent.

16. the antifouling paint compositions of claim 15, wherein said dewatering agent are at least a waterbinding agent that is selected from alkoxyl silicone alkanes and alkyl orthoformate.

17. the antifouling paint compositions of claim 1, with respect to the total amount of per 100 parts by weight polymer (A) and zinc salt (B), said composition also contains 1-50 weight part fatty acid acyl amine dispersion agent.

18. the anti-fouling treatment method that the antifouling paint compositions that uses among the claim 1-17 each is implemented, this method are included in the step that the surface of waiting to be coated with thing forms antifouling coat.

19. one kind by using the antifouling coat that each antifouling paint compositions forms among the claim 1-17.

20. a surface has the coated thing of the antifouling coat of claim 19.

21. a method for preparing antifouling paint compositions, this method may further comprise the steps:

Described antifouling paint compositions

(1) has the weight ratio ((A)/(B)) of the content of 45/55 to 10/90 polymkeric substance (A) content and zinc salt (B);

22. the method for preparing antifouling paint compositions of claim 21, this method may further comprise the steps:

Polymkeric substance (A) is mixed with zinc salt (B);

The use decollator mixes the mixture that obtains and disperses.

23. the method for preparing antifouling paint compositions of claim 21, this method may further comprise the steps:

Polymkeric substance (A) is mixed with zinc salt (B);

Use decollator that this mixture is disperseed simultaneously at blended; With

Adding median size is the Red copper oxide of 10-20 μ m and mixes.