JP6487159B2 - Antifouling paint composition, antifouling film, method for producing antifouling film and antifouling substrate - Google Patents

Description

  The present invention relates to an antifouling coating composition that can form an antifouling film that imparts excellent antifouling performance and that can ensure sufficient pot life.

  An antifouling coating film formed from an organopolysiloxane antifouling coating composition is widely used for preventing adhesion of aquatic organisms to ships, underwater structures, fishing nets, fishing gears and the like. A coating film formed from an organopolysiloxane antifouling coating composition prevents adhesion and fixation of macro organisms such as barnacles and mussels due to its characteristics such as low surface free energy and low elastic modulus. Furthermore, high antifouling performance is also required for micro-organisms, such as prevention of adhesion of slime, which is a coating of bacterial secretions. In order to meet such demand, a method of adding an antifouling agent such as cuprous oxide having physiological activity to the antifouling coating composition has been studied.

  However, while the antifouling component exhibits effective physiological activity, it has high reactivity with main components such as resin, crosslinking agent, curing catalyst and additive of the organopolysiloxane antifouling coating composition. Due to the adverse effects on the above, there has been a problem that there are many cases where there are many restrictions in practical use. As one example, organopolysiloxane antifouling coating compositions are required to have a metal curing catalyst, catalytic activity, and catalytic activity in order to ensure quick drying of the coating film required for construction in the relevant field and the pot life after coating preparation. In general, it is used in combination with a β-diketone compound as a conditioner, but cuprous oxide useful as an antifouling agent in an antifouling coating composition containing a metal curing catalyst and a β-diketone compound, etc. When the metal oxide is added, there arises a problem that the pot life after the preparation of the paint is shortened due to the high reactivity between the metal oxide and the β-diketone compound.

  Patent Document 1 describes a silicone coating system containing a biocide selected from organopolysiloxanes and 3-isothiozolones. This coating system consists essentially of two layers: an adhesive layer containing a biocide selected from 3-isothiozolones and a release layer consisting of an organopolysiloxane coating that may or may not contain a biocide. It is a required lamination system. However, when 3-isothiozolones are added to the organopolysiloxane coating composition, surface abnormalities and poor adhesion due to 3-isothiozolones actually occur during the coating formation process. There is a problem that is difficult.

  Patent Document 2 describes an adhesion-suppressing coating composition containing a binder system based on polysiloxane, a hydrophilic-modified polysiloxane, and a biocide. All of the coating compositions contain a tin-containing curing catalyst and 2,4-pentanedione, and a metal oxide cannot be added thereto.

  In Patent Document 3, (A) polydimethylsiloxane having an alkoxysilyl group at the terminal, (B) a partial hydrolysis-condensation product of alkoxysilane, (C) an organotitanium catalyst, (D) an aliphatic hydrocarbon solvent or A silicone composition for water-repellent coating comprising an ester solvent and (E) an alcohol solvent is described.

  Patent Document 4 includes (A) an organopolysiloxane having an alkoxy group and a polyoxyethylene chain, (B) a silicone resin having a silanol group or an alkoxysilyl group at its terminal, (C) a condensation reaction promoting catalyst, and (D) an alcohol. A coating composition containing a diluent having a flash point of 20 ° C. or higher, comprising a solvent selected from benzene, ketone, and ether is described.

  Patent Document 5 discloses (A) a solution obtained by dissolving a diorganopolysiloxane having a hydroxyl group or a hydrolyzable group, (B) an amine having a melting point of 30 ° C. or higher in an organic solvent such as alcohols, and (C) cross-linking. A room temperature curable organopolysiloxane composition containing an agent, (D) a curing catalyst is described.

  Patent Document 6 describes a hydrophobic surface treatment composition comprising a silicone oil containing polysiloxane or the like and a solvent containing alcohol or the like. The composition described in this document does not show a composition having sufficient performance for marine antifouling applications.

Although the compositions described in Patent Documents 3 to 6 have advantages such as good quick-drying property and storage stability, they are expected to exhibit a high level of antifouling properties required for marine antifouling applications. Can not.
Patent Document 7 discloses (A) highly branched organopolysiloxane (silicone resin), (B) alcohol solvent, (C) hydrocarbon solvent and / or dimethyl silicone, (D) alkoxysilane and / or silane cup. A silicone resin composition for water-repellent coating comprising a ring agent and (E) a catalyst for condensation reaction is described. The coating film formed from the silicone resin composition as described in this document does not have rubber elasticity suitable for marine antifouling applications.

Japanese National Patent Publication No. 10-501272 Special table 2013-515122 gazette JP 2002-356651 A JP 2004-256586 A JP 2008-81663 A JP-T-2006-502837 JP 2007-8967 A

  The present invention is to solve the problems associated with the prior art, and to form an antifouling film having a high antifouling property by blending a metal oxide antifouling agent such as cuprous oxide. It is an object of the present invention to provide an organopolysiloxane antifouling paint composition which can be used and has good curability and pot life.

As a result of intensive studies to solve the above-mentioned problems, the present inventor,
(A) an organopolysiloxane having two or more silanol groups in one molecule;
(B) Organosilane having two or more hydrolyzable groups in one molecule and / or a partial hydrolysis condensate thereof,
(C) a metal curing catalyst,
(D) an oxide of copper or zinc,
(E) alcohol,
And (E) the content ratio of alcohol is 1 to 20% by weight, by using an antifouling paint composition, it is found that an unexpectedly high effect can be obtained and the above-mentioned object can be achieved. The present invention has been completed.

Cuprous oxide is preferred as the copper or zinc oxide (D) contained in the antifouling coating composition.
The alcohol (E) contained in the antifouling coating composition is preferably an alcohol having 5 or less carbon atoms, more preferably N-butanol.

As the metal curing catalyst (C) contained in the antifouling coating composition, a tin curing catalyst is preferable.
The organopolysiloxane (A) having two or more silanol groups in one molecule contained in the antifouling coating composition is preferably one represented by the following general formula [I].

（式中、Ｒ²はそれぞれ独立に、水素原子または炭素原子数１〜１０のアルキル基、アルケニル基、アリール基、アラルキル基、アルコキシ基もしくはハロゲン化アルキル基を示し、
ｒは１〜３の整数であり、
ｓは１０〜１０，０００の整数である。）
上記防汚塗料組成物はさらに、（Ｆ）下記一般式［ＩＩ］で表される（Ａ）以外のオルガノポリシロキサンを含有することが好ましい。

(In the formula, each R ² independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group or a halogenated alkyl group;
r is an integer of 1 to 3,
s is an integer of 10 to 10,000. )
The antifouling coating composition preferably further contains (F) an organopolysiloxane other than (A) represented by the following general formula [II].

（式中、Ｒ³はそれぞれ独立に、炭素原子数１〜１０のアルキル基、アルケニル基、アリール基、アラルキル基、アルコキシ基もしくはハロゲン化アルキル基；または末端が炭素数１〜１０の炭化水素基、水酸基もしくは縮合反応性基をケイ素上にもつシリル基により封止されていてもよい炭素原子数２〜１００のポリオキシアルキレン基であり、ｕは１〜１０，０００の整数である。）

(In the formula, each R ³ independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group or a halogenated alkyl group; or a hydrocarbon group having 1 to 10 carbon atoms at the end. And a polyoxyalkylene group having 2 to 100 carbon atoms which may be sealed with a silyl group having a hydroxyl group or a condensation reactive group on silicon, and u is an integer of 1 to 10,000.)

The antifouling coating composition preferably further contains an antifouling agent other than the component (G) (G).
A kit for preparing the antifouling paint composition, comprising: (A) a main agent component containing an organopolysiloxane and (C) a curing agent component containing a metal curing catalyst. Kits can be provided.

The antifouling film according to the present invention is characterized by curing the antifouling coating composition.
The method of manufacturing an antifouling film according to the present invention is characterized in that the antifouling film is obtained by applying the antifouling coating composition.

The antifouling substrate according to the present invention is characterized in that the substrate is coated with the above antifouling film.
It is preferable that the base material is any one of a ship, an underwater structure, and a fishing gear.
The antifouling method for a substrate according to the present invention is characterized in that the substrate is coated with the antifouling film.

  The method for producing an antifouling substrate according to the present invention comprises a step of applying or impregnating the antifouling coating composition to a substrate, and the antifouling coating composition applied or impregnated on the substrate by the step Or a step of forming a coating film from the antifouling coating composition, curing the coating film to form an antifouling film for application, and applying the antifouling film to a substrate. And a step of performing.

According to the present invention, an organopolysiloxane antifouling coating composition which can form an antifouling film having a high antifouling property and has good curability and pot life can be obtained.
The antifouling coating composition of the present invention is excellent in curability and has a quick drying property required for construction on a substrate for underwater antifouling use. In addition, the antifouling paint composition of the present invention does not use a β-diketone compound having high reactivity with copper or zinc oxide as a catalyst activity regulator, but instead uses alcohol. While maintaining the antifouling function due to the oxide of copper or zinc, the workability after preparation of the composition that tends to conflict with high curability can be ensured for a long time, so that the workability is excellent.

Furthermore, since the antifouling paint composition of the present invention does not contain a diketone compound that is used for general purposes, there is an effect that the packaging can not corrode during storage and the odor during coating can be reduced.
Furthermore, since the antifouling paint composition of the present invention uses copper or zinc oxide as an antifouling agent, the antifouling agent is less altered in the sea than a composition using an organic antifouling agent, An antifouling film that exhibits high antifouling properties for a long period of time can be obtained.

-Antifouling paint composition-
Antifouling paint composition according to the present invention,
(A) an organopolysiloxane having two or more silanol groups in one molecule;
(B) Organosilane having two or more hydrolyzable groups in one molecule and / or a partial hydrolysis condensate thereof,
(C) a metal curing catalyst,
(D) an oxide of copper or zinc,
(E) alcohol,
(E) The content ratio of the alcohol is 1 to 20% by weight.

Hereinafter, each component will be described in order.
<(A) Organopolysiloxane having two or more silanol groups in one molecule>
Specifically, the organopolysiloxane (A) having two or more silanol groups in one molecule is preferably a compound represented by the following general formula [I].

上記一般式［Ｉ］中、Ｒ²はそれぞれ独立に、水素原子または炭素原子数１〜１０のアルキル基、アルケニル基、アリール基、アラルキル基、アルコキシ基もしくはハロゲン化アルキル基である。

In the general formula [I], each R ² independently represents a hydrogen atom or an alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group or halogenated alkyl group having 1 to 10 carbon atoms.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.
Examples of the alkenyl group include a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, heptenyl group, hexenyl group, and cyclohexenyl group.

Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
Examples of the aralkyl group include benzyl group, 2-phenylethyl group, 2-naphthylethyl group, diphenylmethyl group and the like.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, and an ethoxyethoxy group.
Examples of the halogenated alkyl group include groups formed by substituting part or all of the hydrogen atoms contained in the alkyl group with halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom.

R ² is preferably a methyl group.
In said general formula [I], r is an integer of 1-3, Preferably it is 1.
In the above general formula [I], s is an integer of 10 to 10,000, preferably 100 to 1,000.

  The organopolysiloxane (A) having two or more silanol groups in one molecule preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of 500 to 1,000,000. Preferably it is 5,000-100,000, More preferably, it is 10,000-50,000. The viscosity at 23 ° C. is preferably 20 to 100,000 mPa · s, more preferably 100 to 10,000 mPa · s, and still more preferably 500 to 5,000 mPa · s. When the weight average molecular weight and the viscosity are in this range, it is preferable in terms of excellent manufacturing workability of the antifouling coating composition, spray atomization property, coating film curability, and strength of the formed coating film.

  The organopolysiloxane (A) having two or more silanol groups in one molecule is usually contained in the antifouling coating composition in an amount of 20 to 90% by weight, preferably 50 to 70% by weight. The organopolysiloxane (A) is usually contained in an amount of 30 to 95% by weight, preferably 60 to 90% by weight, based on the weight of the solid content contained in the antifouling coating composition. When the content of the organopolysiloxane (A) is within this range, a coating film exhibiting good coating strength and rubber elasticity can be formed, and an antifouling film exhibiting antifouling properties for a long time can be obtained. Can do.

  As the organopolysiloxane (A) having two or more silanol groups in one molecule, commercially available ones can be used. For example, “DMS-S35” (product of GELEST) can be used.

<(B) Organosilane having two or more hydrolyzable groups in one molecule and / or a partially hydrolyzed condensate thereof>
The organosilane having two or more hydrolyzable groups in one molecule is preferably a compound represented by the following general formula [III]. The partially hydrolyzed condensate of organosilane having two or more hydrolyzable groups in one molecule is preferably a partially hydrolyzed condensate of a compound represented by the following general formula [III].

上記一般式［ＩＩＩ］中、Ｒ⁴は独立に炭素原子数１〜６の炭化水素基を示し、例えばメチル基、エチル基、プロピル基などの直鎖状もしくは分枝状アルキル基、シクロヘキシル基などの環状アルキル基、ビニル基などのアルケニル基、またはフェニル基などのアリール基であり、好ましくはメチル基、エチル基である。

In the general formula [III], R ⁴ independently represents a hydrocarbon group having 1 to 6 carbon atoms, such as a linear or branched alkyl group such as a methyl group, an ethyl group, or a propyl group, a cyclohexyl group, or the like. A cyclic alkyl group, an alkenyl group such as a vinyl group, or an aryl group such as a phenyl group, preferably a methyl group or an ethyl group.

  In the above general formula [III], Y is independently a hydrolyzable group, for example, an alkoxy group, an oxime group, an acetyloxy group, an acyloxy group, an alkenyloxy group, an iminoxy group, an amino group, an amide group, an aminooxy group. Group, etc. are mentioned, Preferably it is an alkoxy group or an oxime group.

  As the alkoxy group, those having 1 to 10 carbon atoms are preferable, and an oxygen atom may be interposed at one or more positions between carbon atoms. For example, methoxy group, ethoxy group, propoxy group, butoxy group, A methoxyethoxy group, an ethoxyethoxy group, etc. are mentioned.

  As the oxime group, those having 1 to 10 carbon atoms are preferable, and examples thereof include dimethyl ketoxime, methyl ethyl ketoxime, diethyl ketoxime, and methyl isopropyl ketoxime.

  The acetyloxy group is preferably an aliphatic group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms, such as an acetoxy group, a propyloxy group, a butyloxy group, and a benzoyloxy group. Can be mentioned.

  As the acyloxy group, an aliphatic or aromatic group represented by the formula: RCOO— (wherein R is an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms) is preferable. , Acetoxy group, propionoxy group, butyroxy group, benzoyloxy group and the like.

  The alkenyloxy group is preferably one having 3 to 10 carbon atoms, and examples thereof include an isopropenyloxy group, an isobutenyloxy group, and a 1-ethyl-2-methylvinyloxy group.

  As the iminoxy group (= N—OH; also referred to as oxyimino group or ketoxime group), those having about 3 to 10 carbon atoms are preferable. A cyclopentanoxime group, a cyclohexanoxime group, etc. are mentioned.

  As the amino group, those having 1 to 10 carbon atoms are preferable. For example, N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N , N-diethylamino group, cyclohexylamino group and the like.

The amide group preferably has 2 to 10 carbon atoms in total, and examples thereof include an N-methylacetamide group, an N-ethylacetamide group, and an N-methylbenzamide group.
As the aminooxy group, those having 2 to 10 carbon atoms are preferable, and examples thereof include N, N-dimethylaminooxy group, N, N-diethylaminooxy group and the like.

d is an integer of 0-2, and 0 is preferable.
As such organosilane and its partial hydrolysis condensate, commercially available products can be used. For example, “ethyl silicate 28” (manufactured by Colcoat Co.), “ethyl silicate” (manufactured by Tama Chemical Industry Co., Ltd.) as tetraethyl orthosilicate, and “silicate 40” (Tama as a partial hydrolysis condensate of tetraethyl orthosilicate). Chemical Industry Co., Ltd.), “TES40 WN” (Asahi Kasei Wacker Silicone Co., Ltd.), and alkyltrialkoxysilane include “KBM-13” (Shin-Etsu Chemical Co., Ltd.).

  The organosilane having two or more hydrolyzable groups in one molecule and / or its partially hydrolyzed condensate (B) is generally 0.1 to 50% by weight in the antifouling coating composition. In general, it is contained in an amount of 1 to 30% by weight, preferably 3 to 15% by weight. When the content of the component (B) is within this range, the curing rate of the antifouling coating composition can be appropriately maintained, and the antifouling film obtained by curing exhibits excellent strength and rubber physical properties. Can do.

<(C) Metal curing catalyst>
The metal curing catalyst (C) is an organopolysiloxane (A) having two or more silanol groups in one molecule, an organosilane having two or more hydrolyzable groups in one molecule and / or a partial hydrolysis condensate thereof. It is a catalyst for accelerating each condensation reaction of (B) or the condensation reaction of the component (A) and the component (B), and accelerates the curing reaction of the coating film so that a cured film can be obtained sooner after coating. Like that.

The metal curing catalyst (C) is preferably a tin curing catalyst.
As the metal curing catalyst (C), for example, those described in JP-A-4-106156 (Patent No. 2522854) can be suitably used. Specifically, tin carboxylates such as tin naphthenate and tin oleate; dibutyltin diacetate, dibutyltin acetoacetonate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentoate, Dibutyltin dioctoate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, bis (dibutyltin laurate) oxide, dibutylbis (triethoxysiloxy) tin, bis (dibutyltin acetate) oxide, dibutyltin bis (ethylmalate) and Tin compounds such as dioctyltin bis (ethyl malate); tetraisopropoxy titanium, tetra-N-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetonato) Titanic acid esters or titanium chelate compounds such as titanium and titanium isopropoxyoctyl glycol; zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexoate, cobalt-2-ethylhexo Organic metal compounds such as ate, manganese-2-ethylhexoate, cobalt naphthenate, and alkoxyaluminum compounds; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, and lithium oxalate.

A commercially available metal curing catalyst (C) can be used. For example, “NEOSTAN U-100” (manufactured by Nitto Kasei Co., Ltd.) can be used.
The content of the metal curing catalyst (C) is usually 10% by weight or less, preferably 1% by weight or less in the antifouling coating composition, and the lower limit when using the catalyst is preferably 0.00. It is 001% by weight, particularly preferably 0.01% by weight. When the content of the metal curing catalyst (C) is within this range, an antifouling coating composition having a good balance between the coating film curing rate and the pot life after preparation of the composition is obtained.

<(D) Copper or zinc oxide>
Copper or zinc oxide (D) is a component that improves the antifouling property of the antifouling film obtained from the antifouling coating composition. The copper or zinc oxide (D) is preferably cuprous oxide or zinc oxide, and more preferably cuprous oxide. Further, cuprous oxide and zinc oxide may be used in combination.

  A commercially available cuprous oxide can be used. For example, “RedCopp97N Premium”, “LOLO TINT 97” (manufactured by American Chemette Corporation), “cuprous oxide NC-803” (manufactured by Nisshin Chemco Co., Ltd.) and the like can be mentioned.

  The content of the copper or zinc oxide (D) is usually 1 to 60% by weight, preferably 3 to 40% by weight in the antifouling coating composition. When the content of the copper or zinc oxide (D) is within this range, a high antifouling property can be imparted to the antifouling film formed from the present composition.

<(E) Alcohol>
Alcohol (E) is a component used as a substitute for the β-diketone compound that is generally used as a catalyst activity modifier for the metal curing catalyst in the antifouling coating composition of the present invention. As described above, when a metal oxide such as copper or zinc oxide is added as an antifouling agent to an antifouling coating composition containing a metal curing catalyst and a β-diketone compound such as acetylacetone, the metal oxide and β- Due to the high reactivity with the diketone compound, there arises a problem that the pot life after preparation of the paint is shortened. In the antifouling coating composition of the present invention, by containing alcohol (E) as an alternative to the β-diketone compound, the reaction with the metal oxide is suppressed while maintaining the catalytic activity adjustment function for the metal curing catalyst. As a result, the pot life after the preparation of the paint can be sufficiently secured.

  Examples of the alcohol (E) include linear, branched, and cyclic alcohols in which an ether group may be included in the chain, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and propylene glycol. Examples thereof include monomethyl ether.

  As the alcohol (E), an alcohol having 5 or less carbon atoms is preferable, and N-butanol is particularly preferable. When the alcohol (E) is an alcohol having 5 or less carbon atoms, particularly N-butanol, a long time can be easily obtained as the pot life after mixing the paint.

  Content of alcohol (E) is 1-20 weight% in an antifouling coating composition, Preferably it is 3-10 weight%, More preferably, it is 4-8 weight%. The above effect of the present invention can be obtained if the antifouling paint composition contains alcohol (E). However, if the content of alcohol (E) is 1% by weight or more, it is particularly possible after mixing the paint. A long time can be easily obtained. Moreover, when content of alcohol (E) exceeds 20 weight%, it will become difficult to obtain sufficient sagging prevention property by the excessive fall of the viscosity of an antifouling coating composition.

<Optional component>
The antifouling coating composition according to the present invention comprises an organopolysiloxane (A) having two or more silanol groups in one molecule, an organosilane having two or more hydrolyzable groups in one molecule and / or a partial hydrolysis thereof. In addition to decomposition condensate (B), metal curing catalyst (C), copper or zinc oxide (D), alcohol (E), organopolysiloxane (F) other than organopolysiloxane (A), component (D Antifouling agent (G), silica (H), filler (I), organic solvent (J) other than alcohol (E), anti-sagging, anti-settling agent (K), silane coupling agent (L) , Other coating film forming component (M), inorganic dehydrating agent (N), flame retardant (O), thixotropy imparting agent (P), heat conduction improving agent (Q) and the like may be contained.

[(F) Organopolysiloxane other than organopolysiloxane (A)]
The organopolysiloxane (F) other than the organopolysiloxane (A) is preferably represented by the following general formula [II].

上記一般式［ＩＩ］中、Ｒ³はそれぞれ独立に、炭素原子数１〜１０のアルキル基、アルケニル基、アリール基、アラルキル基、アルコキシ基もしくはハロゲン化アルキル基；または、末端が炭素数１〜１０の炭化水素基、水酸基または縮合反応性基をケイ素上にもつシリル基により封止されていてもよい炭素原子数２〜１００のポリオキシアルキレン基であり、メチル基およびフェニル基、またはメチル基およびポリオキシアルキレン基であることが好ましい。

In the above general formula [II], each R ³ is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group or a halogenated alkyl group; A polyoxyalkylene group having 2 to 100 carbon atoms which may be sealed with a silyl group having 10 hydrocarbon groups, hydroxyl groups or condensation-reactive groups on silicon, a methyl group and a phenyl group, or a methyl group And a polyoxyalkylene group is preferred.

The alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group or halogenated alkyl group is the same as these groups in the general formula [I].
In the polyoxyalkylene group having 2 to 100 carbon atoms, the terminal may be sealed with a silyl group having a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a condensation reactive group on silicon, the carbon number The hydrocarbon group, hydroxyl group or condensation reactive group of 1 to 10 is preferably the hydrolyzable group shown in the general formula [III], more preferably an oxime group. The number of carbon atoms of the polyoxyalkylene group is preferably 12-30, and more preferably 15-21.

In the general formula [II], u is an integer of 1 to 10,000.
Examples of the organopolysiloxane (F) in which R ³ is a methyl group or a phenyl group in the general formula [II] include, for example, “KF-54”, “KF-56”, “KF-50” (Shin-Etsu Chemical Co., Ltd.). (Manufactured by Co., Ltd.), “SH510”, “SH550” (manufactured by Toray Dow Corning Co., Ltd.), “TSF431” (manufactured by Toshiba Silicone Co., Ltd.), and the like.

In the above general formula [II], as the organopolysiloxane (F) in which R ³ is a methyl group and a polyoxyalkylene group, “FZ-2191” (alkylene glycol-modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.), “FZ-2101” (alkylene glycol-modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.), “X-22-4272” (terminal hydroxyl group blocking / alkylene glycol-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.), “ BY16-839 "(alicyclic epoxy-modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.) can be used.

  The content of the organopolysiloxane (F) is usually 0.01 to 30% by weight, preferably 0.1 to 15% by weight in the antifouling coating composition. When the content of the organopolysiloxane (F) is within this range, it is possible to improve sagging resistance by appropriately improving the thixotropy of the antifouling coating composition and to enable thick film coating. The antifouling performance of the antifouling film can be improved.

[An antifouling agent other than (G) component (D)]
The antifouling agent (G) other than the component (D) may be either organic or inorganic.
Examples of organic antifouling agents include pyrithione salt compounds represented by the following general formula [IV], tetramethylthiuram disulfide, and carbamate compounds (eg, zinc dimethyldithiocarbamate, manganese-2ethylenebisdithiocarbamate). 2,4,5,6-tetrachloroisophthalonitrile, 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole, (RS) -4- [1- (2,3- Dimethylphenyl) ethyl] -3H-imidazole, 4,5-dichloro-N-octyl-4-isothiazolin-3-one, pyridinetriphenylborane, p-isopropylpyridinemethyldiphenylborane, and the like. It is preferable that the pyrithione salt compound represented by this is included.

上記一般式［ＩＶ］中、Ｒ³はそれぞれ独立に水素原子、または炭素原子数１〜６のアルキル基、環状アルキル基、アルケニル基、アリール基、アルコキシ基もしくはハロゲン化アルキル基を示し、ＭはＺｎ、Ｃｕ、Ｎａ、Ｍｇ、Ｃａ、Ｂａ、Ｆｅ、またはＳｒの金属原子を示し、ｎは金属Ｍの価数である。

In the general formula [IV], each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group, an alkenyl group, an aryl group, an alkoxy group or a halogenated alkyl group, and M represents Zn, Cu, Na, Mg, Ca, Ba, Fe, or Sr represents a metal atom, and n represents the valence of the metal M.

A conventionally well-known thing can be used as an inorganic type antifouling agent, However, Among these, copper and copper thiocyanate are preferable.
One type of antifouling agent (G) may be used alone, or a plurality of types may be used in combination.

  By containing the antifouling agent (G) other than the component (D), the underwater antifouling property of the formed coating film can be further improved. The content of the antifouling agent (G) is preferably 0.1 to 30% by weight in the antifouling coating composition.

[(H) Silica]
Silica (H) may be kneaded with organopolysiloxane (A) having two or more silanol groups in one molecule as described above or organopolysiloxane (F) other than (A) before use of the composition. Well, before preparing each component containing the organopolysiloxane in the antifouling coating composition, it may be kneaded with the organopolysiloxane in advance.

  Silica (H) is hydrophilic silica (surface untreated silica) such as wet method silica (hydrated silica), dry method silica (fumed silica, anhydrous silica), and hydrophobic wet silica and hydrophobic fumed silica. Hydrophobic silica that has been surface-treated, such as, can be used. These may be used alone or in combination of two or more.

The wet process silica is not particularly limited, but, for example, an adsorbed water content of about 4 to 8%, a bulk density of 200 to 300 g / L, a primary particle diameter of 10 to 30 μm, and a specific surface area (BET surface area) of 10 m ² / g or more. Can be used.

The dry silica is not particularly limited, and for example, a silica having a water content of 1.5% or less, a bulk density of 50 to 100 g / L, a primary particle diameter of 8 to 20 μm, and a specific surface area of 10 m ² / g or more can be used.

Hydrophobic fumed silica is obtained by subjecting dry silica to a surface treatment with an organosilicon compound such as methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane. Hydrophobic fumed silica has little moisture adsorption over time, and the moisture content is usually 0.3% or less, and in many cases 0.1 to 0.2%. Such hydrophobic fumed silica is not particularly limited, and for example, those having a primary particle diameter of 5 to 50 μm, a bulk density of 50 to 100 g / L, and a specific surface area of 10 m ² / g or more can be used.

  As will be described below, the moisture adsorbed on the surface of the silica is physically reduced and removed by heat treatment with the aforementioned organopolysiloxane. As a result, the moisture content of the heat-treated hydrophobic fumed silica is usually 0.2% or less, preferably 0.1% or less, and more preferably 0.05 to 0.1%. Other physical property values such as bulk density remain the same as the hydrophobic silica before heat treatment.

Such a silica can use what is marketed. Examples thereof include “R974” and “RX200” manufactured by Nippon Aerosil.
When silica (H) is used by kneading with the aforementioned organopolysiloxane, a heat-treated product formed by previously heat-treating the organopolysiloxane and silica, or the heat-treated product and the organopolysiloxane not heat-treated Preference is given to using a mixture of siloxanes. This is because the silica is preheated together with part or all of the organopolysiloxane to improve the affinity between the two components and to suppress the silica aggregation. This heat treatment is, for example, heating at a temperature of 100 ° C. or higher and below the decomposition temperature of the blended component, preferably 100 to 300 ° C., more preferably 140 to 200 ° C., usually for about 3 to 30 hours under normal pressure or reduced pressure. do it.

  Silica is contained in a proportion of usually 1 to 100% by weight, preferably 2 to 50% by weight, more preferably 5 to 30% by weight, based on the weight of the aforementioned organopolysiloxane. If the content of silica is within the above range, the antifouling coating composition exhibits suitable thixotropy, so that a desired film thickness can be obtained by one coating, particularly spray coating, and higher strength. A coating film having a hardness can be obtained.

  By using silica as described above, the stability during preparation or storage of the resulting antifouling coating composition is increased, the fluidity and thixotropy are improved, and the thickness is sufficient for vertical coating surfaces, etc. The coating film can be formed with a small number of times of coating, and further effects such as excellent balance of physical properties such as hardness, tensile strength, and elongation of the obtained coating film can be obtained.

[(I) Filler]
As the filler (I), conventionally known various organic and inorganic pigments and other fillers can be used.
Examples of organic pigments include carbon black, phthalocyanine blue, and bitumen.

  Inorganic pigments are neutral and non-reactive such as titanium white (titanium oxide), bengara, barite powder, talc, chalk, iron oxide powder, etc .; lead white, red lead, zinc powder, lead oxide Examples thereof include those that are basic and reactive with acidic substances in the paint, such as powder (active pigments). Other fillers include metal oxides such as diatomaceous earth and alumina; metal carbonates such as calcium carbonate, magnesium carbonate and zinc carbonate; other, asbestos, glass fiber, quartz powder, aluminum hydroxide, gold powder, silver powder, surface Examples thereof include treated calcium carbonate and glass balloon. Moreover, you may use what surface-treated these surfaces with the silane compound. Any one of these fillers may be used alone, or two or more thereof may be used in combination. These fillers can also contain various colorants such as dyes.

  By containing the filler (I) in the antifouling paint composition, the strength of the coating film can be improved, and further, by concealing the undercoat film, the deterioration of the undercoat film due to ultraviolet light can be prevented. it can. The content of the filler (I) is preferably 0.1 to 30% by weight in the antifouling coating composition.

[(J) Organic solvent other than alcohol (E)]
The antifouling paint composition of the present invention can contain an organic solvent (J) other than the alcohol (E) within a range that does not contradict the purpose of the present invention.

  As the organic solvent (J), aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ketones and esters can be used, and preferably aromatic hydrocarbons. .

Examples of the aromatic hydrocarbon-based organic solvent include toluene, xylene, styrene, mesitylene, and the like.
Examples of the aliphatic hydrocarbon organic solvent include pentane, hexane, heptane, and octane.

Examples of the alicyclic hydrocarbon-based organic solvent include cyclohexane, methylcyclohexane, and ethylcyclohexane.
Examples of the ketone organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate.

Examples of the ester organic solvent include propylene glycol monomethyl ether acetate.
By blending the organic solvent (J), the viscosity of the antifouling coating composition can be reduced and the coating workability can be improved.

  The preferable amount of the organic solvent (J) is determined by the viscosity of the antifouling coating composition, but is usually 0 to 50% by weight in the antifouling coating composition. When there is too much content, malfunctions, such as a fall of sagging stop property, will generate | occur | produce.

[(K) Sagging stop, anti-settling agent]
Anti-sagging and anti-settling agent (K) include organic clay wax (Al, Ca, Zn stearate salt, lecithin salt, alkyl sulfonate, etc.), organic wax (polyethylene wax, oxidized polyethylene wax, amide wax) , Polyamide wax, hydrogenated castor oil wax, etc.), mixtures of organic clay wax and organic wax, synthetic fine powder silica, and the like.

As the anti-sagging and anti-settling agent (K), commercially available products can be used. For example, in addition to “Disparon 305” and “Disparon 4200-20” manufactured by Enomoto Kasei Co., Ltd., those commercially available under trade names such as “Disparon A630-20X” can be used.
The content of the anti-sagging and anti-settling agent (K) is usually 0.01 to 10% by weight, preferably 0.1 to 3% by weight in the antifouling coating composition.

[(L) Silane coupling agent]
The silane coupling agent (L) is a silane cup containing one or more groups such as alkoxysilyl group, amino group, imino group, epoxy group, hydrosilyl group, mercapto group, isocyanate group, (meth) acryl group, etc. Ring agents are preferred, and those having an amino group are particularly preferred. Examples of the silane coupling agent having an amino group include 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2- (2- Aminoethyl) aminoethyl) aminopropyltrimethoxysilane and the like. Other silane coupling agents include, for example, 3-glycidoxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenylpropyltrimethoxysilane, N-phenylpropylene. Lutriethoxysilane and the like can also be mentioned. In addition, a mixture of a plurality of these silane coupling agents may be used.

  By blending the silane coupling agent (L), adhesion to the undercoat coating film or the substrate can be made stronger, or the strength of the antifouling coating film can be improved. The content of the silane coupling agent (L) is preferably 0.01 to 1% by weight in the antifouling coating composition.

[(M) Other coating film forming components]
The antifouling coating composition of the present invention contains a film-forming component other than the main resin component, organopolysiloxane, as the other film-forming component (M) within a range not contrary to the object of the present invention. Can do.

  Other coating film forming components (M) include, for example, acrylic resins, acrylic silicone resins, unsaturated polyester resins, fluororesins, polybutene resins, silicone rubbers, urethane resins (rubbers), polyamide resins, and vinyl chloride copolymer resins. , Chlorinated rubber (resin), chlorinated olefin resin, styrene-butadiene copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, alkyd resin, coumarone resin, trialkylsilyl acrylate (co) polymer (silyl resin) ), Poorly water-soluble or water-insoluble resins such as petroleum resins.

[(N) inorganic dehydrating agent]
Examples of the inorganic dehydrating agent (N) include anhydrous gypsum (CaSO ₄ ), synthetic zeolite-based adsorbent (trade name: molecular sieve, etc.), silicates and the like, and anhydrous gypsum and molecular sieve are preferably used. Such inorganic dehydrating agents can be used singly or in combination of two or more.

  The inorganic dehydrating agent (N) also functions as a stabilizer, and the antifouling coating composition contains this component, thereby preventing deterioration due to moisture in the antifouling coating composition and further improving storage stability. Can do. The content of the inorganic dehydrating agent (N) is preferably 0.1 to 10% by weight in the antifouling coating composition.

[(O) Flame retardant]
Examples of the flame retardant (O) include antimony oxide and paraffin oxide.
[(P) thixotropic agent]
Examples of the thixotropic property-imparting agent (P) include polyethylene glycol, polypropylene glycol, and derivatives thereof.
[(Q) Thermal conductivity improver]
Examples of the heat conduction improver (Q) include boron nitride and aluminum oxide.

-Preparation method of antifouling paint composition-
The antifouling coating composition of the present invention can be prepared by mixing the above components.
(Component of antifouling paint composition)
The antifouling paint composition according to the present invention may be provided as a one-component paint comprising one component or may be provided as a multi-component paint comprising two or more components. In the case of a multi-component type comprising two or more components, the antifouling paint composition according to the present invention is prepared by mixing the components.

(Multi-component antifouling paint composition / kit for preparing antifouling paint composition)
When the antifouling paint composition according to the present invention is provided as a multi-component paint comprising two or more components, each of these components (each solution) contains one or a plurality of components, respectively. After being packaged in a container, it is stored and stored in a container such as a can. The antifouling paint composition is prepared by mixing and stirring the contents of these components during painting. That is, in one aspect, the present invention provides a kit comprising the above components for preparing the antifouling coating composition according to the present invention.

  For organopolysiloxane-based antifouling coating compositions, generally, the component containing organopolysiloxane, which is the main component of the binder resin of the antifouling coating composition, is referred to as “main agent” and reacts with the organopolysiloxane. A component containing a compound used to construct a crosslinked structure is referred to as a “curing agent”. Furthermore, if there is a compound that is unsuitable for storage in the presence of coexistence because it reacts with any of the compounds contained in the main component and the hardener component and changes in quality, etc., an additional component referred to as an “additive” etc. . The antifouling paint composition (kit for preparation thereof) according to the present invention may be produced in the form of a two-component type comprising such a main component (X) and a curing agent component (Y). In some cases, it is manufactured in a three-part form consisting of a component (X), a hardener component (Y), and an additive component (Z).

  The antifouling coating composition according to the present invention comprises an organopolysiloxane (A) having two or more silanol groups in one molecule, an organosilane having two or more hydrolyzable groups in one molecule and / or a partial hydrolysis thereof. The anti-stain coating composition according to the present invention is composed of a decomposition condensate (B), a metal curing catalyst (C), an oxide (D) of copper or zinc, an alcohol (E), and other optional components. As an example of one embodiment of the kit, the main component (X) includes an organopolysiloxane (A) having two or more silanol groups in one molecule, an oxide of copper or zinc (D), an alcohol (E) And the curing agent component (Y) includes an organosilane having two or more hydrolyzable groups in one molecule and / or a partial hydrolysis condensate (B) thereof, and a metal curing catalyst (C). It is.

  For other optional components, the main component (X) and curing agent component are selected according to the presence or absence of alteration due to reaction with each component contained in each component as described above, and the viscosity, sedimentation, etc. of each component. You may mix | blend arbitrarily with (Y) and additive component (Z).

-Antifouling film and antifouling substrate-
The antifouling film according to the present invention is obtained by curing the antifouling coating composition. For example, an antifouling film can be obtained by applying the antifouling coating composition to form a coating film and curing the coating film.

  The antifouling film obtained by the present invention further improves the resistance to macro biological fouling obtained with an antifouling coating film formed from an organopolysiloxane antifouling coating composition that does not contain a conventional antifouling agent. In addition to being capable of preventing micro-fouling such as slime, it is highly effective for applications requiring high antifouling properties such as ships that are strongly required to reduce water flow resistance during navigation.

  The antifouling substrate according to the present invention is formed by coating the substrate with the antifouling film. The manufacture of the antifouling substrate comprises, for example, a step of applying or impregnating the antifouling coating composition to the substrate and a step of curing the antifouling coating composition applied to or impregnated on the substrate by the step. It can be performed by a method or a method comprising a step of sticking an antifouling film obtained by curing an antifouling coating composition to a substrate.

  Specific examples of the method of applying or impregnating the antifouling coating composition to the substrate include a method of sufficiently stirring the antifouling coating composition and then applying or impregnating the substrate by spraying or other means. As a method of curing the antifouling coating composition applied to or impregnated on the base material, specifically, a method of leaving it in a normal temperature atmosphere for about 0.5 to 3 days or forcibly blowing and heating under curing is used. Can be mentioned. By this method, an antifouling substrate in which the substrate is coated with an antifouling film can be produced.

  As a method of sticking the antifouling film obtained by curing the antifouling paint composition to a substrate, for example, using a known technique described in JP2013-129724A, the antifouling paint composition is cured. The method of sticking the film containing the antifouling film | membrane obtained by attaching to a base material is mentioned. By this method, an antifouling substrate in which the substrate is coated with an antifouling film can be produced.

  The film thickness of the antifouling film may be formed at a desired thickness depending on the application, but the antifouling coating composition is usually 30 to 400 μm / times, preferably 50 to 300 μm / time, and once to If it hardens | cures after apply | coating several times and the film thickness after hardening shall be 100-1000 micrometers, it will become an antifouling film excellent in film | membrane intensity | strength and antifouling performance.

  In the application of the antifouling paint composition, conventionally known painting means such as brushes, rolls, sprays, dip coaters and the like can be widely used, but the organopolysiloxane antifouling paint composition according to the present invention. The object has suitable properties for spray coating.

  The antifouling paint composition according to the present invention protects the surface of a substrate in contact with seawater or fresh water from adhesion of marine organisms in a wide range of industrial fields such as power generation, harbor / civil engineering construction, and shipbuilding (shipbuilding or repair). It can be used to maintain the original function of the substrate over a long period of time. Such base materials include, for example, ships (shipboards, etc.), fishing materials (ropes, fishing nets, fishing gear, floats, buoys, etc.), underwater structures such as thermal and nuclear power plants, and seawater use Examples include equipment (seawater pumps, etc.), mega floats, gulf roads, submarine tunnels, harbor facilities, sludge diffusion prevention membranes for various civil engineering works such as canals and waterways.

  The antifouling coating composition according to the present invention may be applied or impregnated directly on the substrate. The antifouling paint composition according to the present invention is also applied to a base material whose material is fiber reinforced plastic (FRP), steel, wood, aluminum alloy, etc., such as a water supply / drain port of a nuclear power plant, a mega float, and a ship. Products can be prepared so that the adhesion to the surface of these substrates (materials) is good.

  In addition, the base material to which the antifouling paint composition according to the present invention is applied may have a coating film already formed on the surface. That is, the antifouling coating composition according to the present invention may be applied to the surface of a base material such as a ship or an underwater structure to which a base material (undercoat) such as a rust preventive agent or primer has been applied in advance. Furthermore, the surface of a base material such as a ship that has already been coated with a conventional antifouling paint or that has been coated with the antifouling paint composition of the present invention, particularly an FRP ship or an underwater structure, The antifouling paint composition of the present invention may be overcoated for repair. Although the kind of coating film which the antifouling paint composition according to the present invention directly contacts is not particularly limited, as in the case of applying a general organopolysiloxane antifouling paint, for example, epoxy resin, urethane resin And a coating film formed from a paint mainly composed of a silicone resin or the like. The antifouling paint composition according to the present invention can be prepared such that the adhesion of the coating film to the surface is good.

The following examples further illustrate the present invention. In addition, this invention is not limited to description of a following example, unless the meaning is exceeded.
-Preparation of antifouling paint composition-
Table 1 shows the general names, manufacturers and brand names, etc. of the respective components of the antifouling paint compositions used in the present examples and comparative examples. The weight average molecular weight described in Table 1 was measured by GPC using a standard polystyrene calibration curve.

  Each component of the main component (X) and each component of the curing agent component (Y) shown in Tables 2 to 6 are sufficiently mixed using the disperser with the blending amounts shown in Tables 2 to 6, respectively. The main agent component (X) and the hardener component (Y) are prepared by mixing, and the main agent component (X) and the hardener component (Y) are mixed, and the examples 1 to 10 and the comparative examples 1 to 7 are mixed. An antifouling paint composition was prepared. The numerical value regarding each component of the main ingredient component (X) and the hardening | curing agent component (Y) in Tables 2-6 represents a weight part.

-Evaluation method-
The following physical property tests and antifouling tests were conducted on the antifouling coating compositions of Examples 1 to 10 and Comparative Examples 1 to 7 prepared as described above and the antifouling films formed therefrom. These results are as having described in Tables 2-6.

<Physical property test>
(Coating film curability)
In accordance with JIS K 5600-1-1 4.3, each antifouling coating composition was applied on a glass plate so as to have a film thickness of 200 μm, and the time until reaching the curing and drying was measured. The coating film curability was evaluated by this time.

(Pot life)
After the antifouling coating composition is prepared by mixing the main component (X) and the curing agent component (Y) of the antifouling coating composition, the viscosity of the composition increases with time due to the reaction of the components in each composition. The workability of coating decreases due to the thickening of the composition. The time during which the coating workability is within the allowable range is generally referred to as the pot life (practical pot life).

The pot life was evaluated as follows.
Under the temperature condition of 23 ° C., the viscosity is measured immediately after the preparation of the antifouling paint composition (initial viscosity), and then the viscosity is measured every 30 minutes, and the value of change in viscosity over time is connected with a straight line on the graph. The time until the viscosity exceeds twice the initial viscosity was determined every 10 minutes, and the time until immediately before exceeding the initial viscosity exceeded twice was defined as the pot life. When the viscosity obtained in the measurement at 10 minutes after the preparation was more than twice the initial viscosity, it was described as “less than 10 minutes” in Tables 2-6. If the initial viscosity did not exceed twice the initial viscosity even after 60 minutes, “60 minutes or more” was indicated.

Viscosity was measured using a B-type viscometer (manufacturer: Tokyo Keiki Co., Ltd., product name: B-type viscometer, model: BM) at a detector rotational speed of 60 rpm.
If the pot life measured in this way is 30 minutes or more, it can be said that the pot life of the antifouling paint composition is good.

<Anti-fouling test>
(Test plate preparation)
An epoxy anticorrosive paint (Brand No. 500, manufactured by China Paint Co., Ltd.) is applied to a sandblast plate with a thickness of 100 μm, and a silicone binder paint (Product name: CMP BioClean Thai Coat, manufactured by China Paint Co., Ltd.) is further applied thereto. ) With a thickness of 100 μm. The composition of Examples 1 to 10 and Comparative Example 2 was coated on the binder coating film of this plate so as to have a dry film thickness of 200 μm, and the coating film was dried at room temperature for 1 week to be cured. A fouling film was formed. The test plate thus obtained was subjected to a static antifouling property and a dynamic antifouling property test. In addition, about the comparative examples 1 and 3-7, since the composition became a gel-like lump and the composition could not be normally coated, these tests were not performed.

(Standing antifouling test method)
The test plate was left in the state of being immersed in seawater in Miyajima Bay, Hiroshima Prefecture, and the ratio of the area of the area where attached organisms on the antifouling film surface of the test plate adhered every three months was evaluated by visual observation. . The stationary antifouling property was evaluated at the following evaluation points.

(Dynamic antifouling test method)
The test plate was immersed in seawater off Kure, Hiroshima Prefecture. Using a rotating rotor, a water flow is generated to about 15 knots, and the water flow is applied to the antifouling film of the test plate. The ratio was evaluated by visual observation. The dynamic antifouling property was evaluated at the evaluation points shown below.

(Evaluation points)
0: No aquatic organisms attached 1: Aquatic organisms partially attached 2: Aquatic organisms attached to the entire surface

表２〜６に示された結果は、本発明による防汚塗料組成物が、塗料硬化性および塗料可使時間がバランスよく良好であり、長期にわたり高い防汚性を発揮できることを示している。

The results shown in Tables 2 to 6 indicate that the antifouling coating composition according to the present invention has good balance in coating curability and paint usable time, and can exhibit high antifouling properties over a long period of time.

Claims (14)

(A) an organopolysiloxane having two or more silanol groups in one molecule;
(B) Organosilane having two or more hydrolyzable groups in one molecule and / or a partial hydrolysis condensate thereof,
(C) a metal curing catalyst,
(D) an oxide of copper or zinc,
(E) alcohol,
Containing
The (A) organopolysiloxane is represented by the following general formula [I]:

(In the formula, each R ² independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group or a halogenated alkyl group;
r is an integer of 1 to 3,
s is an integer of 10 to 10,000. )
(E) An underwater antifouling coating composition, wherein the alcohol content is 1 to 20% by weight. The underwater antifouling paint composition according to claim 1, wherein the (D) oxide is cuprous oxide. The underwater antifouling paint composition according to claim 1 or 2, wherein the (E) alcohol is an alcohol having 5 or less carbon atoms. The underwater antifouling paint composition according to claim 3, wherein the (E) alcohol is N-butanol. The underwater antifouling paint composition according to any one of claims 1 to 4, wherein the (C) metal curing catalyst is a tin curing catalyst. The underwater antifouling paint composition according to any one of claims 1 to 5 , further comprising (F) an organopolysiloxane other than (A) represented by the following general formula [II].

(In the formula, each R ³ independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group or a halogenated alkyl group; or a hydrocarbon group having 1 to 10 carbon atoms at the end. And a polyoxyalkylene group having 2 to 100 carbon atoms which may be sealed with a silyl group having a hydroxyl group or a condensation reactive group on silicon, and u is an integer of 1 to 10,000.) Furthermore, the underwater antifouling paint composition as described in any one of Claims 1-6 containing antifouling agents other than (G) component (D). A kit for preparing a water antifouling coating composition according to any one of claims 1 to 7 including the main agent component and the (C) metal curing catalyst comprising said organopolysiloxane (A) A kit for preparing an underwater antifouling paint composition comprising a curing agent component. An antifouling film obtained by curing the underwater antifouling paint composition according to any one of claims 1 to 7 . A method for producing an antifouling film, comprising applying the underwater antifouling paint composition according to any one of claims 1 to 7 to obtain an antifouling film. An antifouling substrate comprising a substrate coated with the antifouling film according to claim 9 . The antifouling substrate according to claim 11 , wherein the substrate is any one of a ship, an underwater structure and a fishing gear. A base material antifouling method, comprising coating the base material with the antifouling film according to claim 9 . A step of coating or impregnating a water antifouling coating composition according to the substrate in any one of claim 1 to 7 is applied to the substrate by the process, or impregnated the water antifouling paint composition Or a step of forming a coating film from the underwater antifouling coating composition, curing the coating film to form an antifouling film for application, and using the antifouling film as a base material. A method for producing an antifouling substrate, comprising a step of applying.