JPWO2016009947A1 - Antifouling paint composition - Google Patents

Abstract

The present invention is an antifouling paint composition comprising (A) an organopolysiloxane having two or more silanol groups in one molecule, (B) a crosslinking agent and (C) inorganic copper. According to the present invention, an organopolysiloxane antifouling coating composition that can suppress dust scattering during spray coating, provides an antifouling coating film that exhibits excellent coating efficiency and exhibits high antifouling properties. Is obtained. The antifouling paint composition of the present invention has excellent coating efficiency during spray coating and can suppress dust scattering, so that the adhesion of paint, etc. on the surrounding coated surface due to spray dust scattering to the surroundings during coating It is possible to reduce adverse effects such as defects and occurrence of repelling, shorten the painting time, and reduce the amount of paint used.

Description

  By using organopolysiloxane and inorganic copper, the present invention can suppress spray dust scattering when spray-coated, and has excellent anti-fouling properties with excellent coating efficiency on the object to be coated. The present invention relates to an antifouling paint composition capable of forming a dirty paint film.

  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. The coating film formed from the organopolysiloxane antifouling paint 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.

  On the other hand, organopolysiloxane antifouling paints, especially when applied by spraying, are likely to scatter as spray dust around them, so the sprayed paint does not adhere to the coated surface, and surfaces other than the coated surface When spraying the surface, the spray dust adhering to the surface causes the adhesion failure and repellency of the sprayed paint. For this reason, when applying an organopolysiloxane antifouling paint, it is necessary to carefully cure the surroundings of the coating area over a wide range in order to prevent dust adhesion, resulting in a problem that the workability is greatly reduced.

  For the organopolysiloxane antifouling coating composition, for example, the techniques described in Patent Documents 1 to 4 are known. Patent Document 1 discloses an organopolysiloxane coating composition containing an antifouling agent, and describes that copper and inorganic copper compounds are preferable as the antifouling agent. In Patent Document 2, a polymer obtained by reacting an unsaturated isocyanate with dimethylpolysiloxane having at least one hydroxyl group in a molecule and copolymerizing a desired vinyl monomer with an inorganic and / or organic antifouling agent. It is described that the combined use with an agent can overcome the disadvantages of conventional organopolysiloxane antifouling paints, form a practical solid coating, and prevent the adhesion of shellfish in water over a long period of time. Yes. Patent Document 3 describes an adhesion-suppressing coating composition containing a binder system based on polysiloxane, a hydrophilic-modified polysiloxane, and a biocide. Patent Document 4 discloses a nitrogen-containing antibacterial effect that is excellent in repelling large adhering organisms in water, including microorganisms that form slime, and that has a long duration, is safe for the human body, and has little environmental pollution. Antifouling materials containing compounds are described.

  However, in these prior arts, nothing is mentioned about the coating efficiency of the paint at the time of painting, especially regarding the suppression of spray dust scattering.

JP 2001-139816 A JP-A-7-305001 Special table 2013-515122 gazette JP-A-9-249507

  The present invention is for solving the problems associated with the prior art, can form an antifouling film having high antifouling properties, has excellent coating efficiency, and spray dust during spray coating. An object of the present invention is to provide an antifouling paint composition capable of suppressing the scattering of water.

As a result of intensive studies to solve the above-described problems, the present inventor,
(A) an organopolysiloxane having two or more silanol groups in one molecule;
The antifouling paint composition containing (B) a crosslinking agent and (C) inorganic copper unexpectedly suppresses spray dust scattering and exhibits excellent coating efficiency, and developed the present invention. It came to do.

  (C) Inorganic copper contained in the antifouling coating composition is preferably cuprous oxide and / or metallic copper.

  The antifouling paint composition preferably further contains copper pyrithione.

  The antifouling coating composition preferably further contains (D) an antifouling agent other than inorganic copper (C) and copper pyrithione. The (D) antifouling property-imparting agent is preferably a pyrithione salt other than copper pyrithione.

  The antifouling coating composition preferably contains 0.5 to 60% by weight of the (C) inorganic copper, and more preferably 5 to 40% by weight.

  The antifouling coating composition preferably further contains (E) silicone oil. The (E) silicone oil is preferably an organopolysiloxane represented by the following general formula [I].

(In the formula, 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; or a hydrocarbon having 1 to 10 carbon atoms at the end. A polyoxyalkylene group having 2 to 100 carbon atoms which may be sealed with a silyl group having a group, a hydroxyl group or a condensation-reactive group on a silicon atom, and u is an integer of 1 to 10,000. )
The antifouling coating composition preferably further contains (F) a metal curing catalyst and / or (G) an organic solvent.

  The antifouling coating film according to the present invention is obtained by curing the above antifouling coating composition.

  The method for producing an antifouling coating film according to the present invention is characterized in that the antifouling coating composition is applied to obtain the antifouling coating film.

  The antifouling substrate according to the present invention is characterized in that the substrate is coated with the above antifouling coating 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 surface of the substrate is coated with the antifouling coating film.

  A method for producing an antifouling substrate according to the present invention includes a step of applying the antifouling coating composition to a substrate, and a step of curing the antifouling coating composition applied to the substrate by the step. .

  ADVANTAGE OF THE INVENTION According to the present invention, an organopolysiloxane antifouling paint composition capable of suppressing dust scattering during spray coating, providing an antifouling coating film having excellent coating efficiency and exhibiting high antifouling properties A thing is obtained.

  The antifouling paint composition of the present invention has excellent coating efficiency during spray coating and can suppress dust scattering, so that the adhesion of paint, etc. on the surrounding coated surface due to spray dust scattering to the surroundings during coating It is possible to reduce adverse effects such as defects and repelling, shorten painting time, and reduce usage.

FIG. 1 is a schematic explanatory diagram of an apparatus for measuring the dust scattering rate during spray coating used in the examples.

-Antifouling paint composition-
The antifouling coating composition according to the present invention contains (A) an organopolysiloxane having two or more silanol groups in one molecule, (B) a crosslinking agent, and (C) inorganic copper. 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 [II].

In the above general formula [II], each R ² is independently 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 [II], r is an integer of 1-3, Preferably it is 1.

  In the said general formula [II], s is an integer of 10-10,000, Preferably it is 100-1,000.

  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 from the viewpoint of excellent manufacturing workability of the coating material, 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 coating film exhibiting antifouling properties for a long period of time is obtained. be able to.

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) Crosslinking agent>
The crosslinking agent (B) is preferably an organosilane having two or more hydrolyzable groups in one molecule represented by the following general formula [III] and / or a partial hydrolysis condensate thereof.

In the above general formula [III], R ⁴ independently represents a hydrocarbon group having 1 to 6 carbon atoms, for example, a linear or branched alkyl group such as a methyl group, an ethyl group or a propyl group, or a cyclohexyl group. A cyclic alkyl group such as a vinyl 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 general formula [III], Y is independently a hydrolyzable group, and examples thereof include an alkoxy group, a ketoxime group, an acyloxy group, an alkenyloxy group, an amino group, an amide group, and an aminooxy group. Are an alkoxy group and a ketoxime group.

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

  Examples of the ketoxime group (also referred to as ketoxime group) include a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, a methyl isopropyl ketoxime group, a cyclopentanoxime group, and a cyclohexanoxime group.

  The acyloxy group is preferably an aliphatic group or an aromatic group represented by the formula: RCOO— (wherein R is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms). Examples thereof include an acetoxy group, a propionoxy group, a butyroxy group, and a benzoyloxy group.

  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 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.

  Such an organosilane can use what was marketed. For example, “ethyl silicate 28” (manufactured by Colcoat Co.), “normal ethyl silicate” (manufactured by Tama Chemical Industries) as tetraethyl orthosilicate, and “silicate 40” (manufactured by Tama Chemical Industries) as a partially hydrolyzed condensate of tetraethyl orthosilicate. ), “TES40 WN” (manufactured by Asahi Kasei Wacker Silicone), and alkyltrialkoxysilane include “KBM-13” (manufactured by Shin-Etsu Chemical Co., Ltd.).

The crosslinking agent (B) is generally contained in the antifouling coating composition in an amount of 0.1 to 50% by weight, usually 1 to 30% by weight, preferably 3 to 15% by weight. Is done. When the content of the crosslinking agent (B) is in this range, the curing rate of the antifouling coating composition can be appropriately maintained, and the coating film obtained by curing exhibits excellent coating strength and rubber properties. can do.
<(C) Inorganic copper>
Inorganic copper (C) can suppress the spray dust scattering of the antifouling coating composition, can improve the coating efficiency to the coating object, and can improve the antifouling property of the antifouling coating film. That is, although inorganic copper is normally used as an antifouling property imparting agent in an antifouling coating composition, the present inventors have found that inorganic copper has an effect of suppressing spray dust scattering, and the inorganic copper (C) By using it, it was possible to improve the antifouling property of the antifouling coating, to suppress the scattering of spray dust and to improve the coating efficiency to the object.

  Examples of the inorganic copper (C) include cuprous oxide, metallic copper, copper oxide, copper thiocyanate, and copper chloride. Among these, cuprous oxide or metallic copper is preferable. Two or more of these may be used in combination.

  Commercially available cuprous oxide and metallic copper can be used. For example, as cuprous oxide, “cuprous oxide NC-803”, “cuprous oxide NC-301” (manufactured by Nisshin Chemco), “RED COPP 97N Premium”, “LOLO TINT LM” (American Chemet Corporation), Examples of metallic copper include “electrolytic copper powder # 6” (manufactured by JX Nippon Mining & Metals).

Content of inorganic copper (C) is 0.5-60 weight% normally in an antifouling coating composition, Preferably it is 5-40 weight%, More preferably, it is 10-35 weight%. When the content of the inorganic copper (C) is in this range, it is possible to impart a high level of anti-fouling properties to the high level spray dust scattering suppression effect and the antifouling coating film.
<Optional component>
The antifouling coating composition according to the present invention includes copper pyrithione, inorganic copper (C) and copper in addition to organopolysiloxane (A) having two or more silanol groups, a crosslinking agent (B), and inorganic copper (C). Antifouling agent other than pyrithione (D), silicone oil (E) other than organopolysiloxane (A), metal curing catalyst (F), organic solvent (G), silica (H), other than silica (H) Filler (I), anti-sagging, anti-settling agent (J), silane coupling agent (K), other coating film forming component (L), inorganic dehydrating agent (M), flame retardant (N), thixotropic properties An agent (O), a heat conduction improving agent (P) and the like may be contained.
[Copper pyrithione and (D) antifouling imparting agent other than inorganic copper (C) and copper pyrithione]
The antifouling property-imparting agent other than inorganic copper (C) may be either organic or inorganic.

  Examples of organic antifouling agents include pyrithione salt compounds, tetramethylthiuram disulfide, and carbamate compounds represented by the following general formula [IV] (eg, zinc dimethyldithiocarbamate, manganese-2 ethylenebisdithiocarbamate) 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.

In the general formula [IV], each R ³ independently represents hydrogen 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, and n is the valence of the metal M.

  Any one type of antifouling agent other than inorganic copper (C) may be used alone, or a plurality of types may be used in combination.

  When the antifouling coating composition contains an antifouling property imparting agent other than inorganic copper (C), the underwater antifouling property of the coating film can be further improved.

  A pyrithione salt is preferred as the antifouling agent.

  Of the pyrithione salts, when copper pyrithione is contained in the antifouling coating composition, the antifouling property can be improved and the spray dust scattering suppression effect brought about by inorganic copper (C) can be further enhanced, and the coating can be applied to the object to be coated. Efficiency can be further improved. The content of copper pyrithione is preferably 0.1 to 30% by weight, more preferably 0.5 to 15% by weight, and still more preferably 1 to 10% by weight in the antifouling coating composition.

  As content of antifouling property imparting agents (D) other than inorganic copper (C) and copper pyrithione, an amount of 0.1 to 30% by weight is preferable in the antifouling coating composition.

Copper pyrithione, inorganic copper (C), and antifouling agent (D) other than copper pyrithione may be used in combination.
[(E) Silicone oil other than organopolysiloxane (A)]
As the silicone oil (E) other than the organopolysiloxane (A), an organopolysiloxane represented by the following general formula [I] is preferably used.

In the general formula [I], 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; or a terminal having 1 to 10 carbon atoms. A polyoxyalkylene group having 2 to 100 carbon atoms which may be sealed with a silyl group having a hydrocarbon group, a hydroxyl group or a condensation reactive group on a silicon atom, a methyl group and a phenyl group, or a methyl group And a polyoxyalkylene group.

  In the above general formula [I], u is an integer of 1 to 10,000.

Examples of the silicone oil (E) in which R ³ is a methyl group and a phenyl group in the general formula [I] include, for example, “KF-54”, “KF-56”, “KF-50” (Shin-Etsu Chemical ( ), “SH510”, “SH550” (manufactured by Toray Dow Corning), “TSF431” (manufactured by Toshiba Silicone Co., Ltd.), and the like.

In the above general formula [I], as the silicone oil (E) in which R ³ is a methyl group and a polyoxyalkylene group, “X-22-6548” (alkylene glycol-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) "FZ-2164" (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.), What is marketed by brand names, such as "BY16-839" (alicyclic epoxy modified silicone oil, Toray Dow Corning Co., Ltd. product), is mentioned.

Content of silicone oil (E) is 0.01-30 weight% normally in an antifouling coating composition, Preferably it is 0.1-15 weight%. When the content of the silicone oil (E) 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 coating film can be improved.
[(F) Metal curing catalyst]
The metal curing catalyst (F) is a catalyst for accelerating each condensation reaction of the organopolysiloxane (A) and the crosslinking agent (B) having two or more silanol groups in one molecule or between them. Accelerating the curing reaction of the coating film so that a cured coating film can be obtained sooner after coating.

  The metal curing catalyst (F) is preferably a tin-containing curing catalyst.

  As the metal curing catalyst (F), 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 dioctyl tin 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 (F) can be used. For example, “NEOSTAN U-100” (manufactured by Nitto Kasei Co., Ltd.) can be mentioned.

The content of the metal curing catalyst (F) 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. 001% by weight, particularly preferably 0.01% by weight. When the content of the metal curing catalyst (F) is within this range, a coating composition having a good balance between the coating film curing rate and the pot life after the preparation of the coating is obtained.
[(G) Organic solvent]
As the organic solvent (G), aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, ketones and esters can be used, and aromatic hydrocarbons and It is preferable to use an alcohol system in combination.

  The alcohol may be a straight chain, branched chain, or cyclic alcohol having an ether group contained in the chain, and examples thereof include methanol, ethanol, propanol, butanol, pentanol, and hexanol.

  As the alcohol, an alcohol having 5 or less carbon atoms is preferable, and n-butanol is more preferable. When alcohol is selected from these, a long time can be obtained as the pot life after mixing the paint.

  The content of the alcohol is usually 1 to 20% by weight, preferably 3 to 10% by weight in the antifouling coating composition. When the alcohol content is within this range, a long time can be obtained as the pot life after mixing the paint.

  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.

  When the antifouling paint composition contains the organic solvent (G), the viscosity of the antifouling paint composition can be reduced and the coating workability can be improved.

A preferable amount of the organic solvent (G) is determined by the viscosity of the antifouling coating composition, and 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, generate | occur | produce.
[(H) Silica]
Silica (H) is an organopolysiloxane (A) or silicone oil (E) having two or more silanol groups in one molecule as described above. Before preparation of each component to be contained, it may be kneaded with an 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 are the same as those of 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 a part or all of the organopolysiloxane to improve the affinity of both components and to obtain effects such as suppressing 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 the organopolysiloxane (A) in a proportion of usually 1 to 100% by weight, preferably 2 to 50% by weight, more preferably 5 to 30% by weight. 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 high strength. A coating film with hardness is obtained.

As described above, by using silica as described above, the stability during preparation or storage of the resulting antifouling coating composition is increased, fluidity and thixotropy are improved, and sufficient for vertical coating surfaces and the like. A coating film having a thickness can be formed with a small number of coatings, and effects such as excellent balance of physical properties such as hardness, tensile strength, and elongation of the resulting coating film can be obtained.
[(I) Fillers other than silica (H)]
As the filler (I) other than silica (H), 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 coating composition, the strength of the coating film can be improved, and further, by concealing the undercoating film, deterioration of the undercoating 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) Anti-sagging, anti-settling agent]
Anti-sagging and anti-settling agent (J) include organic clay waxes (such as Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonates), organic waxes (polyethylene wax, polyethylene oxide 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 (J), commercially available products can be used. For example, “Disparon 305” and “Disparon 4200-20” manufactured by Enomoto Kasei Co., Ltd., as well as “Disparon A630-20X” can be used.

The content of the anti-sagging and anti-settling agent (J) is usually 0.01 to 10% by weight, preferably 0.1 to 3% by weight, in the antifouling coating composition.
[(K) Silane coupling agent]
The silane coupling agent (K) is a silane cup containing one or more groups such as an alkoxysilyl group, an amino group, an imino group, an epoxy group, a hydrosilyl group, a mercapto group, an isocyanate group, and a (meth) acryl group. 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. Moreover, as a silane coupling agent, you may use the mixture of these several things.

By including the silane coupling agent (K) in the antifouling coating composition, adhesion to the undercoat coating film or the substrate can be made stronger, or the strength of the coating film of the antifouling coating composition can be improved. it can. The amount of the silane coupling agent (K) is preferably 0.01 to 1% by weight in the antifouling coating composition.
[(L) Other coating film forming components]
As the other coating film-forming component (L), a coating film-forming component other than the main resin component, organopolysiloxane, can be used within a range not departing from the object of the present invention.

Other coating film forming components (L) 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.
[Inorganic dehydrating agent (M)]
Examples of the inorganic dehydrating agent (M) 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 alone or in combination.

The inorganic dehydrating agent (M) 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 (M) is preferably 0.1 to 10% by weight in the antifouling coating composition.
[(N) flame retardant]
Examples of the flame retardant (N) include antimony oxide and paraffin oxide.
[(O) thixotropic agent]
Examples of the thixotropic property-imparting agent (O) include polyethylene glycol, polypropylene glycol, and derivatives thereof.
[(P) Thermal conductivity improver]
Examples of the heat conduction improver (P) 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 contents of these components are mixed and stirred at the time of painting to prepare an antifouling paint composition. 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). It may be produced in the form of a three-component type consisting of component (X), curing agent component (Y) and additive component (Z).

-Antifouling coating and antifouling substrate-
The antifouling coating film is obtained by curing the antifouling coating composition.

  The antifouling coating film obtained by curing the antifouling coating composition can further improve the resistance to macrobiological fouling, and can also suppress the adhesion of microfouling such as slime. A high effect can be obtained for applications that require high antifouling properties such as ships that are strongly required.

  The antifouling substrate is obtained by coating the substrate with the antifouling coating film. The production of the antifouling substrate is, for example, a method comprising a step of applying the antifouling coating composition to the substrate and a step of curing the antifouling coating composition applied to the substrate by the step, It can be performed by a method including a step of sticking an antifouling film obtained by curing the stain coating composition to a substrate.

  Specific examples of the method for applying the antifouling coating composition to the substrate include a method in which the antifouling coating composition is sufficiently stirred and then applied to the substrate by spraying or other means. Specific examples of the method of curing the applied antifouling coating composition include a method of allowing it to stand for 0.5 to 3 days in a normal temperature atmosphere or to cure by forcibly blowing air under heating. By this method, an antifouling substrate obtained by coating the substrate with an antifouling coating film can be produced.

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

  Although the film thickness of the antifouling coating film may be formed with a desired thickness depending on the application, etc., the antifouling coating composition is usually 30 to 400 μm, preferably 50 to 300 μm / time, and once to plural times. If it is cured after being applied once and the film thickness after curing is, for example, 100 to 1000 μm, an antifouling coating film excellent in coating film strength and antifouling performance is obtained.

  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. The organopolysiloxane antifouling paint composition according to the present invention Has characteristics suitable for spray coating as described above. That is, when the antifouling paint composition according to the present invention is applied by spraying, it is possible to improve the antifouling property of the antifouling coating film, suppress spray dust scattering, and improve the application efficiency to the object.

  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 general names, chemical formulas, and the like of the components of the antifouling coating composition used in the present examples and comparative examples. The weight average molecular weight Mw described in Table 1 was measured by GPC using a standard polystyrene calibration curve.

  By sufficiently mixing each component of the main component (X) shown in Table 2 and each component of the hardener component (Y) in the blending amounts shown in Table 2 using a disperser. Antifouling paint compositions of Examples 1-10 and Comparative Examples 1-2 by preparing the main agent component (X) and the hardener component (Y) and mixing the main agent component (X) and the hardener component (Y) A product was prepared. The numerical values relating to the main component (X) and the hardener component (Y) in Table 2 represent parts by weight.

Measurement test of dust scattering rate during spray coating using antifouling paint compositions of Examples 1 to 10 and Comparative Examples 1 and 2 prepared as described above, and antifouling formed from those antifouling paint compositions An antifouling test was conducted on the dirty coating. These results are as described in Table 2.
[Dust scattering rate during spray painting]
A test was carried out with the measuring device shown in FIG. 1 in order to evaluate the dust scattering rate during spray coating. This measuring device includes an air inlet, a painted surface F, a lower surface B, and a spray gun G.

  The air was sucked from a suction port opened in a rectangular shape with a width of 900 mm and a height of 850 mm so that the wind speed was about 2 m / s.

  A plate material having a painted surface F having a height of 850 mm and a width of 700 mm is installed so that one side of the painted surface F is in contact with one side of the intake port, and the painted surface F and the intake port are perpendicular to each other. A weighed polyethylene sheet was attached.

  A plate member having a lower surface B having a width of 450 mm and a width of 700 mm is installed so that two sides of the lower surface B are in contact with the one side of the intake port and the painted surface F, respectively, and a weighted polyethylene sheet is pasted on the entire lower surface B. I attached.

The antifouling paint composition is inserted into the spray gun G, and the gun tip (discharge point S) is installed at a distance of 700 mm from the painted surface F and at a height of 450 mm from the lower end of the painted surface F. The antifouling paint compositions of Examples 1 to 10 and Comparative Examples 1 and 2 were discharged for 10 seconds from a spray gun at a discharge pressure of 5 kgf / cm ² toward the center of the coating surface F in a direction perpendicular to the surface. .

  Before and after each painting, measure the weight of the spray gun filled with the antifouling paint composition (the sum of the weight of the spray gun and the weight of the antifouling paint composition filled) before painting. The weight of the antifouling paint composition discharged during each coating was calculated by subtracting the weight after coating from the weight of the above. The discharge weight was multiplied by the solid content ratio of each antifouling paint composition to obtain the discharged paint solid weight of the applied antifouling paint composition.

  After coating, the polyethylene sheet affixed to the painted surface F and coated with each antifouling paint composition was dried for 24 hours, and then the weight (weight of the polyethylene sheet and the weight of the antifouling paint composition applied) And the weight of the polyethylene sheet before coating was subtracted from the weight to determine the weight of the coating material.

  After coating, the polyethylene sheet affixed to the lower surface B and coated with each antifouling paint composition was dried for 24 hours, and then the weight (the weight of the polyethylene sheet and the weight of the antifouling paint composition applied) Total) was measured, and the weight of the polyethylene sheet before coating was subtracted from the weight to obtain the weight of the falling paint.

  The dust scattering rate was calculated by the following formula, assuming that the weight of the sprayed paint dust was the weight of the sprayed paint solids minus the weight of the paint applied to the painted surface and dropped to the lower surface.

  The above coating was performed twice for each antifouling paint composition, and the average value and standard deviation of the dust scattering rate obtained are shown in Table 2.

It is evaluated that the lower the dust scattering rate, the less spray dust is scattered during the spray coating operation and the higher the coating efficiency.
[Anti-fouling test]
(Test plate preparation)
An epoxy anticorrosive paint (Brand No. 500, manufactured by China Paint Co., Ltd.) and a silicone-based binder paint (Product name: CMP Bioclin Thai Coat, manufactured by China Paint Co., Ltd.) have a thickness of 100 μm in this order on the sandblast plate. In this way, each of the compositions of Examples 1 to 10 and Comparative Examples 1 and 2 was applied to the plate material obtained by lamination coating so as to have a dry film thickness of 200 μm and cured to obtain a test plate.

(Dynamic antifouling test method)
After the test plate is dried at room temperature for 7 days, it is immersed in seawater off Kure, Hiroshima Prefecture, and a water flow is generated at about 15 knots per hour using a rotating rotor. The water flow is applied to the antifouling coating surface of the test plate. The ratio of the area of the area where aquatic organisms adhered to the antifouling coating film surface of the test plate every three months was evaluated by visual observation. The dynamic antifouling property was evaluated at the evaluation points shown below.

(Standing antifouling test method)
After the test plate is dried at room temperature for 7 days, the test plate is left in a state immersed in seawater in Miyajima Bay, Hiroshima Prefecture, and the ratio of the area of the area where adherent organisms occupy the antifouling membrane surface of the test plate every 3 months Evaluation was made by visual observation. The stationary antifouling property was evaluated at the following evaluation points.

(Anti-fouling test evaluation point)
0: No aquatic organisms attached 1: Aquatic organisms partially attached 2: Aquatic organisms attached to the entire surface

Claims (16)

(A) an organopolysiloxane having two or more silanol groups in one molecule;
An antifouling paint composition comprising (B) a crosslinking agent and (C) inorganic copper.   The antifouling paint composition according to claim 1, wherein the inorganic copper (C) is cuprous oxide and / or metallic copper.   The antifouling paint composition according to claim 1 or 2, further comprising copper pyrithione.   The antifouling paint composition according to any one of claims 1 to 3, further comprising (D) an antifouling property-imparting agent other than inorganic copper (C) and copper pyrithione.   The antifouling paint composition according to claim 4, wherein the antifouling property imparting agent (D) is a pyrithione salt other than copper pyrithione.   The antifouling paint composition according to any one of claims 1 to 5, wherein the inorganic copper (C) is contained in an amount of 0.5 to 60% by weight.   The antifouling paint composition according to any one of claims 1 to 5, comprising 5 to 40% by weight of the (C) inorganic copper.   Furthermore, (E) Silicone oil is contained, The antifouling coating composition as described in any one of Claims 1-7 characterized by the above-mentioned. The antifouling paint composition according to claim 8, wherein the (E) silicone oil is an organopolysiloxane represented by the following general formula [I].

(In the formula, 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; or a hydrocarbon having 1 to 10 carbon atoms at the end. A polyoxyalkylene group having 2 to 100 carbon atoms which may be sealed with a silyl group having a group, a hydroxyl group or a condensation-reactive group on a silicon atom, and u is an integer of 1 to 10,000. )   Furthermore, the antifouling paint composition according to any one of claims 1 to 9, further comprising (F) a metal curing catalyst and / or (G) an organic solvent.   An antifouling coating film obtained by curing the antifouling coating composition according to any one of claims 1 to 10.   An antifouling paint film is obtained by applying the antifouling paint composition according to any one of claims 1 to 10 to obtain an antifouling paint film.   An antifouling substrate comprising a substrate coated with the antifouling coating film according to claim 11.   The antifouling substrate according to claim 12, wherein the substrate is any one of a ship, an underwater structure, and a fishing gear.   A method for antifouling a substrate, comprising coating the surface of the substrate with the antifouling coating film according to claim 11.   A step of applying the antifouling coating composition according to any one of claims 1 to 10 to a substrate, and a step of curing the antifouling coating composition applied to the substrate by the step. A method for producing an antifouling substrate, comprising:

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