JP2009173815A - Antifouling paint composition, antifouling coating film formed using antifouling paint composition, coated object having coating film on surface, antifouling treatment method for forming coating film, and kit for forming antifouling coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifouling paint composition of high environmental safety, capable of forming a coating film of excellent antifouling performance. <P>SOLUTION: This antifouling paint composition contains (A) an organo polysiloxane having a crosslinking reactive functional group, (B) an aluminum compound as a condensation reaction catalyst, and (C) a silicone oil. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antifouling coating composition for preventing the use of or existing in water under water-fouling-fouling organisms for a long period of time, and an antifouling coating film formed using the antifouling coating composition The present invention relates to a coated product having the coating film on its surface, an antifouling treatment method for forming the coating film, and an antifouling coating film forming kit.

  Underwater such as seas, rivers, and lakes are inhabited by aquatic fouling organisms such as barnacles, sea squirts, cell plastics, mussels, crows, chrysanthemum, aonori and aosa.

  Conventionally, vessels; fishing nets (aquaculture nets, stationary nets, etc.), fishing net accessories, etc .; jetty, tetrapots, port facilities, buoys, pipelines, bridges, powerhouse conduits, submarine bases, subsea oil field drilling There is a problem in that the above-described water fouling organisms adhere to an object used or present in water such as an underwater structure such as equipment. Specifically, if a ship or the like has been immersed in water for a long period of time, the above-described water fouling organisms adhere to and grow on contact parts with water, causing a decrease in ship speed, a decrease in water flow, etc. It is known to cause significant resource losses. Therefore, in order to prevent the adhesion of chickenpox fouling organisms, studies have been made to solve the above problem by applying an antifouling paint.

  For example, an antifouling paint containing an antifouling compound such as a trialkyltin compound has been conventionally used as the antifouling paint.

  However, although the antifouling paint is very excellent in antifouling properties, it is highly toxic and there are concerns about safety and environmental impact.

  Therefore, silicone rubber-based antifouling paints that form a coating film of silicone rubber alone or a mixture of silicone rubber and silicone oil have been proposed as non-toxic antifouling paints (Patent Documents 1 to 4).

However, in these antifouling paints, a dialkyltin compound is used as a curing catalyst, and the amount used is very small, but it is desired not to use it from the viewpoint of environmental protection.
JP 51-96830 A Japanese Examined Patent Publication No. 56-26272 Japanese Unexamined Patent Publication No. 63-43973 JP-A-3-255169

  An object of the present invention is to provide an antifouling coating composition that can form a coating film excellent in antifouling performance in water and has high environmental safety.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific non-toxic catalyst as a catalyst for the condensation reaction of organopolysiloxane. The headline and the present invention were completed.

That is, the present invention includes the following antifouling paint composition, an antifouling coating film formed using the composition, a coated product having the coating film on the surface, an antifouling treatment method for forming the coating film, and It relates to an antifouling coating film forming kit.
1. (A) an organopolysiloxane having a crosslinking reactive functional group,
(B) An antifouling coating composition containing an aluminum compound as a condensation reaction catalyst and (C) silicone oil.
2. The antifouling according to item 1, wherein 0.01 to 20 parts by weight of the aluminum compound (B) and 10 to 200 parts by weight of the silicone oil (C) are contained with respect to 100 parts by weight of the organopolysiloxane (A). Paint composition.
3. The aluminum compound (B) has the general formula [1]:
Al (OR ¹ ) ₃ [1]
(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ¹ may be the same or different.)
In the trialkoxyaluminum represented by the general formula [2]:
HO—R ² —OH [2]
(In the formula, R ² is an alkylene group having 2 to 10 carbon atoms, an alkenylene group or an alkynylene group.)
And / or the general formula [3]:
HO-R ³ -Y ^[3]
(Wherein R ³ is an alkylene group having 2 to 10 carbon atoms, Y is a group represented by the formula: —OR ⁴ , or a group represented by the formula: —NR ⁵ R ⁶ ; ⁴ is an alkyl group or aryl group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ are the same or different and are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
Item 3. The antifouling paint composition according to Item 1 or 2, which is an aluminum compound obtained by reacting an alcohol compound represented by the formula:
4). The aluminum compound (B) has the general formula [4]

Wherein R ⁷ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and R ⁸ is a linear or branched alkyl group having 1 to 10 carbon atoms. Or a linear or branched alkoxy group having 1 to 10 carbon atoms, n is 1 or 2, and when n is 2, two R ^{7 s} may be the same or different from each other .)
Item 3. The antifouling coating composition according to Item 1 or 2, which is an aluminum compound represented by the formula:
5. The aluminum compound (B) has the general formula [5]

(In the formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different from each other, and are each a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 2, and n is 2. Sometimes the two R ^9s may be the same or different from each other.)
Item 3. The antifouling coating composition according to Item 1 or 2, which is an aluminum compound represented by the formula:
6). The antifouling processing method which forms an antifouling coating film on the surface of a to-be-coated-film formation object using the antifouling coating material composition in any one of said items 1-5.
7). The antifouling coating film formed using the antifouling paint composition in any one of said items 1-5.
8). 8. A coated product having the antifouling coating film according to item 7 on its surface.
9. In the presence of moisture, an organopolysiloxane having a crosslinking reactive functional group (A) and an aluminum compound (B) as a condensation reaction catalyst are mixed to produce an organopolysiloxane rubber. An antifouling paint composition obtained by mixing silicone oil (C).
10. (1) a container containing an organopolysiloxane (A) having a crosslinking reactive functional group, and (2) a container containing an aluminum compound (B) as a catalyst for condensation reaction, and a silicone oil (C) Is a kit for forming an antifouling coating film, which is contained in the container (1) and / or the container (2).

Antifouling paint composition The antifouling paint composition of the present invention comprises:
(A) an organopolysiloxane having a crosslinking reactive functional group,
(B) an aluminum compound as a condensation reaction catalyst, and (C) a silicone oil.

    By containing the aluminum compound (B), an organopolysiloxane rubber can be suitably formed from the organopolysiloxane (A), and a coating film excellent in antifouling performance capable of suitably exhibiting the antifouling effect for a long period of time. Can be formed. Moreover, the composition of this invention contains an aluminum compound instead of a dialkyl tin compound as a curing catalyst, and is excellent in environmental safety.

  The composition of the present invention can be used as a one-pack type antifouling paint and is excellent in workability.

<Organopolysiloxane (A)>
The organopolysiloxane (A) has at least one crosslinkable functional group on the silicon atom in the molecular chain, and further has an organic group other than the crosslinkable functional group.

  Examples of the crosslinking reactive functional group include an alkoxy group such as a hydroxyl group, a methoxy group, an ethoxy group, and a propoxy group; and an aralkyloxy group such as a benzyloxy group.

  Examples of the organic group generally include organic groups possessed by organopolysiloxane, specifically, alkyl groups such as methyl group, ethyl group, and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl Groups, alkenyl groups such as allyl groups; aralkyl groups such as benzyl groups; aryl groups such as phenyl groups and naphthyl groups; and halogenated alkyl groups such as 3,3,3-trifluoropropyl groups.

  The organopolysiloxane (A) undergoes a condensation reaction in the presence of an aluminum compound (B) described later and in the presence of moisture (or moisture in the air) to form an organopolysiloxane rubber. Specifically, the crosslinkable functional group in the organopolysiloxane (A) undergoes a condensation reaction with the crosslinkable reactive functional group of another organopolysiloxane (A) or the hydrolyzable group in the crosslinker. Rubber is formed and becomes a coating.

  The reaction temperature in such a condensation reaction is usually 80 ° C. or lower, preferably 50 ° C. or lower.

  In the composition of the present invention, the organopolysiloxane (A) may previously form an organopolysiloxane rubber. As such a composition, for example, the organopolysiloxane (A) and the aluminum compound (B) are mixed in the presence of moisture to produce an organopolysiloxane rubber, and then the organopolysiloxane rubber and silicone are mixed. Examples thereof include an antifouling paint composition obtained by mixing with oil (C).

  As said organopolysiloxane (A), what is used as a film formation component of the conventional silicone rubber-type antifouling paint can be used. Specifically, the organopolysiloxane (A) is classified into a deacetone type, a dealcohol type, a deoxime type, a deacetic acid type, and the like depending on the reaction mode. In the present invention, the same type of organopolysiloxane (A) may be used, or two or more different types may be used in combination.

  The organopolysiloxane (A) may be diluted with an arbitrary solvent depending on its physical properties. As the solvent, for example, toluene, xylene and the like can be used.

  The viscosity of the organopolysiloxane (A) and the diluted product thereof is preferably 500 to 100,000 mPa · s, more preferably 1,000 to 80,000 mPa · s. The viscosity can be adjusted by diluting with the above solvent or mixing two or more kinds of organopolysiloxanes (A) at an arbitrary ratio.

  Commercially available products of organopolysiloxane (A) include KE-40RTV, KE-41, KE-42, KE-42RTV, KE-42S, KE-44, KE-44RTV, KE-45, KE-45TS, KE- 45TSRTV, KE-441, KE-445, KE-45TS, KE-47, KE-48, KE-66, KE-348, KE-3479, KE-347, KE-118, KE-347, KE-402, KE-420, KR-2706, KE-4348, KE-66RTV, KE-1251, KE-1253, KE-3490, KE-3491, KE-4525, KE-4866, FE123 (manufactured by Shin-Etsu Chemical Co., Ltd.) , SE5004, SE5007, SE5060, SE5070, SE5400, SE9140, SH237, SH7 0 (above, manufactured by Toray Dow Corning), SilaSeal 3FW, SILASTIC739RTV, RTV3110, SE738 (above, manufactured by Dow Corning), TSE371, Tosseal 380 (above, manufactured by Momentive Performance Materials), Bergan C, FSXR -2622 (above, manufactured by Dow Corning), Rhodorsil 48V (above, manufactured by Rhône-Poulenc), Silicoset 105 (above, manufactured by ICI) and the like.

<Aluminum compound (B)>
The composition of the present invention contains an aluminum compound (B) as a condensation reaction catalyst for promoting the curing reaction (formation of organopolysiloxane rubber) of the organopolysiloxane (A). By using the aluminum compound (B) as a catalyst for the condensation reaction, an antifouling paint composition having high environmental safety can be obtained. Moreover, the antifouling coating film formed can effectively exhibit a desired antifouling performance.

  As the aluminum compound (B), it is particularly preferable to use at least one aluminum compound selected from the group consisting of the following (B-1) to (B-5).

[Aluminum compounds (B-1), (B-2), (B-3)]
The composition of the present invention is represented by the general formula [1] as the aluminum compound (B):
Al (OR ¹ ) ₃ [1]
(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ¹ may be the same or different.)
A trialkoxyaluminum (trialkoxyaluminum [1]) represented by general formula [2]:
HO—R ² —OH [2]
(In the formula, R ² is an alkylene group having 2 to 10 carbon atoms, an alkenylene group or an alkynylene group.)
A diol compound represented by the formula (diol compound [2]) and / or general formula [3]:
HO-R ³ -Y ^[3]
(Wherein R ³ is an alkylene group having 2 to 10 carbon atoms, Y is a group represented by the formula: —OR ⁴ , or a group represented by the formula: —NR ⁵ R ⁶ ; ⁴ is an alkyl group or aryl group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ are the same or different and are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
It is preferable to contain the aluminum compound obtained by making the alcohol compound (alcohol compound [3]) represented by these react.

    In this specification, the reaction product of trialkoxyaluminum [1] and diol compound [2] is the aluminum compound (B-1), and the reaction product of trialkoxyaluminum [1] and alcohol compound [3]. The product is aluminum compound (B-2), and the reaction product of trialkoxyaluminum [1], diol compound [2] and alcohol compound [3] is aluminum compound (B-3).

The alkyl group having 1 to 10 carbon atoms represented by R ¹ may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group. Tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and the like. Preferred are hydrocarbon groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert-butyl group. More preferably, they are a methyl group, an ethyl group, a propyl group, and an isopropyl group.

  Examples of the trialkoxyaluminum [1] include trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, trisec-butoxyaluminum, tritert-butoxyaluminum, and tripentyloxyaluminum. , Trihexyloxyaluminum, triheptyloxyaluminum, trioctyloxyaluminum, trinonyloxyaluminum, tridecyloxyaluminum and the like. In particular, triisopropoxy aluminum is preferable.

The alkylene group having 2 to 10 carbon atoms represented by R ² is a divalent group obtained by removing two hydrogen atoms on different carbon atoms of a linear, branched or cyclic alkane having 2 to 10 carbon atoms. The group of is mentioned. Examples of the linear, branched or cyclic alkane having 2 to 10 carbon atoms include ethane, propane, isopropane, butane, isobutane, pentane, isopentane, neopentane, cyclopentane, hexane, isohexane, cyclohexane, heptane, and octane. , Nonane, decane and the like. Preferably, the bivalent group obtained by remove | excluding two hydrogen atoms on the carbon atom in the 1st-position and the 3rd-position of a C4-C8 linear or branched alkane is mentioned.

The alkenylene group having 2 to 10 carbon atoms represented by R ² is a divalent group obtained by removing two hydrogen atoms on different carbon atoms of a linear, branched or cyclic alkene having 2 to 10 carbon atoms. The group of is mentioned. Examples of the linear, branched or cyclic alkene having 2 to 10 carbon atoms include ethylene, propene, isopropene, cyclopropene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, isopentene, Examples include cyclopentene, hexene, isohexene, cyclohexene, heptene, octene, nonene, decene and the like.

The alkynylene group having 2 to 10 carbon atoms represented by R ² is a divalent group obtained by removing two hydrogen atoms on different carbon atoms of a linear, branched or cyclic alkyne having 2 to 10 carbon atoms. The group of is mentioned. Examples of the linear, branched or cyclic alkyne having 2 to 10 carbon atoms include acetylene, propyne, 1-butyne, 2-butyne, 1-pentyne, 2-pentyne, 1-isopentine, 1-hexyne, 2 -Hexin, 1-isohexyne, 2-isohexyne, heptin, octyne, nonin, decyne and the like.

  Examples of the diol compound [2] include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butane. Diol, cis-2-butene-1,4-diol, 1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,2-dimethyl-1, Examples include 3-propanediol, 2-ethyl-1,3-hexanediol, 1,6-hexanediol, and 2-methyl-2,4-pentanediol. In particular, 2-methyl-2,4-pentanediol is preferable.

The alkylene group having 2 to 10 carbon atoms represented by R ³ is a divalent group obtained by removing two hydrogen atoms on different carbon atoms of a linear, branched or cyclic alkane having 2 to 10 carbon atoms. The group of is mentioned. Examples of the linear, branched or cyclic alkane having 2 to 10 carbon atoms include ethane, propane, isopropane, butane, isobutane, pentane, isopentane, neopentane, cyclopentane, hexane, isohexane, cyclohexane, heptane, and octane. , Nonane, decane and the like. An alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group is particularly preferable.

The alkyl group having 1 to 10 carbon atoms represented by R ⁴ may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl. Group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and the like. Preferred are hydrocarbon groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert-butyl group. More preferably, they are a methyl group, an ethyl group, a propyl group, and an isopropyl group.

Examples of the aryl group represented by R ⁴ include aryl groups such as phenyl group, 1-naphthyl group, 2-naphthyl group, indenyl group, biphenylyl group, anthryl group, and phenanthryl group. Preferably, it is an aryl group having 6 to 10 carbon atoms. More preferred is a phenyl group.

The alkyl group having 1 to 10 carbon atoms represented by R ⁵ and R ⁶ may be linear, branched or cyclic. For example, 1 carbon atom such as methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. -10 linear, branched or cyclic alkyl groups. Preferably, it is a linear or branched alkyl group having 1 to 4 carbon atoms. More preferred is a methyl group.

    Examples of the alcohol compound [3] include 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol monoisopropyl ether, 2-butoxyethanol, ethylene glycol monobenzyl ether, 2-phenoxyethanol, 2-aminoethanol, 2-diethylaminoethanol. , 2- (benzylamino) ethanol, 2-dimethylaminoethanol and the like. In particular, 2-methoxyethanol, 2-butoxyethanol, and 2-dimethylaminoethanol are preferable.

  The aluminum compounds (B-1) to (B-3) are prepared by changing the number of equivalents of the diol compound [2] and / or the alcohol compound [3] to be reacted with the trialkoxyaluminum [1]. Can be manufactured.

  For example, 1 mol of the trialkoxyaluminum [1] is reacted with 1 to 3 mol of the diol compound [2] and / or 1 to 3 mol of the alcohol compound [3] to react with an aluminum compound (B-1). -(B-3) can be manufactured.

As a production method, for example, the trialkoxyaluminum [1] and the diol compound [2] and / or the alcohol compound [3] are added and refluxed in an inert gas atmosphere, and then a by-product alcohol (R ¹ OH) is distilled off under reduced pressure to obtain aluminum compounds (B-1) to (B-3). The reaction temperature is generally about 80 to 120 ° C., and the reaction time is about 2 to 6 hours.

  It should be noted that the chemical structure of the aluminum compound to be produced varies depending on the type and number of equivalents of the diol compound [2] and / or alcohol compound [3] to be added, and may exist as a mixture. It was decided that the aluminum compound obtained in the above will be defined by the production method.

    The aluminum compound (B-1) can be produced by reacting 1 to 3 mol of the diol compound [2] with respect to 1 mol of the trialkoxyaluminum [1]. For example, when 2-methyl-2,4-pentanediol is used as the diol compound [2], an aluminum compound (B-1) represented by the following (a) to (c) is mainly obtained. It is done.

    The aluminum compound (B-2) can be produced by reacting 1 to 3 mol of the alcohol compound [3] with 1 mol of the trialkoxyaluminum [1]. For example, it is considered that an aluminum compound (B-2) represented by the following (d) to (g) is obtained.

    The aluminum compound (B-3) is produced by reacting 1 to 2 mol of the diol compound [2] and 1 to 2 mol of the alcohol compound [3] with respect to 1 mol of the trialkoxyaluminum [1]. Can be manufactured. For example, when 2-methyl-2,4-pentanediol is used as the diol compound [2], it is considered that the aluminum compound (B-3) represented by the following (h) to (i) is obtained.

[Aluminum compound (B-4)]
The composition of the present invention is represented by the general formula [4] as the aluminum compound (B).

Wherein R ⁷ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and R ⁸ is a linear or branched alkyl group having 1 to 10 carbon atoms. Or a linear or branched alkoxy group having 1 to 10 carbon atoms, n is 1 or 2, and when n is 2, two R ^{7 s} may be the same or different from each other .)
It is preferable to contain the aluminum compound (B-4) represented by these.

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms represented by R ⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples include pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, cyclopentyl group, cyclohexyl group and the like. Preferably, it is a linear, branched or cyclic alkyl group having 2 to 8 carbon atoms. More preferred are propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like. .

Examples of the aryl group represented by R ⁷ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an indenyl group, a biphenyl group, an anthryl group, a phenanthryl group, and a benzyl group. Preferably, it is an aryl group having 6 to 10 carbon atoms. More preferably, it is represented by a phenyl group.

Examples of the aralkyl group represented by R ⁷ include a benzyl group and a phenethyl group. It is preferably represented by a benzyl group.

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and pentyl. Group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and the like. Preferably, it is a C1-C4 hydrocarbon group. More preferably, they are a methyl group and an ethyl group.

Examples of the linear or branched alkoxy group having 1 to 10 carbon atoms represented by R ⁸ include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, penloxy group, hexyloxy group, heptyloxy Group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, phenoxy group and the like. Preferably, it is a linear or branched alkyl group having 2 to 8 carbon atoms. More preferred are a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  Among the aluminum compounds represented by the general formula [4], a compound with n = 2 is particularly preferable from the viewpoints of physical properties and stability.

    As specific examples of the aluminum compound (B-4), when n = 2, aluminum acetylacetonate / dimethylate, aluminum acetylacetonate / diethylate, aluminum acetylacetonate / dipropylate, aluminum acetylacetonate / diisopropylate, aluminum Acetylacetonate dibutyrate, aluminum acetylacetonate diisobutyrate, aluminum acetylacetonate disec-butyrate, aluminum acetylacetonate ditert-butyrate, aluminum acetylacetonate diamylate, aluminum acetylacetonate diisoamylate, Aluminum acetylacetonate / di-tert-amylate, aluminum acetylacetonate / Hexylate, Aluminum acetylacetonate / diheptylate, Aluminum acetylacetonate / Dioctylate, Aluminum acetylacetonate / Di-2-ethylhexylate, Aluminum acetylacetonate / Dicyclopentylate, Aluminum acetylacetonate / Dicyclohexylate, Aluminum acetyl Acetonate diphenylate, aluminum acetylacetonate dibenzylate, aluminum alkyl (C1-C10) acetoacetate dimethylate, aluminum alkyl (C1-C10) acetoacetate diethylate, aluminum alkyl (C1-C10) acetoacetate dipropylate, aluminum alkyl (C1-C10) acetoacetate diisopropylate Aluminum alkyl (C1 to C10) acetoacetate dibutyrate, Aluminum alkyl (C1 to C10) acetoacetate diisobutyrate, Aluminum alkyl (C1 to C10) acetoacetate disec-butylate, Aluminum alkyl (C1 to C10) aceto Acetate ditert-butyrate, aluminum alkyl (C1-C10) acetoacetate diamylate, aluminum alkyl (C1-C10) acetoacetate diisoamylate, aluminum alkyl (C1-C10) acetoacetate ditert-amylate, aluminum alkyl (C1 ˜C10) acetoacetate dihexylate, aluminum alkyl (C1 to C10) acetoacetate diheptylate, aluminum a Rukyle (C1 to C10) acetoacetate dioctylate, aluminum alkyl (C1 to C10) acetoacetate di2-ethylhexylate, aluminum alkyl (C1 to C10) acetoacetate dicyclopentylate, aluminum alkyl (C1 to C10) ) Acetoacetate dicyclohexylate, aluminum alkyl (C1 to C10) acetoacetate diphenylate, aluminum alkyl (C1 to C10) acetoacetate dibenzylate and the like.

  When n = 1, aluminum bis (acetylacetonate) methylate, aluminum bis (acetylacetonate) ethylate, aluminum bis (acetylacetonate) propylate, aluminum bis (acetylacetonate) isopropylate, aluminum bis (acetylacetonate) Butyrate, Aluminum bis (acetylacetonate) isobutyrate, Aluminum bis (acetylacetonate) sec-butylate, Aluminum bis (acetylacetonate) tert-butylate, Aluminum bis (acetylacetonate) amylate, Aluminum bis (acetylacetonate) isoamylate Aluminum bis (acetylacetonate) tert-amylate, aluminum bis (acetylacetonate) ) Hexylate, aluminum bis (acetylacetonate) heptylate, aluminum bis (acetylacetonate) octylate, aluminum bis (acetylacetonate) 2-ethylhexylate, aluminum bis (acetylacetonate) cyclopentylate, aluminum bis (acetyl) Acetonate) cyclohexylate, aluminum bis (acetylacetonate) phenylate, aluminum bis (acetylacetonate) benzylate, aluminum bis (alkyl (C1-C10) acetoacetate) methylate, aluminum bis (alkyl (C1-C10) acetate Acetate) ethylate, aluminum bis (alkyl (C1-C10) acetoacetate) propirate, aluminum bis (alkyl (C ˜C10) acetoacetate) isopropylate, aluminum bis (alkyl (C1 to C10) acetoacetate) butyrate, aluminum bis (alkyl (C1 to C10) acetoacetate) isobutyrate, aluminum bis (alkyl (C1 to C10) acetoacetate) sec -Butyrate, aluminum bis (alkyl (C1-C10) acetoacetate) tert-butylate, aluminum bis (alkyl (C1-C10) acetoacetate) amylate, aluminum bis (alkyl (C1-C10) acetoacetate) isoamylate, aluminum bis ( Alkyl (C1-C10) acetoacetate) tert-amylate, aluminum bis (alkyl (C1-C10) acetoacetate) hexylate, aluminum Aluminum bis (alkyl (C1-C10) acetoacetate) heptylate, Aluminum bis (alkyl (C1-C10) acetoacetate) octylate, Aluminum bis (alkyl (C1-C10) acetoacetate) 2-ethylhexylate, Aluminum bis (alkyl (C1-C10) acetoacetate) cyclopentylate, aluminum bis (alkyl (C1-C10) acetoacetate) cyclohexylate, aluminum bis (alkyl (C1-C10) acetoacetate) phenylate, aluminum bis (alkyl (C1- C10) acetoacetate) benzylate and the like.

  The alkyl (C1 to C10) means an alkyl group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group having 2 to 8 carbon atoms, more preferably a methyl group or an ethyl group. Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group.

[Aluminum compound (B-5)]
The composition of the present invention is represented by the general formula [5] as the aluminum compound (B).

(In the formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different from each other, and are each a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 2, and n is 2. Sometimes the two R ^9s may be the same or different from each other.)
It is preferable to contain the aluminum compound (B-5) represented by these.

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ⁹ , R ¹⁰ , R ¹¹ and R ¹² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group. . Preferably, it has 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, amyl group, isoamyl group, and tert-amyl group. And an alkyl group. More preferably, R ⁹ is isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, R ¹⁰ , R ¹¹ and R ¹² are the same or different from each other, methyl, ethyl, Examples include propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

Among the aluminum compounds represented by the general formula [5], in particular, those in which R ⁹ is a butyl group, R ¹⁰ , R ¹¹ and R ¹² are isopropyl groups and n = 2 from the viewpoints of physical properties, stability and production cost. preferable.

  Specific examples of the aluminum compound represented by the formula [5] include isopropoxybis (trimethylsiloxy) aluminum, butoxybis (trimethylsiloxy) aluminum, amyloxybis (trimethylsiloxy) aluminum, isoamyloxybis (trimethylsiloxy) aluminum, tert -Amyloxybis (trimethylsiloxy) aluminum, isopropoxybis (triisopropylsiloxy) aluminum, butoxybis (triisopropylsiloxy) aluminum, amyloxybis (triisopropylsiloxy) aluminum, isoamyloxybis (triisopropylsiloxy) aluminum, tert-amyloxybis (tri Isopropylsiloxy) aluminum, diisopropoxytrimethylsiloxyaluminum, di Toxitrimethylsiloxyaluminum, diamyloxytrimethylsiloxyaluminum, diisoamyloxytrimethylsiloxyaluminum, ditert-amyloxytrimethylsiloxyaluminum, diisopropoxytriethylsiloxyaluminum, dibutoxytriethylsiloxyaluminum, diamyloxytriethylsiloxyaluminum, di Isoamyloxytriethylsiloxyaluminum, ditert-amyloxytriethylsiloxyaluminum, diisopropoxytributylsiloxyaluminum, dibutoxytributylsiloxyaluminum, diamyloxytributylsiloxyaluminum, diisoamyloxytributylsiloxyaluminum, ditert-amyloxytributyl Siloxyaluminum, diisopre Poxytriisopropylsiloxyaluminum, dibutoxytriisopropylsiloxyaluminum, diamyloxytriisopropylsiloxyaluminum, diisoamyloxytriisopropylsiloxyaluminum, ditert-amyloxytriisopropylsiloxyaluminum, tris (trimethylsiloxy) aluminum, tris (triethyl) Siloxy) aluminum, tris (triisopropylsiloxy) aluminum, tris (tributylsiloxy) aluminum and the like.

As the aluminum compound (B-5), for example, trialkoxyaluminum and trialkylsilanol (and other alcohol if necessary) can be obtained, wherein n in the general formula [5] is 0, 1, or 2. In a predetermined molar ratio. Typically, the general formula [6]:
(R ⁹ O) ₃ Al [6]
(Wherein R ⁹ is the same as above)
A trialkoxyaluminum (trialkoxyaluminum [6]) represented by general formula [7]:

(Wherein R ¹⁰ , R ¹¹ and R ¹² are the same as above).
And a silanol compound (silanol compound [7]) represented by general formula [5] is reacted so that n is 0, 1, or 2. Specifically, when 1 mole of silanol compound [7] is reacted with 1 mole of trialkoxyaluminum [6], n = 2, and when 1 mole of silanol compound [7] is reacted, n = 1. When 3 moles of silanol compound [7] are reacted, n = 0.

As a method for producing the aluminum compound (B-5), for example, the trialkoxyaluminum [6] and the silanol compound [7] are stirred and mixed, and then the alcohol (R ⁹ OH) generated by substitution is distilled off under reduced pressure. The method of obtaining the target aluminum compound (B-5) by doing is mentioned. The reaction temperature is generally about 80 to 120 ° C., and the reaction time is about 2 to 4 hours.

  Although content of the said aluminum compound (B) in the composition of this invention is not limited, 0.01-20 weight part is preferable with respect to 100 weight part of organopolysiloxane (A), and 0.03- 10 parts by weight is more preferable. When the content of the aluminum compound (B) is less than 0.01 parts by weight, the catalytic ability may not be sufficiently exhibited. When the content of the aluminum compound (B) exceeds 20 parts by weight, the catalytic performance is not improved as much as it is accompanied, which may be disadvantageous economically.

  In addition to the aluminum compound (B), the composition of the present invention may contain a compound used as a silicone curing catalyst, if necessary. Examples of the compound include zinc naphthenate, cobalt naphthenate, cobalt octylate, zirconium naphthenate, tetrabutyl orthotitanate, tin (II) 2-ethylhexanoate, tin (II) neodecanoate, and 2-ethylhexanoic acid. Examples thereof include bismuth (III), bismuth (III) neodecanoate, diethanolamine, and triethanolamine. These compounds can be used alone or in combination of two or more.

<Silicone oil (C)>
Silicone oil (C) is a component for raising the surface of the coating film formed by the composition of the present invention and imparting antifouling performance. Silicone oil (C) is excellent in compatibility with the organopolysiloxane rubber formed by the condensation reaction of the organopolysiloxane (A). Therefore, according to the composition of this invention, the coating film excellent in the coating-film performance which cannot produce peeling etc. can be formed suitably.

  As the silicone oil (C), silicone oils conventionally used in silicone rubber antifouling paints can be used.

It is preferably 10~100,000mm ² · s viscosity of the silicone oil (C), 100~5,000mm ² · s is more preferable.

  Silicone oil is classified into straight silicone oil and modified silicone oil, and both can be used in the composition of the present invention.

  Examples of the straight silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and the like.

  Commercially available products of straight silicone oil include KF-50, KF-53, KF-54, KF-56, KF-96 (above, Shin-Etsu Chemical Co., Ltd.), SH510, SH550, SH710 (above, Toray Dow) Corning Silicone, Inc.), DKQ8-779 (above, Dow Corning, Inc.), TSF451, TSF4300, TSF437, TSF400, TSF401, TSF484, TSF433, TSF431 (above, Momentive Performance Materials).

  Modified silicone oils are amino-modified, carboxyl-modified, epoxy-modified, polyether-modified, carbinol-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, hydrophilic special modification, higher alkoxy-modified, higher fatty acid depending on the type of modification. It may be classified into inclusion modification, fluorine modification and the like. Any of these modified silicone oils can be used, and amino-modified, epoxy-modified or polyether-modified silicone oils are particularly preferable.

  As commercially available products of modified silicone oil, SF8417 (product of Toray Dow Corning Silicone), ISI4700, ISI4701 (product of Toshiba Silicone), FZ3712, AFL-40 (product of Nihon Unicar), KF-8010, X-22-161, KF-8012 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), TSF4700, TSF4701 (above, Momentive Performance Materials Co., Ltd.), etc. Examples of commercially available products include X142-411 (product of Toshiba Silicone), SF8418 (product of Toray Dow Corning), FXZ3707 (product of Nihon Unicar), X-22-162C (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Epoxy-modified silico SF8411 (product of Toray Dow Corning Silicone), ISI4730, XI42-301 (product of Toshiba Silicone), L-9300, T-29 (product of Nippon Unicar Company), KF-105 (above, Shin-Etsu Chemical) Industrial product), TSF4730 (above, product of Momentive Performance Materials) and the like, and commercially available products of polyether-modified silicone oil are ISI4460, ISI4445, ISI4446 (product of Toshiba Silicone), SH3746, SH8400, SH3749, SH3700 (product of Toray Dow Corning Silicone) KF6009, X22-4822 (product of Shin-Etsu Silicone), TSF4440, TSF4441, TSF4445, TSF4460 (above, Momentive Performance As a commercial product of carbinol-modified silicone oil, X-22-160AS, KF-6001, KF-6002, KF-6003, X-22-170DX, X-22-176. (Above, Shin-Etsu Chemical Co., Ltd. products).

  Although content of the said silicone oil (C) in the composition of this invention is not limited, 10-200 weight part is preferable with respect to 100 weight part of said organopolysiloxane (A), and 50-150 weight part is. More preferred. When the content of the silicone oil (C) is less than 10 parts by weight, the antifouling effect may not be exhibited for a long time. When content of this silicone oil (C) exceeds 200 weight part, there exists a possibility that the intensity | strength of the coating film obtained may fall and antifouling property cannot be maintained.

<Crosslinking agent>
You may make the composition of this invention contain a crosslinking agent as needed.

  The cross-linking agent three-dimensionally cross-links the organopolysiloxane (A) to produce silicone rubber.

  As the cross-linking agent, for example, one molecule of a functional group that is hydrolyzed in the presence of moisture (may be moisture in the air) and reacts with the cross-linking reactive functional group in the organopolysiloxane (A). A polyfunctional silane compound having two or more thereof can be used. Examples of the functional group include acyloxy groups such as an acetoxy group, octanoyloxy group, and benzoyloxy group; alkoxy groups such as a methoxy group, ethoxy group, and propoxy group; ketoxime groups such as a methylethyl ketoxime group and a diethyl ketoxime group; Alkenyloxy groups such as isopropenyloxy group and 1-ethyl-2-methylvinyl group; alkylamino groups such as dimethylamino group, diethylamino group and butylamino group; alkylaminoxy groups such as dimethylaminoxy group and diethylaminoxy group Etc.

  The polyfunctional silane compound may further have an organic group other than the functional group. Examples of the organic group include the same organic groups as those described above which the organopolysiloxane (A) has on a silicon atom.

  Examples of the polyfunctional silane compound include methyltris (methylketoxime) silane, vinyltris (methylethylketoxime) silane, tetra (methylethylketoxime) silane, methyltri (N, N-diethylamino) silane, methyltriacetoxysilane, tetramethoxysilane, Tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, trimethoxyisopropoxysilane, methoxytriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, partial hydrolysis of these Examples include polycondensates. These can be used alone or in admixture of two or more.

  The content of the crosslinking agent in the composition of the present invention is not particularly limited and can be appropriately set according to the type and the like, but is usually 1 to 100 parts by weight of the organopolysiloxane (A). 100 parts by weight, preferably 3 to 80 parts by weight.

<Inorganic filler>
The composition of the present invention may further contain an inorganic filler for the purpose of improving the physical properties of the coating film.

  Examples of the inorganic filler include silica fine powder such as wet method silica and dry method silica, fumed titanium dioxide, diatomaceous earth, aluminum hydroxide, fine particulate alumina, magnesium oxide, zinc oxide, calcium carbonate, zinc carbonate and the like. Is mentioned. In addition, those having a hydrophobic surface treatment with dimethyldichlorosilane, hexamethyldisilazane, cyclic dimethylsiloxane or the like can be used. These inorganic fillers can be used singly or in combination of two or more.

  Content of the inorganic filler in the composition of this invention is 1-30 weight part normally with respect to 100 weight part of organopolysiloxane (A), Preferably it is 3-25 weight part.

<Organic solvent>
The composition of the present invention is usually dissolved and dispersed in an organic solvent. Thereby, it can use suitably as a coating material. Examples of the organic solvent include xylene, toluene, mineral spirits, MIBK, butyl acetate and the like. Of these, xylene is particularly preferable. These organic solvents can be used alone or in admixture of two or more.

<Other additives>
In addition, the antifouling coating composition of the present invention may contain a plasticizer as necessary. Specific examples of the plasticizer include phosphate esters such as tricresyl phosphate, trioctyl phosphate, and triphenyl phosphate; phthalate esters such as dibutyl phthalate and dioctyl phthalate; adipic acid such as dibutyl adipate and dioctyl adipate Esters; sebacic acid esters such as dibutyl sebacate and dioctyl sebacate; epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil; alkyl vinyl ether polymers such as methyl vinyl ether polymer and ethyl vinyl polymer; polyethylene glycol , Polyalkylene glycols such as polypropylene glycol, etc., ethylenically unsaturated carboxylic acid ester polymer, t-nonylpentane sulfide, chlorinated paraffin, solid paraffin, liquid paraffin Vaseline, and the like. The content of the plasticizer is usually about 20 parts by weight or less, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the organopolysiloxane (A).

  Furthermore, if necessary, pigments such as coloring pigments, extender pigments, rust preventive pigments, sagging inhibitors, silane coupling agents, antifouling agents and the like can be appropriately blended.

Method for Producing Antifouling Paint Composition The antifouling paint composition of the present invention comprises the above-mentioned organopolysiloxane (A), aluminum compound (B), silicone oil (C), if necessary, a crosslinking agent, an inorganic filler, an organic It can be prepared by mixing and dispersing a solvent, a plasticizer and the like.

  What is necessary is just to adjust suitably the addition amount of the said organopolysiloxane (A) etc. so that content of the said organopolysiloxane (A) etc. may become the range mentioned above in the said composition, respectively.

  When a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane, or tetrapropoxysilane is used as a crosslinking agent, the viscosity of the paint tends to increase. Therefore, after adding silicone oil (C), It is desirable from the viewpoint of coating workability to add and mix a crosslinking agent.

  As a method for producing a composition in which the organopolysiloxane (A) in the composition of the present invention has been converted to an organopolysiloxane rubber in advance, for example, the organopolysiloxane (A) and the aluminum compound ( B) is mixed, and usually at 25 to 80 ° C., preferably at 25 to 50 ° C., the crosslinking reactive functional group in the organopolysiloxane (A) and the crosslinking reactive functional group of another organopolysiloxane (A). And a method in which an organopolysiloxane rubber is produced by a condensation reaction with a hydrolyzable group in a crosslinking agent, and then the organopolysiloxane rubber and silicone oil (C) are mixed.

Antifouling treatment method The antifouling treatment method of the present invention is characterized in that an antifouling coating film is formed on the surface of a coating film forming article using the antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film is gradually dissolved from the surface and the coating film surface is constantly renewed, thereby preventing the adhesion of waterpox fouling organisms over a long period of time. Moreover, after dissolving a coating film, the antifouling effect can be exhibited continuously by overcoating the said composition.

  Since the coating composition of the present invention absorbs moisture in the air and cures gradually, it is preferable to prepare it immediately before use and to paint as soon as possible after preparation.

Examples of coating formations include ships; fishing nets (aquaculture nets, stationary nets, etc.), fishing net accessories, etc .; jetty, tetrapots, port facilities, buoys, pipelines, bridges, powerhouse conduits, seabeds Examples include underwater structures such as bases and offshore oil field drilling facilities.
The antifouling coating film of the present invention can be formed by applying the above antifouling coating composition to the surface (entirely or partly) of the coating film forming product.

  Application of the antifouling coating composition can be carried out by means known per se, by a single application or by repeated application.

  Examples of the application method include brush coating, spraying, dipping, flow coating, and spin coating. These may be performed alone or in combination of two or more.

  After application, moisture (for example, moisture in the air) is absorbed and curing proceeds to form the antifouling coating film of the present invention. Curing proceeds even at room temperature (25 ° C.), but curing can be promoted by heating to a temperature up to about 80 ° C., for example.

Antifouling coating film and coated article The antifouling coating film of the present invention can be formed using the composition of the present invention.

  What is necessary is just to set suitably the thickness of the antifouling coating film of this invention according to the kind etc. of to-be-coated-film formation thing. Generally, the cured film thickness is in the range of 50 to 300 μm, preferably 100 to 200 μm.

  The coated article of the present invention has the antifouling coating film on the surface. The coated product of the present invention may have the antifouling coating film on the entire surface or a part thereof.

  Since the painted product of the present invention can continuously exhibit the antifouling effect, it can be suitably used as the above-mentioned ship (particularly the ship bottom), fishing equipment, underwater structure and the like.

  For example, when the antifouling coating film is formed on the ship bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, and the coating film surface is constantly renewed, thereby preventing adhesion of waterpox fouling organisms. it can.

  In addition, the antifouling coating film is suitably suppressed in hydrolysis rate in seawater. Therefore, the ship can maintain antifouling performance for a long period of time. For example, even in a stationary state such as during berthing or during outfitting, there is little adhesion and accumulation of Minamata fouling organisms, and the antifouling effect can be exhibited for a long period of time.

  In addition, even after a long period of time, the antifouling coating on the surface is basically free from cracks or peeling. Therefore, it is not necessary to perform another operation such as forming a coating film after the coating film is completely removed. Therefore, an antifouling coating film can be suitably formed by directly overcoating the antifouling coating film composition. Thereby, it is possible to easily and continuously maintain the antifouling performance at a low cost.

Antifouling coating film forming kit The antifouling coating film forming kit of the present invention is
(1) a container containing the organopolysiloxane (A), and (2) a container containing the aluminum compound (B), and the silicone oil (C) comprises the container (1) and / or It is contained in this container (2).

  The kit can be used as a two-component antifouling paint, and is particularly excellent in storage stability. The said kit can form the antifouling coating film excellent in antifouling performance similarly to the case where the said antifouling paint composition is used.

  The shape, size, and the like of the container (1) and the container (2) are not particularly limited, and may be appropriately selected according to the target coating film forming object. For example, a tube-like container is preferable in terms of excellent workability.

  The contents of the aluminum compound (B) and the silicone oil (C) in the kit are within the ranges explained in the items <Aluminum compound (B)> and <Silicone oil (C)>. It is preferable to set.

  You may make the said container (1) and / or the said container (2) contain the said crosslinking agent, an inorganic filler, an organic solvent, another additive, etc. as needed.

  The said kit can form the antifouling coating film excellent in antifouling performance in the coating-film formation object similarly to the said antifouling paint composition.

  As a method of forming a coating film using the kit, for example, immediately before coating, the contents of the container (1) and the contents of the container (2) are mixed, and the resulting mixture is coated. Examples thereof include a method of coating the film-formed product, a method of coating the content of the container (1) on the film-formed product, and a method of coating the content of the container (2) thereon.

  In the presence of moisture, the contents of the container (1) and the contents of the container (2) are mixed, or after the contents of the container (1) are applied to the coating film formation, By applying the contents of the container (2), an organopolysiloxane rubber can be suitably formed from the organopolysiloxane (A), and a coating film excellent in antifouling performance can be formed.

  The antifouling coating composition and the antifouling coating film forming kit of the present invention can form an antifouling coating film having excellent antifouling performance. Moreover, since the composition and kit of the present invention contain an aluminum compound instead of a dialkyltin compound as a curing catalyst, it is highly environmentally safe and has almost no problem of marine pollution even when dissolved in seawater.

  Examples and the like are shown below to further clarify the features of the present invention. However, the present invention is not limited to these examples.

Production Production Example 1 of Aluminum Compound (B) (Production of Aluminum Compound (B-1))
In a 500 ml eggplant-shaped flask equipped with a nitrogen introduction tube, 153.2 g (0.75 mol) of triisopropoxyaluminum, 132.94 g of 2-methyl-2,4-pentanediol (hereinafter referred to as hexylene glycol) (1 .13 mol) was weighed and refluxed for 30 minutes, and then the produced isopropyl alcohol was distilled off under reduced pressure to obtain 298.8 g (yield 99%) of a light yellow viscous liquid aluminum compound (B-1). This compound was analyzed by FT-IR, and it was confirmed that there was no hydroxyl group absorption (3367 cm ⁻¹ ) of hexylene glycol. Moreover, from the result of the following elemental analysis, it was confirmed that the molar ratio of triisopropoxyaluminum to hexylene glycol was a reaction product of 2: 3.

Production Example 2 (Production of aluminum compound (B-2))
A 500 ml eggplant-shaped flask equipped with a nitrogen inlet tube was weighed with 153.2 g (0.75 mol) of triisopropoxyaluminum and 66.9 g (2.25 mol) of 2-dimethylaminoethanol, and was refluxed for 30 minutes. The isopropyl alcohol was distilled off under reduced pressure to obtain 211.9 g (yield 97%) of a light yellow liquid aluminum compound (B-2). This compound was analyzed by FT-IR, and it was confirmed that there was no hydroxyl group absorption (3398 cm ⁻¹ ) of 2-dimethylaminoethanol. Moreover, from the result of the following elemental analysis, it was confirmed that the molar ratio of triisopropoxyaluminum to 2-dimethylaminoethanol was a 1: 3 reaction product.

Production Example 3 (Production of aluminum compound (B-3))
To a 500 ml eggplant-shaped flask equipped with a nitrogen introduction tube, 153.2 g (0.75 mol) of triisopropoxyaluminum and 88.7 g (0.75 mol) of hexylene glycol were weighed and refluxed for 30 minutes. The alcohol was distilled off under reduced pressure. Next, 66.9 g (0.75 mol) of 2-dimethylaminoethanol was weighed and refluxed for 30 minutes, and then the produced isopropyl alcohol was distilled off under reduced pressure to obtain a pale yellow liquid aluminum compound (B-3). 0 g (yield 98%) was obtained. This compound was analyzed by FT-IR, and it was confirmed that there was no hydroxyl group absorption (3350 to 3400 cm ⁻¹ ) of each alcohol. Moreover, from the result of the following elemental analysis, it confirmed that the molar ratio of triisopropoxy aluminum, hexylene glycol, and 2-dimethylaminoethanol was 1: 1: 1.

Production Example 4 (Production of aluminum compound (B-4))
24.63 g (0.10 mol) of tributoxyaluminum and 10.0 g (0.10 mol) of acetylacetone were weighed into a 100 ml eggplant-shaped flask equipped with a nitrogen introduction tube, and thoroughly mixed with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature, and then the produced butyl alcohol was distilled off under reduced pressure to obtain 26.1 g (yield) of a light yellow viscous liquid aluminum compound (B-4-1). 96%). The disappearance of the ketone of acetylacetone (1750 cm ⁻¹ ) and the absorption of aluminum carbonyl (1650 cm ⁻¹ , 1525 cm ⁻¹ ) were confirmed for this compound by FT-IR. Moreover, it confirmed that it was aluminum acetylacetonate dibutyrate from the result of the following elemental analysis.

Production Example 5 (Production of aluminum compound (B-4))
24.63 g (0.10 mol) of tributoxyaluminum and 20.0 g (0.20 mol) of acetylacetone were weighed into a 100 ml eggplant-shaped flask equipped with a nitrogen introduction tube, and thoroughly mixed with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature, and then the generated butyl alcohol was distilled off under reduced pressure to obtain 28.6 g (yield) of a light yellow viscous liquid aluminum compound (B-4-2). 96%). The disappearance of the ketone of acetylacetone (1750 cm ⁻¹ ) and the absorption of aluminum carbonyl (1650 cm ⁻¹ , 1525 cm ⁻¹ ) were confirmed for this compound by FT-IR. Moreover, it confirmed that it was aluminum bisacetylacetonate * butyrate from the result of the following elemental analysis.

Production Example 6 (Production of aluminum compound (B-4))
To a 100 ml eggplant type flask equipped with a nitrogen introduction tube, 24.6 g (0.10 mol) of tributoxyaluminum and 26.1 g (0.20 mol) of ethyl acetoacetate were weighed and mixed thoroughly with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature, and then the produced butyl alcohol was distilled off under reduced pressure to obtain 34.4 g (yield) of a light yellow viscous liquid aluminum compound (B-4-3). 96%). The disappearance of the ketone (1750 cm ⁻¹ ) of ethyl acetoacetate and the absorption of aluminum carbonyl (1650 cm ⁻¹ , 1525 cm ⁻¹ ) were confirmed for this compound by FT-IR. Moreover, it confirmed that it was aluminum bisethyl acetoacetate butyrate from the result of the following elemental analysis.

Production Example 7 (Production of aluminum compound (B-5))
To a 100 ml eggplant type flask equipped with a nitrogen introduction tube, 24.6 g (0.10 mol) of tributoxyaluminum and 17.4 g (0.10 mol) of triisopropylsilanol were weighed and mixed thoroughly with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature, and then the produced butyl alcohol was distilled off under reduced pressure to obtain 33.9 g (yield 98%) of a pale yellow liquid aluminum compound (B-5-1). ) This compound was analyzed by FT-IR, and it was confirmed that there was no silanol absorption (3435 cm ⁻¹ ). Moreover, it confirmed that it was dibutoxy triisopropyl siloxy aluminum from the result of the following elemental analysis.

Production Example 8 (Production of aluminum compound (B-5))
To a 100 ml eggplant type flask equipped with a nitrogen introduction tube, 24.6 g (0.10 mol) of tributoxyaluminum and 21.6 g (0.10 mol) of tributylsilanol were weighed and mixed thoroughly with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature, and then the produced butyl alcohol was distilled off under reduced pressure to obtain 38.1 g (yield 98%) of a pale yellow liquid aluminum compound (B-5-2). ) This compound was analyzed by FT-IR, and it was confirmed that there was no silanol absorption (3435 cm ⁻¹ ). Moreover, it confirmed that it was dibutoxy tributyl siloxy aluminum from the result of the following elemental analysis.

Production Example 9 (Production of aluminum compound (B-5))
20.4 g (0.10 mol) of triisopropoxyaluminum and 7.41 g (0.10 mol) of butyl alcohol were weighed into a 100 ml eggplant type flask equipped with a nitrogen introduction tube, and thoroughly mixed with a magnetic stirrer. After the generated isopropyl alcohol was distilled off under reduced pressure, 17.44 g (0.10 mol) of triisopropylsilanol was weighed and mixed well with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature, and then the produced isopropyl alcohol was distilled off under reduced pressure to obtain 32.2 g (yield) of a light yellow viscous liquid aluminum compound (B-5-3). 97%). This compound was analyzed by FT-IR, and it was confirmed that there was no silanol absorption (3435 cm ⁻¹ ). Moreover, it confirmed that it was isopropoxybutoxy triisopropyl siloxy aluminum from the result of the following elemental analysis.

Test Example 1 (Curability test of organopolysiloxane composition)
The aluminum compound (B) obtained in Production Examples 1 to 9 and various additives shown in Table 10 with respect to 100 parts by weight of the organopolysiloxane (A) shown in Table 10 are the proportions shown in Table 10 ( Each of the organopolysiloxane compositions was prepared by mixing in a stir mixer in the absence of moisture (Reference Examples 1 to 15 and Comparative Reference Examples 1 to 4). The mixing and mixing operations of each material were performed at 25 ° C. in the absence of moisture.

  Each of the obtained organopolysiloxane compositions was coated on a glass plate so that the dry film thickness was 200 μm, and then left to stand in an atmosphere of 20 ° C. and 60% RH. The time until disappearance (curing time) was measured by finger touch.

  The results are shown in Table 10.

Examples 1 to 15 and Comparative Examples 1 to 5 (Production of antifouling coating composition)
In the air, the organopolysiloxane compositions of Reference Examples 1 to 15 and Comparative Reference Examples 1 to 4 and the silicone oil (C) shown in Table 11 were blended in the proportions (parts by weight) shown in Table 11, and mixed by stirring. An antifouling coating composition was produced by uniformly mixing and dispersing in the machine.

Test example 2 (antifouling test)
A coated plate obtained by coating a sandblasted steel plate (100 × 300 × 2 mm) with an epoxy resin heavy-duty anticorrosive coating so that the dry coating film has a thickness of 200 μm was used. The coating composition obtained in Examples 1 to 15 and Comparative Examples 1 to 5 was brush-coated on the coated surface of this plate so that the dry coating film was about 150 μm, and dried in the air (in the presence of moisture). A test plate was prepared. This test plate was immersed in seawater in Owase Bay (Owase City, Mie Prefecture) 1.5 m below the sea level, and the degree of fouling by water fouling organisms was observed for 12 months.

  The adhesion area (%) of the fouling organism is shown in Table 11.

Example 16 (Anti-fouling coating film forming kit)
It is obtained by uniformly mixing 100 parts by weight of Tosseal 371 (organopolysiloxane (A)), 15 parts by weight of tetraethoxysilane (crosslinking agent) and 15 parts by weight of xylene in a stirring mixer in the absence of moisture. The mixture was filled into tubes. This was designated as a container (1).

  Further, 0.5 parts by weight of the aluminum compound (B-1) obtained in Production Example 1 and 100 parts by weight of KF96-100 (silicone oil (C)) were uniformly mixed in a stirring mixer in the absence of moisture. The mixture obtained by mixing was filled into a tube. This was designated as a container (2).

  As described above, an antifouling coating film forming kit comprising the container (1) and the container (2) was produced.

  Using the obtained kit, the same tests as in Test Examples 1 and 2 were performed.

  Specifically, the mixture of the container (1) was coated on a glass plate so that the dry film thickness was 200 μm, and then the mixture of the container (2) was coated thereon. Then, it was left to stand in an atmosphere of 20 ° C. and 60% RH, and the time (curing time) until tackiness (stickiness) on the coating film surface disappeared was measured by finger touch. The curing time was 4.0 hours.

  Moreover, instead of applying the coating compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 5, after applying the mixture of the container (1), the mixture of the container (2) is applied from above. The antifouling test was conducted in the same manner as in Test Example 2. After 3 months, 6 months and 12 months, the attached area of the fouling organisms was 0%.

Claims (10)

(A) an organopolysiloxane having a crosslinking reactive functional group,
(B) An antifouling coating composition containing an aluminum compound as a condensation reaction catalyst and (C) silicone oil. The antifouling agent according to claim 1, comprising 0.01 to 20 parts by weight of the aluminum compound (B) and 10 to 200 parts by weight of the silicone oil (C) with respect to 100 parts by weight of the organopolysiloxane (A). Paint composition. The aluminum compound (B) has the general formula [1]:
Al (OR ¹ ) ₃ [1]
(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ¹ may be the same or different.)
In the trialkoxyaluminum represented by the general formula [2]:
HO—R ² —OH [2]
(In the formula, R ² is an alkylene group having 2 to 10 carbon atoms, an alkenylene group or an alkynylene group.)
And / or the general formula [3]:
HO-R ³ -Y ^[3]
(Wherein R ³ is an alkylene group having 2 to 10 carbon atoms, Y is a group represented by the formula: —OR ⁴ , or a group represented by the formula: —NR ⁵ R ⁶ ; ⁴ is an alkyl group or aryl group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ are the same or different and are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
The antifouling paint composition according to claim 1, which is an aluminum compound obtained by reacting an alcohol compound represented by the formula: The aluminum compound (B) has the general formula [4]

Wherein R ⁷ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and R ⁸ is a linear or branched alkyl group having 1 to 10 carbon atoms. Or a linear or branched alkoxy group having 1 to 10 carbon atoms, n is 1 or 2, and when n is 2, two R ^{7 s} may be the same or different from each other .)
The antifouling paint composition according to claim 1, which is an aluminum compound represented by the formula: The aluminum compound (B) has the general formula [5]

(In the formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different from each other, and are each a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 2, and n is 2. Sometimes the two R ^9s may be the same or different from each other.)
The antifouling paint composition according to claim 1, which is an aluminum compound represented by the formula: The antifouling processing method which forms an antifouling coating film on the surface of a coating-film formation object using the antifouling paint composition in any one of Claims 1-5. The antifouling coating film formed using the antifouling paint composition in any one of Claims 1-5. A coated product having the antifouling coating film according to claim 7 on a surface thereof. In the presence of moisture, an organopolysiloxane having a crosslinking reactive functional group (A) and an aluminum compound (B) as a condensation reaction catalyst are mixed to produce an organopolysiloxane rubber. An antifouling paint composition obtained by mixing silicone oil (C). (1) a container containing an organopolysiloxane (A) having a crosslinking reactive functional group, and (2) a container containing an aluminum compound (B) as a catalyst for condensation reaction, and a silicone oil (C) Is a kit for forming an antifouling coating film, which is contained in the container (1) and / or the container (2).