JP5186079B2 - Organopolysiloxane composition, paint additive and antifouling paint composition - Google Patents

Description

The present invention relates to an organopolysiloxane composition comprising a polyoxyethylene group-bonded diorganopolysiloxane and a polyoxyethylene compound, a coating additive capable of continuously imparting slightly hydrophilicity to the coating film surface, and after curing The present invention relates to an antifouling coating composition that exhibits excellent antifouling performance, in particular, antifouling performance against aquatic organisms over a long period of time.

There are many organisms such as barnacles, sea squirts, cell plastics, mussels, crows mussels, chrysanthemum moths, aonori, aosa in the water such as seas, rivers, lakes and marshes. , Fish nets (hereinafter collectively referred to as “underwater moving objects”), port facilities, buoys, pipelines, bridge girder bridges, tetrapots, power station conduit pipes, submarine bases, subsea oil field drilling equipment, aquaculture nets, stationary nets ( If the so-called “underwater structure” is soaked for a long period of time, there is a problem that these organisms attach and grow innumerably from the splashed part to the surface of the submerged part, causing various damages.

Conventionally, antifouling paints containing toxic antifouling agents such as organotin compounds have been used for the prevention of biological adhesion of the above-mentioned underwater moving objects and underwater structures, but they are non-toxic in terms of environmental protection and safety and health. As an antifouling paint, an antifouling paint containing a non-silicone film-based preparation and an oxyalkylene group-containing chain organopolysiloxane having an HLB of 3 to 12 (Japanese Patent Publication No. 6-104793 [Patent Document 1]), an HLB of 2 Antifouling paint comprising a room temperature curable silicone rubber composition containing 12 to 12 polyoxyalkylene group-containing chain organopolysiloxane (JP-A-4-142373 [Patent Document 2]), room temperature curable silicone containing silicone oil An antifouling coating composition comprising a rubber composition (JP-A-10-316933 [Patent Document 3]), containing a polyoxyalkylene group-containing chain polyorganosiloxane Antifouling coating agent comprising a warm vulcanizable polyorganosiloxane composition (Japanese Patent Laid-Open No. 11-12541 [Patent Document 4]), and an antifouling paint comprising an organopolysiloxane fluid-containing room temperature curable organopolysiloxane composition having a polar group A composition for underwater structures comprising a composition (Japanese Patent Laid-Open No. 2002-291456 [Patent Document 5]) and a room temperature-curable organopolysiloxane composition containing an organopolysiloxane having an HLB of 1 to 8 and having a polyoxyalkylene group An antifouling paint (Japanese Patent Laid-Open No. 2004-143331 [Patent Document 6]) has been proposed.

However, the antifouling paint of Patent Document 3 uses both dimethyl silicone oil and polyethylene glycol-modified silicone oil. However, dimethyl silicone oil is extremely hydrophobic, so it is very difficult to elute from silicone rubber. Only polyethylene glycol-modified silicone oil is used. There is a problem that it is not different from the antifouling paint containing selenium.
Antifouling paints of patent documents other than Patent Document 3 contain only one type of polyoxyalkylene group-containing organopolysiloxane having a specific HLB, and have a large HLB and a highly hydrophilic polyoxyalkylene group-containing organopolysiloxane. When siloxane is contained, the compatibility with silicone rubber is poor, so after the coating film is formed, the polyoxyalkylene group-containing organopolysiloxane elutes quickly in the water that comes into contact with it. There is a problem of lacking. On the contrary, when polyoxyalkylene group-containing organopolysiloxane having a small HLB and low hydrophilicity is contained, it takes a long time for the polyoxyalkylene group-containing organopolysiloxane to bleed out to the coating film surface. There is a problem that the initial antifouling effect is poor.

Japanese Patent Publication No. 6-104793 JP-A-4-142373 JP 10-316933 A Japanese Patent Laid-Open No. 11-12541 JP 2002-294156 A JP 2004-143331 A

The present invention has been made to solve the above-described problems, and an organopolysiloxane composition capable of continuously imparting antifouling properties to the coating film surface over a long period from the initial stage of formation and addition of a coating material It aims at providing the agent and its manufacturing method. In addition, antifouling paints that can prevent the growth of underwater organisms on the surface of moving membranes of underwater moving objects and underwater structures for a long period of time, and can easily wash and wash the dirt adhering to the surface of coated membranes such as ground buildings. It is intended to provide a composition.

As a result of repeated studies to achieve the above object, the present inventors
[1] (A) It is liquid at normal temperature, HLB is 0.2-1.5, General formula (1):
_{^{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -SiMe 2 R 3 (1)
(Wherein Et is an ethylene group, Me is a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³⁾ Is an alkyl group having 1 to 20 carbon atoms, n is 2 to 20, and m is an integer of 10 to 100)
100 parts by weight,
(B) HLB is 13-18, General formula (2):
R ⁴ —O— (EtO) _n —R ⁴ (2)
In the formula, Et is an ethylene group, and R ⁴ is the same or different and is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a hydrogen atom. , N is an integer of 2 to 20), an organopolysiloxane composition comprising 1 to 20 parts by weight and having a viscosity at 25 ° C. of 20 to 1000 mPa · s.
[2] (A) It is liquid at normal temperature, HLB is 0.2-1.5, General formula (1):
_{^{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -SiMe 2 R 3 (1)
(Wherein Et is an ethylene group, Me is a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group having 1 to 20 carbon atoms, n is 2 to 20, and m is an integer of 10 to 100)
100 parts by weight,
(B) HLB is 13-18, General formula (2):
R ⁴ —O— (EtO) _n —R ⁴ (2)
In the formula, Et is an ethylene group, and R ⁴ is the same or different and is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a hydrogen atom. , N is an integer from 2 to 20) 1 to 20 parts by weight,
(C) It is liquid at normal temperature, HLB is 0.4-1.5, General formula (3):
_{^{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -R 2 -O- (EtO) n -R 1 (3)
(Wherein Et is an ethylene group, Me is a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and n is 2 to 20, m is an integer of 10 to 100) An organopolysiloxane composition comprising 1 to 400 parts by weight and having a viscosity at 25 ° C. of 20 to 1000 mPa · s.
[3] Furthermore, per 100 parts by weight of component (A) (D) is liquid at ordinary temperature, and is represented by the general formula (4):
_{^{R 3 - (SiMe 2 O)}} m -SiMe 2 R 3 (4)
Containing 10 to 100 parts by weight of a diorganopolysiloxane represented by the formula (wherein Me is a methyl group, R ³ is an alkyl group having 1 to 20 carbon atoms, and m is an integer of 10 to 100). [2] The organopolysiloxane composition according to [2].
[4] In General Formula (1), R ³ is an alkyl group having 4 to 18 carbon atoms, and in General Formula (2), one of R ⁴ is an alkenyl group having 2 to 4 carbon atoms, and the other is a carbon atom. The organopolysiloxane composition according to [1], which is an alkyl group of formulas 1 to 4 or a hydrogen atom.
[5] In general formula (1) and general formula (4), R ³ is an alkyl group having 4 to 18 carbon atoms, and in general formula (2), one of R ⁴ is an alkenyl group having 2 to 4 carbon atoms. And the other is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, [1], [2] or [3].
[6] General formula obtained by living polymerization using a metal alkyl initiator (wherein the alkyl group is R ³ ) in a solvent obtained by dehydrating hexamethylcyclotrisiloxane and stopping the polymerization with dimethylhalosilane. (5): H- (SiMe ₂ O) _m -SiMe ₂ R ³ (5)
(Wherein, Me is a methyl group, R ³ is an alkyl group having 4 to 18 carbon atoms, and m is an integer of 10 to 100), and an excess amount of the general formula ( 6): R ⁵ —O— (EtO) _n —R ⁵ (6)
(In the formula, one of R ⁵ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, the other of R ⁵ is an alkenyl group having 2 to 4 carbon atoms, and n is an integer of 2 to 20). The method for producing an organopolysiloxane composition according to [4], wherein the one-terminal alkenyl group-blocked polyoxyethylene compound is hydrosilylated in the presence of a platinum catalyst.
[7] General formula (7) obtained by equilibrium polymerization of dimethylcyclopolysiloxane and 1,1,3,3-tetramethyldisiloxane using an acidic catalyst:
H- (SiMe ₂ O) _m -SiMe ₂ H (7)
(In the formula, Me is a methyl group, m is an integer of 10 to 100), and the both-end functional dimethylpolysiloxane represented by the general formula (6) has a single-end alkenyl group-capped polyoxyethylene compound and carbon. The method for producing an organopolysiloxane composition according to [5], wherein an α-olefin having 4 to 18 atoms is hydrosilylated in the presence of a platinum catalyst simultaneously or stepwise.
[8] A paint additive comprising the organopolysiloxane composition according to any one of [1] to [5].
[9] An antifouling paint composition comprising the paint additive according to [8].
[10] The antifouling coating composition according to [9], wherein the film-forming component in the antifouling coating composition is a room temperature curable organopolysiloxane composition (E).
[11] (E) 100 parts by weight of a room temperature curable organopolysiloxane composition, 10 to 80 parts by weight of the paint additive according to [8], and (F) an organic solvent 4 to 100 having a boiling point of 100 ° C. to 200 ° C. [10] The antifouling coating composition according to [10], comprising parts by weight.
[12] The component (E) has (a) a viscosity at 25 ° C. of 20 to 1,000,000 mPa · s, and at least two silicon atom-bonded hydroxyl groups or silicon atom-bonded hydrolyzable groups in one molecule. From 100 parts by weight of diorganopolysiloxane, (b) from 5 to 100 parts by weight of an organosilicon compound having at least two silicon-bonded hydrolyzable groups in one molecule, and (c) from 0 to 10 parts by weight of a curing catalyst It was found that the above-mentioned problems can be solved by the antifouling paint composition according to [10] or [11], characterized in that the present invention has been completed.

The organopolysiloxane composition and paint additive of the present invention are formed on the surface of a coating film when blended with a paint composition, particularly a paint composition in which the film-forming component is a room temperature curable organopolysiloxane composition. Slightly hydrophilic can be imparted from the initial stage over a long period of time, and as a result, the situation where underwater organisms adhere to and grow on the coating film surface of underwater moving objects and underwater structures can be prevented for a long period of time. . In addition, the coating film surface of other coatings can be imparted with a slight hydrophilicity for a long time from the initial stage of the formation, and as a result, dirt adhering to the coating film surface can be easily washed with water. it can.
When the organopolysiloxane composition of the present invention is blended with rubber or plastic, particularly silicone rubber, it can continuously impart a slight hydrophilicity to the surface over a long period of time from the initial stage. It is possible to prevent adhesion of dirt and charging.
The antifouling paint composition of the present invention, in particular, the antifouling paint composition in which the film-forming component is a room temperature curable organopolysiloxane composition, is applied to the surface of the coating film for a long period from the initial stage of formation. As a result, it is possible to prevent a long-term situation in which aquatic organisms adhere to and grow on the surface of a coating film of an underwater moving object or an underwater structure. In addition, the coating film surface of other coatings can be imparted with a slight hydrophilicity for a long time from the initial stage of the formation, and as a result, dirt adhering to the coating film surface can be easily washed with water. it can.
The antifouling paint composition of the present invention does not substantially contain a highly toxic antifouling agent such as a tributyltin compound or a metal complex, and exhibits excellent antifouling properties for a long period of time immediately after coating. Since it is a non-toxic antifouling paint, it is very useful and advantageous from the viewpoint of environmental protection and safety and health.

The organopolysiloxane composition of the present invention comprises:
(A) It is liquid at normal temperature, HLB is 0.2-1.5, General formula (1):
_{^{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -SiMe 2 R 3 (1)
(Wherein Et is an ethylene group, Me is a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³⁾ Is an alkyl group having 1 to 20 carbon atoms, n is 2 to 20, and m is an integer of 10 to 100)
100 parts by weight,
(B) HLB is 13-18, General formula (2):
R ⁴ —O— (EtO) _n —R ⁴ (2)
In the formula, Et is an ethylene group, and R ⁴ is the same or different and is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a hydrogen atom. , N is an integer of 2 to 20), and has a viscosity at 25 ° C. in the range of 20 to 1000 mPa · s.

When component (A) is combined with component (B) in a coating composition, particularly a coating composition in which the film-forming component is a room temperature curable organopolysiloxane composition, component (A) and component (B) Because the period from the coating film to bleed-out is different, the surface of the coating film can be imparted with a slight hydrophilicity immediately after the formation of the coating film, and the slight hydrophilicity can be maintained over a long period of time. Last. In addition, when blended with rubber or plastic, especially silicone rubber, the surface of rubber or plastic, especially silicone rubber, maintains a moderate level of hydrophilicity due to the different bleed-out periods of component (A) and component (B). Is granted.

In the general formula (1), R ¹ is an alkyl group having 1 to 4 carbon atoms and includes a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group. R ² is an alkylene group having 2 to 4 carbon atoms, preferably a propylene group. R ³ is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 4 to 18 carbon atoms.
Component (A) is liquid at room temperature. When the component (A) has an HLB greater than the upper limit, bleeding out from the coating film is quick, and the sustainability of a moderately hydrophilic property-imparting effect is reduced. On the other hand, when the HLB is less than the lower limit, the component (A) does not sufficiently bleed out from the coating film, so that sufficient hydrophilicity cannot be imparted to the coating film. The group represented by the formula R ¹ — (EtO) n—O—R ² — bonded to one end of dimethylpolysiloxane is a hydrophilic group, and when the degree of polymerization exceeds 20, Uniformity tends to be insufficient. R ³ bonded to the other end of dimethylpolysiloxane is a hydrophobic group and preferably has 4 to 18 carbon atoms.

Since the component (B) has a polyoxyethylene chain and the HLB is 13 to 18, it is excellent in compatibility with the component (A), and more quickly from the coating film surface than the component (A). Bleeding out has the effect of imparting slight hydrophilicity to the surface immediately after the formation of the coating film. Component (B) is preferably liquid at normal temperature.
One of R ^{4 at} both ends is preferably an alkenyl group having 2 to 4 carbon atoms and the other is an alkyl group having 1 to 4 carbon atoms from the viewpoint of ease of production of this component and HLB.

The compounding quantity of a component (B) is 1-20 weight part with respect to 100 weight part of component (A), Preferably it is 1-15 weight part, More preferably, it is 1-10 weight part. If it exceeds 20 parts by weight, the compatibility and dispersibility with the coating composition, particularly with the room temperature curable organopolysiloxane composition will be reduced, and the adhesion and adhesion of the coating film to the substrate will be easily inhibited. If it is less than 1 part by weight, it is difficult to impart slight hydrophilicity to the surface of the coating film immediately after formation.

An organopolysiloxane composition comprising component (A) and component (B) can be easily prepared by, for example, synthesizing component (A) and component (B) separately by a well-known method and mixing them uniformly. Can be manufactured. However, in the general formula (1), R ³ is an alkyl group having 4 to 18 carbon atoms, in the general formula (2), one of R ⁴ is an alkenyl group having 2 to 4 carbon atoms, and the other is a carbon atom. The organopolysiloxane composition having an alkyl group of 1 to 4 or a hydrogen atom is prepared by using a metal alkyl initiator (provided that the alkyl group has 4 to 18 carbon atoms) in a solvent in which hexamethylcyclotrisiloxane is dehydrated. General formula (5) obtained by living polymerization using dimethylhalosilane and termination of polymerization with dimethylhalosilane: H- (SiMe ₂ O) _m -SiMe ₂ R ³ (5)
(Wherein Me is a methyl group, R ³ is an alkyl group having 4 to 18 carbon atoms, and m is an integer of 10 to 100), and a dimethylpolysiloxane containing one terminal hydrosilyl group, and an excess amount of the general formula (6): R ⁵ —O— (EtO) _n —R ⁵ (6)
(In the formula, one of R ⁵ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, the other of R ⁵ is an alkenyl group having 2 to 4 carbon atoms, and n is an integer of 2 to 20). It can be easily produced by subjecting the one-terminal alkenyl group-blocked polyoxyethylene compound to a hydrosilylation reaction in the presence of a platinum-based catalyst. The organopolysiloxane composition produced by this production method is preferable because the uniformity of the components and the dispersibility upon blending are good.

The organopolysiloxane composition is further (C) liquid at normal temperature, HLB is 0.4 to 1.5, and the general formula (3):
^{_{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -R 2 -O- (EtO) n -R 1 (3)
(Wherein Et is an ethylene group, Me is a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and n is 2 to 20, m may be an integer of 10 to 100) and may contain 1 to 400 parts by weight. That is,
(A) It is liquid at normal temperature, HLB is 0.2-1.5, General formula (1):
^{_{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -SiMe 2 R 3 (1)
(Wherein Et is an ethylene group, Me is a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkyl group having 1 to 20 carbon atoms, n is 2 to 20, and m is an integer of 10 to 100)
100 parts by weight,
(B) HLB is 13-18, General formula (2):
R ⁴ —O— (EtO) _n —R ⁴ (2)
(Wherein Et is an ethylene group, R ⁴ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a hydrogen atom, and n is 2) 1 to 20 parts by weight)
(C) It is liquid at normal temperature, HLB is 0.4-1.5, General formula (3):
^{_{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -R 2 -O- (EtO) n -R 1 (3)
(Wherein Et is an ethylene group, Me is a methyl group, R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and n is 2 to 20, m is an integer of 10 to 100), and is an organopolysiloxane composition having a viscosity of 1 to 400 parts by weight and a viscosity at 25 ° C. in the range of 20 to 1000 mPa · s.

Since component (C) has a polyoxyethylene block and a dimethylpolysiloxane block, it is excellent in compatibility with component (A) and component (B), and more slowly than component (B). Bleeding out from the surface of the coating film more quickly gives the coating film surface a slightly hydrophilic property for a long period of time.
Component (C) is liquid at normal temperature. The HLB of the component (C) is preferably 0.4 to 1.5 from the viewpoint of sustaining the effect of imparting slight hydrophilicity to the coating film surface. The component (C) has a polyoxyethylene chain (R ^1- (EtO) n—O—R ² —) having a polymerization degree of 2 to 20 at both ends. The polyoxyethylene chain is a hydrophilic group, and the degree of polymerization is preferably 2 to 20 from the point of uniformity of the coating film. The compounding quantity of a component (C) is 1-400 weight part with respect to 100 weight part of component (A), and it is preferable that it is 30-100 weight part.

The organopolysiloxane composition comprising the component (A), the component (B) and the component (C) preferably has a viscosity at 25 ° C. of 20 to 1000 mPa · s from the viewpoint of imparting moderate hydrophilicity.

The organopolysiloxane composition composed of the component (A), the component (B) and the component (C) can be produced by, for example, synthesizing each component separately by a known method and mixing them uniformly. However, in General Formula (1) and General Formula (4), R ³ is an alkyl group having 4 to 18 carbon atoms, and in General Formula (2), one of R ⁴ is an alkenyl group having 2 to 4 carbon atoms. And the other is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and dimethylcyclopolysiloxane (e.g., octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane) and 1,1, General formula (7) obtained by equilibrium polymerization of 3,3-tetramethyldisiloxane with an acidic catalyst (for example, acidic clay):
H- (SiMe ₂ O) _m -SiMe ₂ H (7)
(Wherein, Me is a methyl group, m is an integer of 10 to 100), and the both-terminal hydrosilyl group-containing dimethylpolysiloxane is represented by a single-terminal alkenyl group-blocked polyoxyethylene compound represented by the general formula (6) It can be easily produced by subjecting an α-olefin having 4 to 18 carbon atoms to a hydrosilylation reaction simultaneously or stepwise in the presence of a platinum-based catalyst. The organopolysiloxane composition produced by this production method is preferable because the uniformity of the components and the dispersibility upon blending are good.

The organopolysiloxane composition comprising the component (A), the component (B) and the component (C) is further (D) liquid at ordinary temperature, and the general formula (4):
^{_{R 3 - (SiMe 2 O)}} m -SiMe 2 R 3 (4)
(Wherein Me is a methyl group, R ³ is an alkyl group having 1 to 20 carbon atoms, and m is an integer of 10 to 100). A preferable compounding amount is 10 to 100 parts by weight per 100 parts by weight of the component (A).

The organopolysiloxane composition comprising component (A) and component (B) of the present invention and the organopolysiloxane composition comprising component (A), component (B) and component (C) are useful as paint additives, for example. It is. The antifouling paint composition to be added is a film-forming component comprising a resin or rubber such as an acrylic resin, a polyester resin, an epoxy resin, an alkyd resin, a silicone resin or rubber, and a crosslinking agent blended as necessary. An antifouling paint composition can be mentioned, and the coating film surface can be continuously imparted with a slight hydrophilicity over a long period from the initial stage of its formation. Adhesion can be prevented for a long time, and dirt adhering to the coating film surface can be easily washed with water. Preferably, the coating film forming component of the antifouling coating composition is a room temperature curable organopolysiloxane composition, since the coating film has the property of deforming rubber and is difficult for organisms in water to adhere. Paint additive which is an organopolysiloxane composition comprising the above component (A) and component (B), and paint additive which is an organopolysiloxane composition comprising component (A), component (B) and component (C) The amount added to the antifouling paint composition is not particularly limited as long as the desired antifouling effect is obtained, but it is 10 to 80 per 100 parts by weight of the film-forming component of the antifouling paint composition. It is preferable that it is a weight part.

The room temperature curable organopolysiloxane composition (E) includes a room temperature curable silicone resin composition and a room temperature curable silicone rubber composition, with the latter being preferred in terms of coating film characteristics. The room temperature curable silicone rubber composition has (a) a viscosity at 25 ° C. of 20 to 100,000 mPa · s in terms of curability, coating film formability and cured film properties, and at least 2 in one molecule. 100 parts by weight of diorganopolysiloxane having one silicon atom-bonded hydroxyl group or silicon atom-bonded hydrolyzable group, (b) an organosilicon compound having at least two silicon atom-bonded hydrolyzable groups in one molecule The composition preferably comprises 100 parts by weight and (c) 0 to 10 parts by weight of a curing catalyst.

A room temperature curable silicone rubber composition is one in which a condensation reaction is initiated by moisture in the air at room temperature to cure to form a silicone rubber. For example, a dealcohol-free type, a deoxime type, a deacetic acid type, a deketone type Room temperature curable silicone rubber compositions of the type, deamine type, deamid type and dehydroxyamine type.

Component (a) is the main component of the room temperature curable silicone rubber composition. Examples of the molecular chain terminal silicon atom-bonded hydrolyzable group include dialkyl ketoxime groups such as dimethyl ketoxime group and methyl ethyl ketoxime group; Alkoxy groups such as ethoxy groups; acyloxy groups such as acetoxy groups; alkylamino groups such as N, N-diethylamino groups and N-butylamino groups; N-alkylacylamide groups such as methylacetamide groups; N, N-diethylaminoxy An N, N-dialkylaminoxy group such as a group; and an alkenyloxy group such as a propenoxy group . Among these, an alkoxy group is preferable. The organic group bonded to the silicon atom in the diorganopolysiloxane is an alkyl group such as a methyl group, an ethyl group or a propyl group; an alkenyl group such as a vinyl group or an allyl group; an unsubstituted group such as an aryl group such as a phenyl group. Examples thereof include a monovalent hydrocarbon group, a perfluoroalkyl group such as a 3,3,3-trifluoropropyl group, and a nonafluorohexyl group. Among such diorganopolysiloxanes, dimethylpolysiloxane having both molecular chain ends blocked with silanol groups and dimethylpolysiloxane having both molecular chain ends blocked with methyldimethoxysiloxy groups or trimethoxysiloxy groups are preferable. The viscosity at 25 ° C. is 20 to 100,000 mPa · s, preferably 40 to 15,000 mPa · s. Two or more diorganopolysiloxanes having different viscosities may be used in combination.

Component (b) is a crosslinking agent of component (a), and a typical example is a hydrolyzable group-containing organosilane represented by the general formula: R _a SiX _4-a . R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkyl group such as a methyl group, an ethyl group, a propyl group, a tert-butyl group or a 2-ethylhexyl group; an alkenyl group such as a vinyl group or an allyl group; An aryl group such as a phenyl group is exemplified. Among these, an alkyl group and an alkenyl group are preferable, and a methyl group is particularly preferable. X is a hydrolyzable group and is a dialkyl ketoxime group such as a dimethyl ketoxime group or a methyl ethyl ketoxime group; an alkoxy group such as a methoxy group or an ethoxy group; an acyloxy group such as an acetoxy group; an N, N-diethylamino group, an N- Examples thereof include alkylamino groups such as butylamino group; N-alkylacylamide groups such as methylacetamide group; N, N-dialkylaminoxy groups such as N, N-diethylaminoxy group; alkenyloxy groups such as propenoxy group. a is an integer of 0 to 2, preferably 1, and then 0. Examples of such component (b) include tetrakis (methyl ethyl ketoxime) silane, methyl tris (methyl ethyl ketoxime) silane, vinyl tris (methyl ethyl ketoxime) silane, methyl trimethoxy silane, methyl triethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane. , Methyltriacetoxysilane, tetramethoxysilane, tetraethoxysilane, methyltri (isopropenoxy) silane, tetra (isopropenoxy) silane, and methyltri (N, N-diethylamino) silane. Component (b) may be an organosiloxane having two or more, preferably three or more silicon-bonded hydrolyzable groups. The amount of component (b) is sufficient for component (a) to crosslink, but as a guideline it is 5 to 100 parts by weight with respect to 100 parts by weight of component (a), which is preferable from the viewpoint of curability. Is in the range of 8-40 parts by weight

The room temperature curable silicone rubber composition preferably contains (c) a curing catalyst in order to improve the hydrolysis reaction of the hydrolyzable group and the condensation reaction curability between the silanol group and the hydrolyzable group. Specific examples include organotin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate; isopropyl triisostearoyl titanate, isopropyl tris Organic titanate compounds such as (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraalkyl titanate; tetrabutyl zirconate, tetrakis (acetylacetonate) zirconium, tetraisobutyl zirconate, butoxytris (acetylacetonate) ) Organic zirconium compounds such as zirconium and zirconium naphthenate; Tris (ethylacetoacetate) ) Organoaluminum compounds such as aluminum and tris (acetylacetonate) aluminum; Carboxylic acid metal salts such as zinc naphthenate, cobalt naphthenate and cobalt octylate; amines not containing organosilicon compounds such as diethylamine and triethanolamine System catalysts. The compounding amount of the catalyst for condensation reaction is 0 to 10 parts by weight with respect to 100 parts by weight of component (a), and is preferably in the range of 0.1 to 5 parts by weight from the viewpoint of curability.

The silicone rubber composition can contain a reinforcing silica filler (d) from the viewpoint of coating strength. (D) The reinforcing silica filler is a reinforcing filler of a room temperature curable silicone rubber composition, and a dry process silica filler is representative. That whose BET method specific surface area is 50-400 m < ² > / g is preferable. The reinforcing silica filler is preferably a surface hydrophobized with an organosilicon compound such as hexamethyldisilazane, dimethyldichlorosilane, or cyclic dimethylsiloxane. The compounding amount of the component (d) is preferably 4 to 30 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoint of the viscosity of the composition and the physical properties of the cured product.

The silicone rubber composition may contain an organosilicon compound-based adhesion promoter in order to improve adhesion to a substrate that is in contact with the curing process. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3 Aminoalkylalkoxysilanes such as (2-aminoethyl) aminopropylmethyldimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, etc. Examples include silane coupling agents such as epoxyalkylalkoxysilanes and reactants of the above aminoalkylalkoxysilanes and epoxyalkylalkoxysilanes. The compounding quantity of an adhesion promoter is 0.1-6 weight part with respect to 100 weight part of component (a), Preferably it is the range of 0.5-4 weight part.

The room temperature curable silicone rubber composition may contain a non-reactive silicone fluid. This silicone fluid is an organopolysiloxane which is liquid at room temperature and does not contain a condensation reactive group such as a silanol group or a hydrolyzable group in a molecule other than the organopolysiloxane composition of the present invention. Specific examples include dimethylpolysiloxane fluid, dimethylsiloxane / methylphenylsiloxane copolymer fluid, dimethylsiloxane / methylvinylsiloxane copolymer fluid, dimethylsiloxane / diphenylsiloxane copolymer, both ends of which are blocked with trimethylsiloxy groups. A polymer fluid is mentioned. The viscosity at 25 ° C. is preferably in the range of 10 to 10,000 mPa · s, more preferably in the range of 50 to 5000 mPa · s. The amount of such non-reactive silicone fluid is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of component (a).

(F) The organic solvent having a boiling point of 100 ° C. to 200 ° C. may be blended in an amount sufficient for the antifouling coating composition to be liquid, and the room temperature curable organopolysiloxane composition (E) has a low viscosity. Yes, blending is unnecessary when there is no problem in coatability. However, in order to improve the coatability, it is usually preferable to blend. Component (F) may be any component that dissolves or disperses component (E). Specifically, aromatic hydrocarbons such as toluene, xylene, and naphthene (trade name Naphthezol LL; manufactured by Nippon Petrochemical Co., Ltd.); Ketones such as 2-pentanone and 4-methyl-2-pentanone; aliphatic hydrocarbons such as isoparaffin and normal paraffin (trade names Isosol 200, 300, normal paraffin SL; manufactured by Nippon Petrochemical Co., Ltd.); butyl acetate, isobutyl acetate Examples thereof include carboxylic acid esters such as low molecular weight methylpolysiloxanes such as hexamethyldisiloxane and octamethyltrisiloxane. The compounding amount of the component (F) varies depending on the viscosity of the component (E) and the type of the base material to be coated, so it is difficult to define, but in an example, 4 to 100 parts per 100 parts by weight of the component (E). Parts by weight, preferably 10 to 50 parts by weight.

The antifouling coating composition is a pigment, for example, an inorganic pigment such as titanium oxide, ultramarine blue, bitumen, zinc white, bengara, yellow lead, white lead, carbon black, iron oxide, aluminum powder; azo pigment, triphenylmethane Organic pigments such as pigments, quinoline pigments, anthraquinone pigments, phthalocyanine pigments; quartz fine powder, calcium carbonate powder, diatomaceous earth powder, aluminum hydroxide powder, fine particulate alumina, magnesia powder, zinc oxide powder, hollow filling It may contain a flame retardant such as a platinum compound, fumed titanium dioxide, zinc carbonate powder and manganese carbonate powder.

The antifouling coating composition of the present invention is an organopolysiloxane composition comprising component (A) and component (B) or an organopolysiloxane composition comprising component (A), component (B) and component (C), Consists of component (E) and, if necessary, component (F), and further contains additives such as a rust inhibitor, ultraviolet absorber, light stabilizer, sagging inhibitor, and leveling agent as necessary. May be.

The antifouling coating composition of the present invention is an organopolysiloxane composition comprising component (A) and component (B) or an organopolysiloxane composition comprising component (A), component (B) and component (C), Component (E) or the component of this component, and optionally component (F), etc. are mixed into known kneaders, such as Ross mixer, Hobart mixer, trero mixer, Henschel mixer, kneader mixer, flow jet mixer, It can be easily manufactured by putting it in a kneading apparatus such as a ball mill, a vibration mill, a paddle mixer, or a ribbon mixer, and preferably kneading in a sealed state. Heating may be performed at the time of kneading, and the heating temperature is preferably 30 to 200 ° C. The order of kneading each component is arbitrary, but the method of kneading all the components at the same time, and kneading component (E) and component (F) to prepare A liquid, separately, component (A) and component ( B) or component (A) to component (C) are kneaded to prepare B liquid, and finally, A liquid and B liquid are mixed.

Examples of the coating method of the antifouling coating composition of the present invention include conventionally known methods such as dipping, spraying, brush coating, and blade coating. The coating method may be repeated not only once but also multiple times. . After coating, it is usually left at room temperature to cure as it is. Although the thickness of a coating film is arbitrary, it is preferable to set it as 1-500 micrometers.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following Example. In the examples, “parts” means “parts by weight”. Further, the BET specific surface area represents a specific surface area measured by a nitrogen adsorption method by the BET method.
[Chemical structure]
The chemical structural formulas of components (A) to (D) obtained by the synthesis reaction were identified by measuring ²⁹ Si-NMR with JNM-EX400 manufactured by JEOL Ltd. in a deuterated chloroform solution.
[Abundance ratio of polyoxyethylene-modified polydimethylsiloxane and polyoxyethylene]
¹³ C-NMR was measured by JNM-EX400 manufactured by JEOL Ltd. using a deuterated chloroform solution, and the value was calculated based on the integration ratio between the peak of carbon bonded to silicon and the peak of unreacted vinyl group.
[HLB]
In the examples, HLB (hydrophilic new oil balance) is HLB of Griffin.
HLB is a numerical value representing the hydrophilicity of the surfactant, and represents a value calculated by the following equation.
HLB = (molecular weight of hydrophilic group portion / total molecular weight) × (100/5)
= {Hydrophilic group weight / (Hydrophobic group weight + Hydrophilic group weight)} × (100/5)
Note that HLB = 0 when there is no hydrophilic group.
[BET specific surface area]
The BET specific surface area in an Example represents the specific surface area measured by the nitrogen adsorption method using the BET method.
[viscosity]
It measured at 25 degreeC using the E-type viscosity meter (DIKITAL VISCOMETER by TOKIOMEC company).
[Water contact angle]
An antifouling coating composition is applied on a glass plate and allowed to stand at room temperature for a week to cure, thereby forming a uniform coating film having a diameter of 5 cm. After dropping one drop of water on the coating film, After 1 minute, the contact angle of water at 25 ° C. was measured using CA-P (manufactured by Kyowa Interface Science Co., Ltd.).

[Slight hydrophilicity of the coating film surface]
When the contact angle of water on the surface of the coating film was measured and the contact angle of water was 65 to 75 °, it was determined to be slightly hydrophilic.
[Immersion test of coating film]
A 450 cc glass bottle was filled with a 3.5% by weight aqueous solution of sodium chloride, and an aluminum plate having a coating film was immersed therein and allowed to stand for 6 months. Six months later, the aluminum plate having the coating film was taken out and dried at room temperature, and the contact angle of water was measured for the coating film.
[Anti-fouling]
A zinc-rich epoxy shop primer is applied to a sandblasted plate with a size of 100 mm x 300 mm x 3 mm to a dry film thickness of 15 μm, and then an epoxy resin heavy-duty coating is applied to a dry film thickness of 200 μm. did. On the surface of the coating film, each antifouling coating composition was brush-coated and dried so that the dry film thickness was about 150 μm, thereby preparing an antifouling coating plate. The obtained antifouling coating plate was subjected to a suspended immersion sea test in Orido Bay (Shimizu City, Shizuoka Prefecture) for 24 months, and the antifouling property was visually observed every 6 months.

[Example 1]
100 ml of dehydrated tetrahydrofuran and 100 g of hexamethylcyclotrisiloxane were added to a flask equipped with a stirrer and a thermometer, and 12.5 ml of a 1.6M hexane solution of butyl lithium was added by a syringe, followed by stirring at room temperature for 3 hours. Next, 2 g of dimethylchlorosilane was added to stop the polymerization. Subsequently, stripping was performed at 100 ° C. under reduced pressure for 2 hours to remove volatile components, followed by cooling and filtration. The filtrate is put into a flask equipped with a stirrer and a thermometer, and the polyoxyethylene compound represented by the formula (8) (however, the polymerization degree 4 is an average value)
_{CH 2 = CHCH 2 -O- (C} 2 H 4 O) 4 -CH 3 (8)
10 g was added, and then 0.2 g of platinum / 1,3-divinyltetramethyldisiloxane complex (platinum metal amount 4 wt%) was added, the temperature was raised to 90 ° C., and the mixture was stirred for 1 hour. Volatiles were removed by stripping at 130 ° C. for 2 hours under reduced pressure. The viscosity of the fluid which is a residue was 95 mPa · s.
The obtained fluid was analyzed by ¹³ C-NMR and ²⁹ Si-NMR. As a result, it was found that it had a formula of —CH ₂ CH ₂ CH ₂ —O— (C ₂ H ₄ O) ₄ — with a silicon atom bond at one end. Dimethylpolysiloxane having a polyoxyethylene chain represented by CH ₃ (degree of polymerization 4) and having a silicon atom-bonded butyl group at the other end (HLB = 0.8, degree of polymerization 50) and represented by formula (8) It was found to be a composition comprising a polyoxyethylene compound (HLB = 17.6) and having a weight ratio of 94: 6 in this order. The obtained fluid was designated as organopolysiloxane composition A.

[Example 2]
100 g of dimethylpolysiloxane having a silicon atom-bonded hydrogen atom at both terminals with a degree of polymerization of 60 in a flask equipped with a stirrer and a thermometer and a polyoxyethylene compound represented by formula (8) (however, the degree of polymerization of 4 is an average value)
_{CH 2 = CHCH 2 -O- (C} 2 H 4 O) 4 -CH 3 (8)
5.3 g was added, 0.2 g of platinum / 1,3-divinyltetramethyldisiloxane complex (platinum metal amount 4 wt%) was added, the temperature was raised to 90 ° C., and the mixture was stirred for 1 hour. 4 g of 1-octene was added, 0.2 g of platinum / 1,3-divinyltetramethyldisiloxane complex (platinum metal amount 4 wt%) was added, the temperature was raised to 120 ° C., and the mixture was stirred for 1 hour. Volatiles were removed by stripping at 130 ° C. for 2 hours under reduced pressure. The viscosity of the fluid which is a residue was 100 mPa · s. The obtained fluid was analyzed by ¹³ C-NMR and ²⁹ Si-NMR. As a result, it was found that it had a formula of —CH ₂ CH ₂ CH ₂ —O— (C ₂ H ₄ O) ₄ — with a silicon atom bond at one end. Dimethylpolysiloxane having a polyoxyethylene chain represented by CH ₃ (degree of polymerization 4) and having a silicon atom-bonded octyl group at the other end (degree of polymerization 60, HLB = 0.7), represented by formula (8) Polyoxyethylene compound (HLB = 17.6), polyoxyethylene chain represented by the formula —CH ₂ CH ₂ CH ₂ —O— (C ₂ H ₄ O) ₄ —CH ₃ having a silicon atom bond at both ends (polymerization) Dimethylpolysiloxane having a degree of polymerization 4) (degree of polymerization 60, HLB = 1.3) is composed of 24% by weight, dimethylpolysiloxane having a silicon atom-bonded octyl group at both ends (degree of polymerization 60), and the weight ratio is 48 in order. : It turned out that it is a composition which is 4:24:24. The obtained fluid was designated as organopolysiloxane composition B.

[Comparative Example 1]
The organopolysiloxane composition B obtained in Example 2 was dissolved in toluene, and the polyoxyethylene compound represented by the formula (8) was separated and removed by molecular weight fractionation GPC (gel permeation chromatography). Toluene was stripped from the resulting solution. The resulting fluid had a viscosity of 110 mPa · s.
The obtained fluid was analyzed by ¹³ C-NMR and ²⁹ Si-NMR. As a result, it was found that it had a formula of —CH ₂ CH ₂ CH ₂ —O— (C ₂ H ₄ O) ₄ — with a silicon atom bond at one end. 50% by weight of dimethylpolysiloxane (polymerization degree 60, HLB = 0.7) having a polyoxyethylene chain represented by CH ₃ (polymerization degree 4) and a silicon atom-bonded octyl group at the other end, at both ends Dimethylpolysiloxane having a polyoxyethylene chain (polymerization degree 4) represented by the formula —CH ₂ CH ₂ CH ₂ —O— (C ₂ H ₄ O) ₄ —CH ₃ having a silicon atom bond (polymerization degree 60, HLB = 1.3) was found to be a composition comprising 25% by weight and dimethylpolysiloxane having a silicon atom-bonded octyl group at both ends (polymerization degree 60) consisting of 25% by weight. The obtained fluid was designated as organopolysiloxane composition C.

[Comparative Example 2]
In a flask equipped with a stirrer and a thermometer, 100 g of dimethylpolysiloxane containing silicon atom-bonded hydrogen atoms at both ends with a polymerization degree of 60 and a polyoxyethylene compound represented by formula (9) (however, the polymerization degree of 10 is an average value)
_{CH 2 = CHCH 2 -O- (C} 2 H 4 O) 10 -CH 3 (9)
13.5 g was added, 0.2 g of platinum / 1,3-divinyltetramethyldisiloxane complex (platinum metal amount 4% by weight) was added, the temperature was raised to 90 ° C., and the mixture was stirred for 1 hour. Next, 4 g of 1-octene was added, 0.2 g of platinum / 1,3-divinyltetramethyldisiloxane complex (platinum metal amount 4 wt%) was added, the temperature was raised to 120 ° C., and the mixture was stirred for 1 hour. Further, volatile matters were removed by stripping at 130 ° C. for 2 hours under reduced pressure. The viscosity of the fluid which is a residue was 120 mPa · s. The obtained fluid was analyzed by ¹³ C-NMR and ²⁹ Si-NMR. As a result, it was found that it had a formula of —CH ₂ CH ₂ CH ₂ —O— (C ₂ H ₄ O) ₁₀ − having a silicon atom bond at one end. 48% by weight of dimethylpolysiloxane (polymerization degree 60, HLB = 2.0) having a polyoxyethylene chain represented by CH ₃ (polymerization degree 10) and having a silicon atom-bonded octyl group at the other end is represented by the formula (9 4% by weight of the polyoxyethylene compound (HLB = 17.1) represented by the formula: —CH ₂ CH ₂ CH ₂ —O— (C ₂ H ₄ O) ₁₀ —CH ₃ having both ends bonded to silicon atoms 24% by weight of dimethylpolysiloxane having a polyoxyethylene chain (degree of polymerization of 10) shown (degree of polymerization 60, HLB = 3.0) and having silicon atom-bonded octyl groups at both ends (degree of polymerization 6) 0) was found to be a composition comprising 24% by weight. The resulting fluid was designated as organopolysiloxane composition D.

[Example 3]
Surface-hydrophobized dry silica (product name: Aerosil 200BS (Nippon Aerosil) with a viscosity of 4,000 mPa · s, 100 parts of silanol-group-blocked dimethylpolysiloxane with a viscosity of 4,000 mPa · s, and a BET specific surface area of 160 m ² / g. Co., Ltd.) 20 parts, 18 parts of methyltris (methylethylketoxime) silane, 1.5 parts of 3-aminopropyltriethoxysilane, 0.5 parts of dibutyltin dilaurate, 38 parts of xylene and mixed uniformly under sealing A xylene dispersion of a room temperature curable silicone rubber composition was prepared, to which 40 parts of the organopolysiloxane composition A obtained in Example 1 was added and further mixed to prepare a room temperature curable antifouling paint composition. This composition was applied to an aluminum plate and allowed to stand at room temperature for 1 week to cure to form a coating film. The water contact angle of the coated film was measured to be 70 °, and the aluminum sheet with the coated film was immersed in water for 6 months and dried, and then the water contact angle was measured for the coated film. When measured, the contact angle was maintained at 70 °.

[Example 4]
A mixer with a stirrer, 100 parts of dimethylpolysiloxane blocked with silanol groups at both ends of a molecular chain with a viscosity of 2,000 mPa · s, surface hydrophobized silica with a BET specific surface area of 160 m ² / g (product name: Aerosil 200BS (Nippon Aerosil) 20 parts, 18 parts methyltris (methylethylketoxime) silane, 0.4 parts dibutyltin dilaurate, 1.5 parts 3- (2-aminoethyl) aminopropyltrimethoxysilane, trimethylsiloxy at both ends with a viscosity of 100 mPa · s 10 parts of base-blocked dimethylpolysiloxane fluid and 14 parts of xylene were added and uniformly mixed under sealing to prepare a xylene dispersion of room temperature curable silicone rubber composition. Add 30 parts of polysiloxane composition A, mix further and harden at room temperature An antifouling antifouling paint composition was prepared, which was applied to an aluminum plate and then allowed to stand at room temperature for 1 week to cure to form a coating film.The water contact angle of this coating film was measured. As a result, the aluminum plate with a coating film was immersed in water for 6 months and dried, and then the contact angle of water was measured for the coating film, and the contact angle was maintained at 70 °. Was.

[Example 5]
Surface-hydrophobized dry silica (product name: Aerosil 200BS (Nippon Aerosil) with a viscosity of 4,000 mPa · s, 100 parts of silanol-group-blocked dimethylpolysiloxane with a viscosity of 4,000 mPa · s, and a BET specific surface area of 160 m ² / g. Co., Ltd.) 20 parts, 18 parts of methyltris (methylethylketoxime) silane were added and mixed uniformly under airtightness, and 1.5 parts of 3- (2-aminoethyl) aminopropyltrimethoxysilane and dibutyltin dilaurate 0 0.5 parts, 38 parts of xylene, and 30 parts of the organopolysiloxane composition B obtained in Example 2 were charged under sealing, and further mixed to prepare a room temperature curable antifouling paint composition. After coating on the plate, it was allowed to stand for 1 week at room temperature and cured to form a coating film. As a result, the aluminum plate with a coating film was immersed in water for 6 months and dried, and then the contact angle of water was measured for the coating film, and the contact angle was maintained at 70 °. Was.

[Example 6]
Surface-hydrophobized dry silica (product name: Aerosil 200BS (Nippon Aerosil) with a viscosity of 4,000 mPa · s, 100 parts of silanol-group-blocked dimethylpolysiloxane with a viscosity of 4,000 mPa · s, and a BET specific surface area of 160 m ² / g. Co., Ltd.) 20 parts, 18 parts of methyltris (methylethylketoxime) silane was added and mixed uniformly under hermetically sealed, 1.5 parts of 3- (2-aminoethyl) aminopropyltrimethoxysilane, 0 parts of dibutyltin dilaurate .5 parts, 38 parts of xylene and 30 parts of the organopolysiloxane composition B obtained in Example 2 were put in a sealed state and further mixed to prepare a room temperature curable antifouling paint composition. It was applied to a plate and allowed to stand at room temperature for 1 week to be cured to form a coating film, and the contact angle of water was measured for this coating film. The aluminum plate with the coating film was immersed in water for 6 months and dried, and then the contact angle of water was measured for the coating film, and the contact angle was maintained at 70 °. It was.

[Comparative Example 3]
In Example 3, a room temperature curable antifouling coating composition was prepared under the same conditions except that the organopolysiloxane composition A obtained in Example 1 was not added. This composition was applied to an aluminum plate and allowed to stand at room temperature for 1 week to be cured to form a coating film. When the contact angle of water was measured for this coated film, the contact angle was 100 °, indicating water repellency.

[Comparative Example 4]
In Example 3, in place of the organopolysiloxane composition A obtained in Example 1, 30 parts of the organopolysiloxane composition C obtained in Comparative Example 1 were added under the same conditions except that 30 parts of the organopolysiloxane composition C was obtained. A coating composition was prepared.
This composition was applied to an aluminum plate and allowed to stand at room temperature for 1 week to be cured to form a coating film. When the contact angle of water was measured for this coated film, the contact angle was 90 °, indicating water repellency.

[Comparative Example 5]
In Example 3, instead of the organopolysiloxane composition A obtained in Example 1, the components other than the addition of 30 parts of the organopolysiloxane composition D obtained in Comparative Example 2 were cured at room temperature under the same conditions. An antifouling paint composition was prepared. This composition was applied to an aluminum plate and allowed to stand at room temperature for 1 week to be cured to form a coating film. When the contact angle of water was measured for this coating film, the contact angle was 70 °. The aluminum plate with the coating film was immersed in water for 6 months and then dried, and then the contact angle of water with respect to the coating film was measured. As a result, the contact angle was 90 ° and the hydrophilicity was lowered.

[Example 7]
A zinc-rich epoxy shop primer is applied to a sandblasted plate with a size of 100 mm x 300 mm x 3 mm to a dry film thickness of 15 μm, and then an epoxy resin heavy-duty coating is applied to a dry film thickness of 200 μm. did. The antifouling coating composition prepared in Example 3 was applied to the coated surface with a brush so that the dry film thickness was about 150 μm and dried to prepare an antifouling coating plate. The obtained coated plate was subjected to a suspended immersion sea test in Orido Bay (Shimizu City, Shizuoka Prefecture) for 24 months, and the antifouling property was visually measured every 6 months. The results are shown in Table 2.

[Example 8]
In Example 7, instead of applying the antifouling paint composition prepared in Example 3, a suspended immersion sea test was conducted under the same conditions except that the antifouling paint composition prepared in Example 4 was applied. The results are shown in Table 2.

[Example 9]
In Example 7, instead of applying the antifouling paint composition prepared in Example 3, a suspended immersion sea test was performed under the same conditions except that the antifouling paint composition prepared in Example 5 was applied. The results are shown in Table 2.

[Example 10]
In Example 7, suspended Hitaumi test instead of applying the antifouling coating composition manufactured by tone in Example 3 was applied, except for applying the antifouling coating composition manufactured by tone in Example 6 under the same conditions Went. The results are shown in Table 2.

[Comparative Example 6]
In Example 7, the same suspended immersion sea test was conducted except that the antifouling paint composition prepared in Example 3 was applied instead of the antifouling paint composition prepared in Example 3. The results are shown in Table 2.

[Comparative Example 7]
In Example 7, the same suspended immersion sea test was conducted except that the antifouling paint composition prepared in Example 3 was applied instead of the antifouling paint composition prepared in Comparative Example 4. The results are shown in Table 2.

[Comparative Example 8]
In Example 7, instead of applying the antifouling paint composition prepared in Example 3, a suspended sea test was conducted under the same conditions except that the antifouling paint composition prepared in Comparative Example 5 was applied. The results are shown in Table 2.

The organopolysiloxane composition of the present invention is useful as a paint additive, particularly an antifouling paint additive, a rubber or plastic, particularly a silicone rubber additive, and a surface treatment agent for various materials.
The paint additive of the present invention is useful as an additive for an antifouling paint.
The antifouling paint composition of the present invention is particularly useful as an antifouling paint for coating underwater moving objects and underwater structures, particularly underwater moving objects and underwater structures in the sea. Metal, mortar, slate, concrete, It is useful as a low-contamination paint and anti-contamination paint for buildings, civil engineering structures, vehicles, and industrial products made of wood, plastic, glass, ceramics, etc.

Claims (12)

(A) It is liquid at normal temperature, HLB is 0.2-1.5, General formula (1):
_{^{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -SiMe 2 R 3 (1)
Di organopolysiloxane (formula represented in, Et is an ethylene group, Me is a methyl group, ^{R 1} is an alkyl group having 1 to 4 carbon atoms, ^{R 2} is 2 to 4 carbon atoms an alkylene group, ^{R 3} is an alkyl group having a carbon number of 1 to 20, n is 2 to 20, m is an integer of 10 to 100)
100 parts by weight,
(B) HLB is 13-18, General formula (2):
R ⁴ —O— (EtO) _n —R ⁴ (2)
In polyoxyethylene compound represented (wherein, Et represents an ethylene group, R ⁴ is identical or different alkyl or alkenyl group having 2 to 20 carbon atoms carbon atoms 1 to 20, n is An organopolysiloxane composition comprising 1 to 20 parts by weight (which is an integer of 2 to 20) and a viscosity at 25 ° C. of 20 to 1000 mPa · s. (A) It is liquid at normal temperature, HLB is 0.2-1.5, General formula (1):
_{^{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -SiMe 2 R 3 (1)
In the diorganopolysiloxane (formula represented, Et is an ethylene group, Me is a methyl group, ^{R 1} is an alkyl group having 1 to 4 carbon atoms, ^{R 2} is 2 carbon atoms a 4 alkylene group, ^{R 3} is an alkyl group having a carbon number of 1 to 20, n is 2 to 20, m is an integer of 10 to 100)
100 parts by weight,
(B) HLB is 13-18, General formula (2):
R ⁴ —O— (EtO) _n —R ⁴ (2)
In polyoxyethylene compound represented (wherein, Et represents an ethylene group, R ⁴ is identical or different alkyl or alkenyl group having 2 to 20 carbon atoms carbon atoms 1 to 20, n is 1 to 20 parts by weight)
(C) It is liquid at normal temperature, HLB is 0.4-1.5, General formula (3):
_{^{R 1 O- (EtO) n -R}} 2 - (SiMe 2 O) m -SiMe 2 -R 2 -O- (EtO) n -R 1 (3)
Di organopolysiloxane (formula represented in, Et is an ethylene group, Me is a methyl group, ^{R 1} is an alkyl group having 1 to 4 carbon atoms, ^{R 2} is 2 to 4 carbon atoms of an alkylene radical, n is 2 to 20, m is an integer of 10 to 100) consists of 1 to 400 parts by weight, the organopolysiloxane, wherein the viscosity at 25 ° C. is 20~1000mPa · s Composition. Furthermore, per 100 parts by weight of component (A), (D) liquid at ordinary temperature , general formula (4):
_{^{R 3 - (SiMe 2 O)}} m -SiMe 2 R 3 (4)
Diorganopolysiloxane represented in (wherein, Me is a methyl group, ^{R 3} is an alkyl group having a carbon number of 1 to 20, m is an integer of 10 to 100) 10 to 100 parts by weight 3. The organopolysiloxane composition according to claim 2, which is contained. In the general formula (1), R ³ is an alkyl group having 4 to 18 carbon atoms, in the general formula (2), one of R ⁴ is an alkenyl group having 2 to 4 carbon atoms, and the other is 1 to 1 carbon atoms. the organopolysiloxane composition of claim 1, wherein from 4 alkyl group. In General Formula (1) and General Formula (4), R ³ is an alkyl group having 4 to 18 carbon atoms, and in General Formula (2), one of R ⁴ is an alkenyl group having 2 to 4 carbon atoms, other organopolysiloxane composition 請 Motomeko 3 wherein you characterized in that the alkyl group having 1 to 4 carbon atoms. A general product obtained by living polymerization using a metal alkyl initiator (wherein the alkyl group has 4 to 18 carbon atoms) in a solvent obtained by dehydrating hexamethylcyclotrisiloxane and stopping the polymerization with dimethylhalosilane. Formula (5): H- (SiMe ₂ O) _m -SiMe ₂ R ³ (5)
(Wherein, Me is a methyl group, ^{R 3} is an alkyl group having 4 to 18 carbon atoms, m is an integer of 10 to 100) and one end hydrosilyl group-containing dimethyl polysiloxane represented by excess General formula (6) of the amount: R ⁵ —O— (EtO) _n —R ⁵ (6)
(Wherein, one of R ⁵ is an alkyl group having 1 to 4 carbon atoms, the other of R ⁵ is an alkenyl group having 2 to 4 carbon atoms , and n is an integer of 2 to 20). The method for producing an organopolysiloxane composition according to claim 4, wherein the one-terminal alkenyl group-blocked polyoxyethylene compound is hydrosilylated in the presence of a platinum-based catalyst. General formula (7) obtained by equilibrium polymerization of dimethylcyclopolysiloxane and 1,1,3,3-tetramethyldisiloxane using an acidic catalyst:
H- (SiMe ₂ O) _m -SiMe ₂ H (7)
(Wherein, Me is a methyl group , and m is an integer of 10 to 100), the hydrosilyl group-containing dimethylpolysiloxane represented by the general formula (6) :
_{^{R 5 -O- (EtO) n -R}} 5 (6)
(Wherein , one of R ⁵ is an alkyl group having 1 to 4 carbon atoms, the other of R ⁵ is an alkenyl group having 2 to 4 carbon atoms, and n is an integer of 2 to 20) . 6. The hydrosilylation reaction of the polyoxyethylene compound blocked with one terminal alkenyl group and the α-olefin having 4 to 18 carbon atoms is carried out simultaneously or stepwise in the presence of a platinum catalyst. A method for producing an organopolysiloxane composition. A coating additive comprising the organopolysiloxane composition according to any one of claims 1 to 5. An antifouling paint composition comprising the paint additive according to claim 8. The antifouling paint composition according to claim 9, wherein the film-forming component in the antifouling paint composition is a room temperature curable organopolysiloxane composition (E). (E) 100 parts by weight of room temperature curable organopolysiloxane composition, 10 to 80 parts by weight of paint additive according to claim 8, and (F) 4 to 100 parts by weight of organic solvent having a boiling point of 100 ° C to 200 ° C. The antifouling paint composition according to claim 10. Component (E) is a diorganopolysiloxane having component (E) (a) having a viscosity of 20 to 100,000 mPa · s at 25 ° C. and having at least two silicon atom-bonded hydroxyl groups or silicon atom-bonded hydrolyzable groups in one molecule. A composition comprising 100 parts by weight, (b) 5 to 100 parts by weight of an organosilicon compound having at least two silicon atom-bonded hydrolyzable groups in one molecule, and (c) 0 to 10 parts by weight of a curing catalyst The antifouling paint composition according to claim 10 or 11, wherein: