JP2001181509A - Curable composition, coating composition, coating material, antifouling coating material, its cured product, and antifouling method of substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide curable compositions which can form thick films and excel in the strength and hardness of coated films and can exhibit good long- term antifouling performance when used as the antifouling coating material. SOLUTION: The curable compositions comprise (A) an organopolysiloxane, both molecular terminals of which are condensation reactivity functional groups, and (B) a mixture of a hydrophobic silica and a hydrophilic silica. It is preferred that component (A) is represented by the formula: W3-a(R1a)Si(R2)O[Si(R2)O]n-Si(1a)W3-a, wherein W is a hydroxyl group or a hydrolyzable group; R1 and R are each a monovalent hydrocarbon groups; n is an integer of not smaller than 5; and a is 0, 1 or 2. Further, when W in the formula is a hydroxyl group and, at the same time, a is 2, it is preferred to incorporate (C) an organosilane represented by the formula: R1aSiX4-a, wherein R1 is a monovalent hydrocarbon group; X is a hydrolyzable group; and a is 0 or 1 or its partial hydrolyzate in addition to components (A) and (B) into the compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition, a coating composition, a paint, an antifouling paint, a cured product thereof, and a method for fouling a substrate. More specifically, the present invention is, for example, excellent in spray coating properties, it is possible to increase the film thickness by one coating and shorten the coating work period, and furthermore, the coating film having a uniform thickness can be obtained. The coating film obtained is excellent in coating strength, coating film hardness, rubber properties, etc., exhibits good antifouling properties for a long period of time, and is a curable composition having excellent storage stability before coating, Coating compositions, paints,
The present invention relates to an antifouling paint, a cured product thereof, and an antifouling method for a substrate such as an underwater structure or a ship outer panel.

[0002]

BACKGROUND OF THE INVENTION Conventionally, in the production of a curable silicone composition, regardless of whether it is a one-pack type or a two-pack type, various properties after curing such as surface smoothness and rubber strength are sufficiently exhibited. And hydrophilic silica or hydrophobic silica surface-treated with hexamethyldisilazane or the like.

However, hydrophilic silica has poor affinity for silicone oil, and aggregates of fillers such as silica are formed in the curable silicone composition. Even if such a composition is cured, it is excellent. No rubber with properties is obtained. In addition, the hydrophobic silica has a good affinity for silicone oil, does not cause much aggregation in the composition, the silica is relatively well dispersed, the thixotropy is relatively good, and the vertical surface and the like. It is expected that the thickness of the coating film can be increased by one coating. However, this composition has high viscosity and poor spray coating properties, and when diluted with a solvent, rapidly loses thixotropy, causing problems such as sagging of the coating film and reduction in smoothness of the coating film. There is.

For example, JP-A-10-316933 discloses that (a) a silicone rubber having a number average molecular weight of 20,000 to 100,000 which can be cured at room temperature, and (b) a silicone rubber having a number average molecular weight of 500 to 20,000 which can be cured at room temperature. A coating composition containing silicone rubber and (c) silicone oil as main components is disclosed, and a coating composition containing hydrophobic fumed silica (d) is also disclosed. In the case of a coating composition in which hydrophobic fumed silica is blended with two kinds of silicone rubbers having different molecular weights as described above, it is possible to form a thick film by applying once, but the storage stability of the coating is lacking. Silica 2 when stored
Because of the agglomeration, which is considered to be due to the following agglomeration, the spray coatability at the time of coating is poor, and the coating film surface becomes non-uniform (the film thickness, color tone, etc. are non-uniform and there are spots) when forming the coating, There is a problem that it is not possible to form a good coating film such as film thickness and rubber strength.

[0005] Since underwater structures, fishing nets and the like are used for a long time in the water, especially in the seawater, a large number of parts such as hydropests, flies, mosses, serpentine, oysters, etc. When marine organisms attach and propagate, the original functions of underwater structures, fishing nets and the like may be impaired. In particular, underwater structures such as water supply and drainage ports for thermal and nuclear power plants are constructed and fixed at predetermined locations in the sea, and aquaculture nets and stationary nets are left standing in seawater for a long period of time. Propagation is remarkable, and frequent replacement, removal cleaning, etc. must be performed, resulting in a large economic loss.

[0006] In order to solve these problems, antifouling paints have been widely applied to surfaces of underwater structures, fishing nets, seawater utilization equipment and the like for the purpose of preventing the adhesion of marine organisms. For example, Japanese Patent Publication No. 63-2959 discloses a non-toxic antifouling paint composition comprising a mixture of a chemical reaction-curable silicone rubber, a petrolatum or liquid paraffin mixture, and a low-viscosity silicone oil. In the gazette,
It is described that if this composition is applied to a water-contacting portion of a marine structure, the growth of marine organisms can be prevented for a long period of time. However, with this non-toxic antifouling paint composition, it is difficult to obtain a sufficiently thick film by a single application, and the obtained coating film has poor strength and hardness and is apt to be damaged. is there.

[0007] The applicants of the present invention have previously proposed: Patent No. 2
No. 522,854 discloses that (A) an organopolysiloxane in which both ends of a molecular chain are blocked with a silanol group or a hydrolyzable group, and (B) a compound represented by the formula “R ¹ _a SiX _4-a (where R ¹ is carbon An unsubstituted or substituted monovalent hydrocarbon group represented by Formulas 1 to 8, X represents a hydrolyzable group, and a represents 0 or 1, and an organosilane or a partial hydrolyzate thereof; C) Formula in one molecule: ＲSiR ² OSiR ³ _b Y
_3-b (wherein, R ² represents a divalent hydrocarbon group containing a divalent hydrocarbon group or an ether bond unsubstituted or substituted, R ³
Is an unsubstituted or substituted monovalent hydrocarbon group, Y is a hydrolyzable group, and b is 0, 1 or 2. However, when R ² is a divalent hydrocarbon group containing an ether bond, except for an organopolysiloxane in which two or more trimethylsiloxy groups are bonded to a Si atom in which a carbon atom of the hydrocarbon group is directly bonded) A curable organopolysiloxane composition containing an organopolysiloxane containing at least one of the groups shown as a main component and a cured product thereof are disclosed. The publication also states that as a filler, besides fine powdered silica, fumed silica, precipitated silica, etc., those whose surfaces have been subjected to a hydrophobic treatment with silane or the like may be blended. The publication also states that the cured product has a long-lasting antifouling effect without fear of environmental pollution. However, the curable organopolysiloxane composition described in this publication has room for improvement in terms of the thickness of the coating film, strength, hardness, and the like, and has a problem that it is easily damaged.

[0008] The above-mentioned Japanese Patent Application Laid-Open No. 10-316933.
In the antifouling paint composition described in JP-A No.
It is possible to make the film thicker by simply applying it multiple times, but it lacks storage stability as a paint, has poor spray coatability at the time of painting, and has an uneven coating surface (film thickness, color tone, etc.) Is nonuniform and has uneven coating), and a good coating film cannot be formed. In particular, when used as an antifouling coating film, there is a problem that the long-term antifouling property is poor.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and to achieve a good balance of low viscosity, high thixotropy, etc., and to achieve a thick film by one coating. It is an object of the present invention to provide a curable composition which is possible and has a well-balanced excellent cured coating film in rubber strength and surface smoothness.

Further, the present invention, when used as a coating material, especially as a coating material, has excellent spray coating properties, enables a thick film to be formed by a single coating, shortens the coating work period, and makes the coating film surface uniform by the coating. A good coating film with excellent properties is obtained, and the obtained coating film has excellent coating strength and coating hardness, and when used as an antifouling paint, exhibits excellent antifouling performance for a long time. Another object of the present invention is to provide a curable composition having excellent storage stability before coating, in particular, a coating composition, a curable paint composition, and an antifouling paint composition.

Further, the present invention provides an electric part, a building material, a craft, a garment industrial article, and a medical article which are excellent in coating film strength, coating film hardness, surface smoothness and the like when used as a coating material, especially as a coating material as described above. Along with the object of providing an antifouling coating film which exhibits excellent antifouling performance for a long time when used as an antifouling paint, or an underwater structure coated with the coating film, a ship outer panel, etc. It is intended to provide.

The present invention provides a method for producing a curable composition, a coating composition, and a curable (antifouling) paint composition such that a thick film having the above characteristics is preferably obtained by a single application. It is intended to be. Further, the present invention provides a coating film having excellent properties as described above on the surface of various substrates such as the surface of an underwater structure, which is safe for workers, and has no danger of environmental pollution, and can form a coating film efficiently. It is an object of the present invention to provide a method for forming a coating film on a surface of an electric component or the like, and a method for soiling a surface of a base material such as a ship outer panel, an underwater structure, and a fishing net.

[0013]

SUMMARY OF THE INVENTION A curable composition according to the present invention comprises (A) an organopolysiloxane in which both terminals of a molecule are condensation-reactive functional groups, and (B) hydrophobic silica and hydrophilic silica. It is characterized by:

In the present invention, the organopolysiloxane (A) is represented by the following formula [α]:

[0015]

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(In the formula [α], W represents a hydroxyl group or a hydrolyzable group, and R ¹ and R each independently represent a C 1-12 carbon atom.
Represents an unsubstituted or substituted monovalent hydrocarbon group;
¹ and R may be the same or different from each other, n represents an integer of 5 or more, and a represents 0, 1 or 2. ) Is desirable.

In the present invention, when W in the formula [α] is a hydroxyl group and a is 2, in addition to the component (A) and the component (B), C) Formula [I]: R ¹ _a SiX _4-a (In the formula [I], R ¹ has ¹ carbon atom.
And X represents an unsubstituted or substituted monovalent hydrocarbon group, X represents a hydrolyzable group, and a represents 0 or 1. ) Or a partial hydrolyzate thereof.

In the present invention, at least hydrophilic silica, preferably both hydrophilic silica and hydrophobic silica, of the above component (B) is heat-treated with the above component (A) at a temperature of 100 ° C. or higher. Is desirable. In the present invention, the component (B) is replaced with the component (A) 100
It is desirable to contain it in an amount of 1 to 100 parts by weight based on parts by weight.

The component (C) is replaced with the component (A)
It is desirable to contain it in an amount of 1 to 20 parts by weight based on 100 parts by weight. In the present invention, the weight ratio of the hydrophobic silica (a) to the hydrophilic silica (b) ((a) / (b)) = 1/99 to 99.
/ 1 is desirable. In the present invention, further,
The silicone oil (D) is desirably contained in an amount of 0.1 to 200 parts by weight based on 100 parts by weight of the component (A).

In the present invention, it is desirable to further include a catalyst, an antifouling agent and / or a colorant. In the method for producing a curable composition according to the present invention, when producing the curable composition, the component (A) and at least the hydrophilic silica of the component (B) are treated at a temperature of 100 ° C. or higher. And a heat treatment step.

The coating composition according to the present invention comprises any of the curable compositions described above. In the present invention, the coating composition is preferably used as a paint or an antifouling paint. The cured product according to the present invention is obtained by curing any of the curable compositions described above.

The coating film and the antifouling coating film according to the present invention are obtained by applying and curing the above-mentioned curable composition. The substrate with a coating film according to the present invention is characterized in that the surface of the substrate is coated with a coating film obtained by curing the curable composition according to any of the above, and Examples include electrical parts, electronic supplies, building materials, craft supplies, clothing industry supplies, medical supplies, and the like.

According to the method of forming a coating film on the surface of a substrate according to the present invention, the surface of a substrate such as the electric component is coated or impregnated with a coating material comprising the curable composition as described above. Then, the coating material is cured to form a coating film. Antifouling substrate according to the present invention, the surface of the substrate in contact with seawater or fresh water,
It is characterized by being coated with a coating film obtained by curing any of the curable compositions described above, and the substrate is preferably an underwater structure, a ship outer plate, a fishing net, or a fishing gear.

In the method for soil-fouling a substrate according to the present invention, the surface of a substrate such as the above-mentioned underwater structure is coated or impregnated with an antifouling paint comprising the curable composition described in any of the above. It is characterized in that the antifouling paint is cured to form an antifouling coating film. According to the present invention, low viscosity, high thixotropy, etc. are well-balanced, and a thick film can be formed by one coating, and the obtained cured coating film has excellent balance in rubber strength, surface smoothness, etc. A curable composition is provided.

Further, according to the present invention, especially when used as a coating composition or a coating material, it is excellent in spray coating properties, can be formed into a thick film by a single coating, can shorten the coating work period, and more uniformly by the coating. A coating film having a film thickness is obtained, and the obtained coating film has excellent coating film strength and coating film hardness, and particularly when used as an antifouling paint, exhibits good antifouling performance for a long time. Before the process, a curable composition having excellent storage stability is provided.

Such a curable composition is suitably used as a coating composition, in particular, a curable paint composition and an antifouling paint composition. The cured product according to the present invention, in particular, the cured coating material has excellent balance of rubber properties such as surface gloss, rubber hardness, and tensile strength.
The underwater structure or ship outer panel having the base material surface coated with the antifouling coating film has properties such as long-term antifouling properties.

According to the method for producing a curable composition according to the present invention, a desired thick film can be applied to a surface of a vertically erected substrate or the like by one coating, and a coating material having high coating efficiency can be obtained. A curable composition such as a paint, particularly an antifouling paint, can be produced. According to the method of antifouling the surface of a substrate according to the present invention, a coating film having excellent characteristics as described above is applied to the surface of various substrates such as the surface of an underwater structure, which is safe for workers, and also poses a risk of environmental pollution. Thus, a desired coating film can be efficiently formed.

[0028]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the curable composition, coating composition, paint, antifouling paint, cured product thereof, and method of antifouling a substrate according to the present invention will be described in detail. <Curable composition> The curable composition according to the present invention includes:
(A) an organopolysiloxane in which both ends of a molecule (chain molecule or molecular main chain) are condensation-reactive group functional groups,
(B) Hydrophobic silica and hydrophilic silica are contained.

Hereinafter, first, the organopolysiloxane (A)
Will be described. <Organopolysiloxane (A)> As the organopolysiloxane (A), a polymer which is a main component of an organosilicone as described in Japanese Patent No. 2522854, particularly preferably a liquid polymer is used. As such organopolysiloxane (A), the following formula:
[α]:

[0030]

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(In the formula [α], W represents a hydroxyl group (—OH) or a hydrolyzable group, and R ¹ and R each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. And a plurality of R ¹ and R may be the same or different from each other, and n represents an integer of 5 or more, and a represents 0, 1 or 2.)

In the formula [α], when a = 0 and 1, W is a hydrolyzable group, and when a = 2, W is a hydroxyl group (—OH). desirable. In the present invention, when W in the formula [α] is a hydroxyl group and a is 2, in addition to the component (A) and the component (B), furthermore, (C)
Formula [I]: R ¹ _a SiX _4-a (wherein R ¹ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, X represents a hydrolyzable group, a represents 0 or 1.), or a partial hydrolyzate thereof.

Hereinafter, the organopolysiloxane (A) represented by the formula [α] will be described first. The above formula
When w in [α] is a hydrolyzable group, examples of such a hydrolyzable group include an alkoxy group, an acyloxy group, an alkenyloxy group, an iminoxy group, an amino group, an amide group, and an aminooxy group. And an alkoxy group is preferable.

The above alkoxy group has a total carbon number of 1
To 10 are desirable, and one or more oxygen atoms may be interposed between carbon atoms. For example, a methoxy group,
Examples thereof include an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, and an ethoxyethoxy group. As the acyloxy group, a compound represented by the formula: RCOO- (wherein, R is a group having 1 to 1 carbon atoms)
Aliphatic or aromatic ones represented by the following formula (10): an alkyl group, an aromatic group having 6 to 12 carbon atoms), for example, an acetoxy group, a propionoxy group, a butyroxy group,
And a benzoyloxy group.

The alkenyloxy group may have 3 to 3 carbon atoms.
About 10 is desirable, and examples thereof include an isopropenyloxy group, an isobutenyloxy group, and a 1-ethyl-2-methylvinyloxy group. Iminoxy group (= N
Also called —OH, oximino group, and ketoxime group. )
It is desirable that they have about 3 to 10 carbon atoms, such as a ketoxime group, a dimethylketoxime group, a methylethylketoxime group, a diethylketoxime group, a cyclopentanoxime group, and a cyclohexanoxime group.

The amino group preferably has 1 to 10 carbon atoms, for example, N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino Group, N, N-diethylamino group, cyclohexylamino group and the like. The amide group preferably has 2 to 10 carbon atoms, and examples thereof include an N-methylacetamide group, an N-ethylacetamide group, and an N-methylbenzamide group.

The aminooxy group includes a total of 2 to 1 carbon atoms.
0 is desirable, and examples thereof include an N, N-dimethylaminooxy group and an N, N-diethylaminooxy group. R ¹ and R each independently have 1 to 1 carbon atoms.
2, more preferably 1 to 10, particularly preferably 1 to 8
Represents an unsubstituted or substituted monovalent hydrocarbon group. Examples of such a monovalent hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group and an aralkyl group.

The alkyl group may be any type of linear, branched or alicyclic alkyl group, and may have 1 to 10, preferably about 1 to 8 carbon atoms. Alkyl group; a cycloalkyl group having 3 to 6 carbon atoms; Examples of such a linear or branched alkyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group, and an octyl group, and particularly preferably a methyl group. Examples of the cyclic alkyl group include a cyclohexyl group and a cyclopentyl group.

The alkenyl group has 2 to 1 carbon atoms.
0, preferably about 2 to 8, for example,
Examples include a vinyl group, a hexenyl group, and an allyl group. The aryl group has 6 to 15 carbon atoms, preferably 6 to 15 carbon atoms.
About 12 are desirable, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a diphenyl group, and a phenyl group is particularly preferable.

The cycloalkyl group may have 3 to 8 carbon atoms.
And a cyclohexyl group, for example. The aralkyl group has a total carbon number of 7 to 10,
Preferably, it is about 7 to 8 and examples thereof include a benzyl group and a 2-phenylethyl group. Some or all of the hydrogen atoms bonded to the carbon atoms in these groups R ¹ may be substituted with halogen atoms such as F, Cl, Br, I, cyano groups, and the like. For example, a chloromethyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethyl group and the like can be mentioned.

As R, an unsubstituted monovalent hydrocarbon group is preferable, and a methyl group and a phenyl group are particularly preferable. Incidentally, in such an organopolysiloxane represented by the formula [α] (A), a plurality of R ^1, when a plurality of R are present, a plurality of R ¹ each other these, a plurality of R each other Or R ¹ and R may be the same or different from each other.

Such an organopolysiloxane (A)
The viscosity at 25 ° C. is different depending on the use of the curable composition to be used and is not determined unconditionally, but in consideration of the paintability of the obtained composition, the viewpoint of preventing sagging when the obtained composition is diluted with a solvent, and the like. , Usually 25 cS to 1,5
00,000 cS (1.5 million cS), preferably 25 to
500,000 cS, more preferably 500 to 20
000 cS, particularly preferably 1,000 to 100,
000 cS is desirable.

<Hydrophobic silica, hydrophilic silica (B)> Silica includes hydrophilic silica (surface-untreated silica) such as wet-process silica (hydrated silica) and dry-process silica (fumed silica, anhydrous silica). Surface treated hydrophobic silica such as hydrophobic wet silica and hydrophobic fumed silica.

In the present invention, hydrophobic silica and hydrophilic silica are used in combination as the silica component (B). For this reason, when the obtained curable composition is used for a coating material (composition for coating), a paint, especially an antifouling paint, etc., it has excellent stability during preparation, storage and storage, and has sufficient thixotropy, Thick film can be made by one coating, and the resulting coating film is
It is excellent in rubber properties such as hardness, tensile strength and elongation in a well-balanced manner, and when used as an antifouling coating film, it is also excellent in antifouling properties.

In the present invention, these silica components include:
Although those having the following characteristics may be used as they are, in a preferred embodiment, as described later in detail, the silica component (B), that is, at least the hydrophilic silica out of the hydrophobic silica and the hydrophilic silica, It is preferable that the heat treatment is performed together with part or all of the component (A), and that both the hydrophilic silica and the hydrophobic silica are heat-treated together with part or all of the component (A). desirable.

Of these silicas (B), wet-process silica usually has an adsorbed water content (also referred to as water content) of about 4 to 8%, a bulk density of 200 to 300 g / L, The primary particle diameter is 10 to 30 mμ, and the specific surface area (BET surface area) may be 10 m ² / g or more, preferably 50 to 800 m ² / g, more preferably about 100 to 300 m ² / g. is there.

Dry silica (fumed silica) usually has a water content of 1.5% or less. In addition, this dry process silica has an initial water content of, for example, 0.
Although it is as low as 3% or less, the moisture content gradually increases when left to stand, and the water content increases, and at a point several months after the production, it becomes, for example, about 0.5 to 1.0%. Further, the bulk density of such a dry-processed silica varies depending on its type and is not determined unconditionally. For example, the bulk density is 50 to 100 g / L, the primary particle diameter is 8 to 20 mμ, and the specific surface area (BET surface area)
Is preferably at least 10 m ² / g, but is preferably at least 10 m ² / g.
0 to 400 m ² / g, more preferably 180 to 300
It is about m ² / g.

[0048] Hydrophobic fumed silica is obtained by converting dry-process silica to methyltrichlorosilane, dimethyldichlorosilane,
Surface-treated with an organosilicon compound such as hexamethyldisilazane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, etc., the water absorption over time is small, the water content is usually 0.3% or less, and in many cases 0.1 to 0.2%, and the specific surface area may be 10 m ² / g or more, preferably 100 to 300 m ² / g,
More preferably, it is 120 to 230 m ² / g, the primary particle size is 5 to 50 mμ, and the bulk density is 50 to 100 g.
/ L.

The hydrophobic fumed silica heat-treated with the component (A) (heat-treated hydrophobic fumed silica)
In the method, water adsorbed on the surface of the hydrophobic silica is physically reduced and removed, and the water content is usually 0.2%.
Or less, preferably 0.1% or less, particularly 0.05 to 0.1
% And other physical properties such as bulk density are the same as those of the above-mentioned hydrophobic silica.

The above component (B) is obtained by mixing the above component (A)
It is desirable that the curable composition of the present invention is usually contained in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, particularly preferably 5 to 30 parts by weight, based on 100 parts by weight. When the silica component (B) is contained in the curable composition in such an amount, the coating film strength and the coating film hardness are excellent, the thixotropy is good, the appropriate viscosity is obtained, and the coating is performed well. Spray coating is preferable, for example, even when the substrate surface stands upright, etc., because a single coating can increase the thickness of the coating film.

If the amount of the component (B) is less than the above range, sufficient coating strength and coating hardness cannot be obtained, and desired thixotropy cannot be obtained. If the component (B) is more than the above range, the viscosity of the coating becomes excessively high, and it is necessary to dilute the coating with a solvent such as a thinner to an appropriate viscosity suitable for coating. In some cases, it is not possible to achieve a thick film by spray coating.

In the present invention, as the silica component (B), a hydrophobic silica (a) such as the above-mentioned hydrophobic fumed silica is used.
And hydrophilic silica (b) such as surface-untreated silica in a weight ratio ((a) / (b)) of 1/99 to 99/1, preferably 20
/ 80-80 / 20, particularly preferably 30 / 70-70
It is desirable to use these in such an amount as to give / 30. When the hydrophobic fumed silica (a) and the hydrophilic silica (b) are used together in such a ratio, the resulting curable composition has excellent paint stability during preparation, storage, and storage, and has sufficient thixotropic properties. A coating film obtained by curing the composition tends to have excellent coating film strength and coating film hardness.

<Organosilane or partial hydrolysis thereof
Product (C)> In the present invention, the component (A) has the formula
In the case where W in the formula [α] is a hydroxyl group and a is 2 represented by [α], in addition to the component (A) and the component (B), (C) Formula [I]: R ¹ _a SiX _4-a (In the formula [I], R ¹ has ¹ carbon atom.
And X represents an unsubstituted or substituted monovalent hydrocarbon group similar to R, R ¹ and the like in the formula [α], and X represents a hydrolyzable group similar to W in the formula [α]. , A represents 0 or 1. )
It is preferable that the organosilane or a partial hydrolyzate thereof is contained.

That is, in the present invention, as the component (A), an organopolysiloxane in which both ends of its molecule (chain molecule, molecular chain) are hydroxyl groups (—OH), specifically, The terminal is a silanol group (≡Si-O
When a curable organopolysiloxane blocked with H) is used, it is particularly preferable to use such a component (A) in combination with a component (C) as a crosslinking agent / curing agent. Further, for example, when a curable organopolysiloxane having both molecular ends blocked with a hydrolyzable group is used as the component (A), it can be cured sufficiently without the curing agent component (C). However, in such a case, it is more preferable to include the component (C).

X is the same hydrolyzable group as W in the formula [I]. Specific examples of the organosilane represented by the formula [I] or the (partial) hydrolyzate thereof include, for example, methyltrimethoxysilane, methyltri (methylethylketoxime) silane, methyltripropenyloxysilane, methyl Examples include triacetoxysilane and silane compounds in which the methyl group of these silane compounds is substituted with a vinyl group, a phenyl group, a trifluoropropyl group, and the like, and further, partially hydrolyzed products thereof.
In this case, the hydrolyzable group is preferably a ketoxime group.

These organosilanes or their hydrolysates (C) can be used as the organopolysiloxane (A) 10
Although it can be used in an amount of 1 to 60 parts by weight with respect to 0 parts by weight, it is usually used in an amount of 1 to 20 parts by weight, preferably 2 to 1 part by weight.
Desirably, it is contained in the curable composition of the present invention in an amount of 0 parts by weight. When the organosilane or its hydrolyzate (C) is contained in the above composition in such an amount, the crosslinking reaction of the component (A) proceeds favorably, and the obtained coating film has an appropriate hardness. And tends to be excellent in economic efficiency.

<Silicone Oil (D)> The curable composition according to the present invention may contain a silicone oil (D).
The non-reactive (non-condensable) silicone oil and the silicone oil which bleeds out from the cured product of the curable composition are not particularly limited, but preferably the component (D) different from the component (A), and Preferred are silicone oils represented by the formulas [II] and [IV], and silicone oils having a group represented by the following formula [III].

Among these silicone oils (D), silicone oils [II] and [IV] do not show reactivity or self-condensation with component (A) and the like, so that It is considered to have the function of forming an antifouling functional layer (film), and the silicone oil [III] reacts with the component (A) which is a coating forming component to form a cured coating, When immersed in seawater for a long period of time, it is hydrolyzed with time, and the terminal group bleeds out to the surface of the coating film as an alcoholic hydroxyl group “≡SiR ⁴ OH” etc. It is thought that it will do.

(R ² ) ₃ SiO (SiR ³ ₂ O) _n Si (R ² ) ₃ ... [II] (In the formula [II], a plurality of R ² may be the same or different. Represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a fluoroalkyl group, a plurality of R ³ may be the same or different from each other, and each R ³ is an alkyl group having 1 to 10 carbon atoms, Represents an aryl group, an aralkyl group or a fluoroalkyl group, and n represents a number of 0 to 150.) {SiR ⁴ OSiR ⁵ _b Y _3-b ... [III] (in the formula [III], R ⁴ represents a divalent hydrocarbon group containing a divalent hydrocarbon group or an ether bond unsubstituted or substituted, R ⁵
Is an unsubstituted or substituted monovalent hydrocarbon group, Y is a hydrolyzable group, and b is 0, 1 or 2. ) R ⁶ _x Si (R ⁷ -Z) _y O _{(4-xy) / 2} ... [IV] (In the formula [IV], R ⁶ is a hydrogen atom, and each has 1 to 1 carbon atoms.)
0 represents an alkyl group, an aryl group, or an aralkyl group; R ⁷ represents an ether group, an ester group, or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have an interposed —NH—; Represents a monovalent polar group that is an amino group, a carboxyl group, an epoxy group, or a polyethylene glycol or polypropylene glycol group whose terminal may be blocked with an alkyl group or an acyl group having 1 to 6 carbon atoms, and x, y Are 0.01 ≦ x <3.99, respectively.
0.02 ≦ y <4, and 0.02 ≦ x + y <4
Is shown. ).

Among the above silicone oils (D), silicone oil [II] is described in Japanese Patent Application Laid-Open No. 10-316933.
JP-A No. 195/1992 can be used and has a number average molecular weight of 180 to 20,000, preferably 1,000.
Desirably, the viscosity is 20 to 30,000 centistokes, preferably 50 to 3,000 centistokes.

Examples of such a silicone oil [II] include dimethyl silicone oil in which all of R ² and R ³ are methyl groups, and those dimethyl silicone oils in which some of the methyl groups are substituted with phenyl groups. Phenyl methyl silicone oil is mentioned, and among them, methyl phenyl silicone oil is preferable. As such a methylphenyl silicone oil, specifically, for example, “KF-54, KF-56, KF-50” (product of Shin-Etsu Chemical Co., Ltd.), “SH510, SH550” (manufactured by Toray Dow Corning Silicone Co., Ltd.) ), "TSF431, TS
F433 "(manufactured by Toshiba Silicone Co., Ltd.).

The silicone oil having a group represented by the above formula [III] (silicone oil [III]) includes
Those described in Japanese Patent No. 25222854 proposed by the present applicant can be used, and the number average molecular weight is 250
~ 20,000, preferably 1,000 ~ 10,000
Having a viscosity of 20 to 30,000 centistokes,
Preferably 50 to 3000 centistokes is desirable.

≡SiR ⁴ OSiR ⁵ _b Y _3-b ... [III] (In the formula [III], R ⁴ is an unsubstituted or substituted divalent hydrocarbon group or a divalent hydrocarbon containing an ether bond.) A group represented by R ⁵
Is an unsubstituted or substituted monovalent hydrocarbon group, Y is a hydrolyzable group, and b is 0, 1 or 2. As the above R ⁴ , specifically, for example, a methylene group,
Ethylene, propylene, butylene, divalent hydrocarbon group such unsubstituted or substituted as and hexamethylene group; or _{"- (CH 2) p -O- (} CH 2) q - " (wherein,
p and q each independently represent an integer of 1 to 6. ) And the like, and a divalent hydrocarbon group containing an ether bond;

R^FiveAre represented by the formula [I] of the component (C).
R¹Similarly to the above, unsubstituted or substituted having 1 to 8 carbon atoms
Shows a monovalent hydrocarbon group. Y is the formula [I] of the component (C).
And a group similar to the hydrolyzable group X in the above. like this
Silicon having at least one group represented by the formula [III]
Specific examples of the oil [III] include, for example, those described above.
As described in Japanese Patent No. 2522854,
(CH_Three)_ThreeSiO [(CH_Three)_TwoSiO]_m[R⁷R⁸Si
O]_n(CH_Three)_TwoSiC _ThreeH₆-OH, HO-C_ThreeH₆−
[(CH_Three)_TwoSiO] [(CH_Three)_TwoSiO]_m[R⁷R⁸
SiO]_n− (CH_Three)_TwoSi-C_ThreeH₆-OH, (CH_Three)
_ThreeSiO [(CH_Three)_TwoSiO]_m[R⁷R⁸SiO]
_n[(CH_Three) (C_ThreeH ₆—OH) SiO]_l[(CH_Three)_Two
SiCH_Three], The hydroxyl group of the silicone oil represented by
Those blocked with a hydrolysis group are exemplified. However,
In each formula, R⁷, R⁸As phenyl group, tolyl group, etc.
Aryl group; benzyl group, β-phenylethyl group, etc.
Aralkyl group; halogenated amino such as trifluoropropyl group
R, such as a alkyl group;⁷, R⁸At least one of
Is an unsubstituted or substituted group selected from a group other than a methyl group
And monovalent hydrocarbon groups. m, n and l are all positive numbers
Is shown.

In addition, the storage stability of the obtained composition is
As exemplified below, the above silicone oil
With the formula: "R^Five _bSiY_3-b(R^Five, Y, b are of the formula [III]
Same as the case. )
It may be something. (CH_Three)_ThreeSiO [(CH_Three)_TwoSiO]
_m[R⁷R⁸SiO]_n(CH_Three)_TwoSiC _ThreeH₆-OR^Five _bS
iY_3-b, HO-C_ThreeH₆-[(CH_Three)_TwoSiO] [(C
H_Three)_TwoSiO]_m[R⁷R⁸SiO]_n− (CH_Three)_TwoSi-
C_ThreeH₆-OR^Five _bSiY_3-b, (CH_Three)_ThreeSiO [(C
H_Three)_TwoSiO]_m[R⁷R⁸SiO]_n[(CH_Three) (C_ThreeH
₆-OR^Five _bSiY_3-b) SiO]_l[(CH_Three)_TwoSiC
H_Three]Such.

Specific examples of the silicone oil [IV] include those described in JP-A-10-316933, which have a number average molecular weight of 250 to 30,
000, preferably 1,000 to 20,000, and a viscosity of 20 to 30,000 centistokes, preferably 5
Desirable is 0-3,000 centistokes.

R ⁶ _x Si (R ⁷ -Z) _y O _{(4-xy) / 2} ... [IV] (In the formula [IV], R ⁶ is a hydrogen atom, each having 1 to 1 carbon atoms.
0 represents an alkyl group, an aryl group, or an aralkyl group; R ⁷ represents an ether group, an ester group, or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have an interposed —NH—; Represents a monovalent polar group that is an amino group, a carboxyl group, an epoxy group, or a polyethylene glycol or polypropylene glycol group whose terminal may be blocked with an alkyl group or an acyl group having 1 to 6 carbon atoms, and x, y Are 0.01 ≦ x <3.99, respectively.
0.02 ≦ y <4, and 0.02 ≦ x + y <4
Is shown. ).

As such a silicone oil [IV], preferably, in the above formula [IV], R ⁶ is a methyl group or a phenyl group, and R ⁷ is a methylene group, an ethylene group or a propylene group. Things are desirable. When Z is a polyethylene glycol or polypropylene glycol group whose terminal may be blocked with an alkyl group or an acyl group having 6 or less carbon atoms, the number of oxyethylene and oxypropylene as a repeating unit is 10 to 60. preferable. Further, as the alkyl group for terminal blocking, methyl group, ethyl group, propyl group,
Examples of the acyl group for blocking the terminal include a ketoxime group, an acetyl group, and a propionyl group.

Specifically, examples of the silicone oil in which the polar group Z is an amino group include “SF8417” (manufactured by Toray Dow Corning), “ISI4700, ISI470”.
1 (manufactured by Toshiba Silicone Co., Ltd.), "FZ3712, AFL
-40 "(manufactured by Nippon Unicar). As the silicone oil wherein the polar group Z is a carboxyl group,
“XI42-411” (manufactured by Toshiba Silicone Co., Ltd.), “SF
8418 "(manufactured by Toray Dow Corning Silicone Co., Ltd.),
“FXZ4707” (manufactured by Nippon Unicar) and the like. Examples of silicone oils whose polar group is an epoxy group include “SF8411” (manufactured by Toray Dow Corning Silicone), “XI42-301” (manufactured by Toshiba Silicone), and “L-93, T-29” (manufactured by Nippon Unicar) Manufactured). Examples of the silicone oil in which the polar group Z is an alkyl group or an acyl group include “ISI4460, I
SI4445, ISI4446 "(manufactured by Toshiba Silicone Co., Ltd.)," SH3746, SH8400, SH3749,
SH3700 "(manufactured by Dow Corning Toray Silicone Co., Ltd.) and" KF6009 "(manufactured by Shin-Etsu Silicone Co., Ltd.).

In the present invention, such a silicone oil (D), preferably one or more of silicone oil [II], silicone oil [III] and silicone oil [IV], The above component (A) 100
It is desirable that the total amount is 0.1 to 200 parts by weight, preferably 20 to 100 parts by weight, based on parts by weight.

When the amount of the silicone oil (D) is in the above range, for example, when the silicone oil (D) is used as an antifouling paint, a (antifouling) coating film excellent in both antifouling properties and coating strength tends to be obtained. When the amount is less than the above range, the antifouling property is reduced, and when the amount is more than the above range, the coating film strength may be reduced. [Production of curable composition] Such a curable composition according to the present invention, in particular, a coating composition, a curable paint composition and an antifouling paint composition are prepared in advance with a part of component (A) or All and at least the hydrophilic silica of the component (B), preferably both the hydrophilic silica and the hydrophobic silica, are subjected to a normal temperature or a reduced pressure at a temperature not lower than 100 ° C. and not higher than the decomposition temperature of the component, preferably not higher than 100 ° C. After heating at a temperature of about 300 ° C., more preferably about 140 ° C. to 200 ° C., usually for about 30 minutes to 3 hours, the remaining component (A)
In addition to (B) and the component (C) used as needed, it can be manufactured by further blending the component (D) if necessary. In addition, conventionally known organosiloxane curing catalysts, antifouling agents, thixotropy-imparting agents, plasticizers, inorganic dehydrating agents (stabilizers), anti-sagging / sedimentation inhibitors (thickeners), coloring pigments, dyes, and others Once a predetermined ratio of coating film forming components, solvent (eg, xylene), bactericide, antifungal agent, antioxidant, antioxidant, antistatic agent, flame retardant, heat conduction improver, adhesion promoter, etc. Or in any order, followed by stirring / mixing, and dissolving / dispersing in a solvent.

When at least hydrophilic silica of component (B), preferably both hydrophilic silica and hydrophobic silica, of component (B) is heat-treated with component (A), component (A) in the resulting composition is heat-treated. ) And (B) are excellent in affinity, and there is no aggregation of the filler components such as component (B). For example, the obtained coating composition, for example, the antifouling paint composition has an appropriate fluidity and thixotropic property. The coating film having a desired and sufficient thickness can be formed with a small number of coatings such as one coating even on a vertical coating surface.

When the above components are stirred and mixed, a conventionally known mixing and stirring device such as a loss mixer, a planetary mixer or a universal Shinagawa stirrer is appropriately used. As the above-mentioned catalyst, for example, Japanese Patent No. 252
No. 2854 can be preferably used, and specifically, for example, tin carboxylate such as tin naphthenate, tin oleate; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin Tin compounds such as tindiolate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin; tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetonato )
Titanates such as titanium and titanium isopropoxyoctyl glycol or titanium chelate compounds; zinc naphthenate, zinc stearate, zinc-2-ethyloctoate, iron-2-ethylhexoate, cobalt-2 -Ethylhexoate, manganese-2
Organometallic compounds such as -ethylhexoate, cobalt naphthenate and alkoxyaluminum compounds; aminoalkyl-substituted alkoxysilanes such as 3-aminopropyltrimethoxysilane and N-β (ammonoethyl) γ-ammonopropyltrimethoxysilane Hexylamine,
Amine compounds such as dodecyldodecylamine phosphate, dimethylhydroxylamine and diethylhydroxylamine and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate and lithium bromide Silanes or siloxanes containing a guanidyl group, such as tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane; and the like.

These catalysts are used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the component (A).
Further, it is used in an amount of 1 part by weight or less, and a preferable lower limit when used is 0.001 part by weight or more, particularly 0.01 part by weight.
More than parts by weight. <Optional Components> As described above, when the curable composition according to the present invention is used as, for example, a coating composition, particularly a paint composition or an antifouling paint composition, and especially as a curable antifouling paint composition, Is an antifouling agent, a plasticizer, an inorganic dehydrating agent, or a carboxylic acid as described in detail below, if necessary, in addition to the components (A) and (B) and the component (C) used as necessary. Metal salts, anti-sagging / anti-settling agents (thixotropic agents), pigments, other film-forming components, other fillers, flame retardants, thixotropy-imparting agents, heat conduction improvers, solvents, fungicides, antibacterial agents And various components such as a matting agent and a fragrance.

<Anti-fouling agent> The anti-fouling agent may be either inorganic or organic. As the inorganic anti-fouling agent, conventionally known inorganic anti-fouling agents can be used. Compounds are preferred. Organic antifouling agent As the organic antifouling agent, metal-pyrithiones represented by the following formula (vi) [wherein R ^{1 to} R ⁴ each independently represent hydrogen, an alkyl group, an alkoxy group, or a halogenated alkyl group. ,
M is Cu, Zn, Na, Mg, Ca, Ba, Pb, F
e represents a metal such as Al, and n represents a valence]:

[0076]

Embedded image

[0077] tetramethylthiuram disulfide,
Carbamate compounds (eg, zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate), 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 4,
5-dichloro-2-n-octyl-3 (2H) isothiazoline, 2,4,6-trichlorophenylmaleimide,
2-methylthio-4-t-butylamino-6-cyclopropyls-triazine and the like can be mentioned.

Among the above organic antifouling agents, copper pyrithione (M = Cu in the formula (vi)), zinc pyrithione (formula (vi)
Medium, M = Zn), N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-
Methylthio-4-tert-butylamino-6-cyclopropyls-triazine, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,5,6-tetrachloroisophthalonitrile preferable.

Of these organic antifouling agents, metal pyrithiones and / or 4,5-dichloro-2-n-octyl-4-isothizolin-3-one are preferred. Is preferred because it is excellent,
In particular copper pyrithione and / or 4,5-dichloro-2
It is preferable to use -n-octyl-4-isothiazolin-3-one, and it is more preferable to use them in combination.

In the antifouling paint composition containing such an organic antifouling agent, for example, in addition to the copper and / or inorganic copper compound, the organic antifouling agent is usually 0.1 to 20% by weight,
Preferably, it is contained in an amount of 0.5 to 10% by weight. Further, the solid content in the coating composition is 100%.
The organic antifouling agent is usually 0.1 to 150 parts by weight, preferably 0.1 to 100 parts by weight, based on parts by weight.
Desirably, it is contained in parts by weight.

<Plasticizer (Chlorinated Paraffin)> Examples of the plasticizer include TCP (tricresyl phosphate), chlorinated paraffin, polyvinyl ethyl ether and the like. These plasticizers can be used alone or in combination of two or more. These plasticizers are coated films (also referred to as "antifouling coating films") comprising the obtained antifouling coating composition.
Contributes to the improvement of crack resistance.

<Inorganic dehydrating agent> The inorganic dehydrating agent also functions as a stabilizer and can further improve the storage stability of the antifouling paint composition. As such an inorganic dehydrating agent, anhydrous gypsum (CaSO ₄ ), synthetic zeolite-based adsorbents (trade name: molecular sieve, etc.), silicates, etc., and anhydrous gypsum and molecular sieve are preferably used. Such an inorganic dehydrating agent can be used alone or in combination of two or more.

In the curable coating composition containing such an inorganic dehydrating agent, the inorganic dehydrating agent is usually contained in the non-tin-based coating composition of the present invention in an amount of 0.1 to 10% by weight, preferably 0 to 10% by weight. 0.1 to 5% by weight. <Carboxylic acid metal salt> The curable coating composition according to the present invention may further contain a carboxylic acid metal salt.

As the metal carboxylate, those having a molecular weight of usually 50 to 1,000, preferably 100 to 600 are used. Examples of the carboxylic acid constituting such a metal carboxylate include a carboxylic acid having an alicyclic structure (eg, naphthenic acid) and a carboxylic acid having an aromatic ring structure (eg, α- (2-carboxyphenoxy) stearic acid). And rosin-based resin acids and fatty acids, and naphthenic acid, rosin-based resin acids and fatty acids are preferred.

<Anti-sagging / Anti-settling agent (Thixotropic agent)> As an anti-sagging / anti-settling agent (Thixotropic agent), organoclay A
l, Ca, Zn stearate salts, lecithin salts, salts such as alkylsulfonates, polyethylene wax, amide wax, hydrogenated castor oil wax system, polyamide wax system and mixtures thereof, synthetic finely divided silica, polyethylene oxide system Wax and the like, preferably,
Polyamide wax, synthetic finely divided silica, polyethylene oxide wax, and organic clay are used. Examples of such anti-sagging and anti-settling agents are those marketed under the trade names such as "Dispalon A630-20X" in addition to "Disparon 305" and "Disparon 4200-20" manufactured by Kusumoto Kasei Co., Ltd. Is mentioned.

The anti-sagging / anti-settling agent is incorporated into the curable coating composition in an amount of, for example, 0.1 to 10% by weight. <Pigment> As the pigment, conventionally known various organic and inorganic pigments can be used. Examples of the organic pigment include carbon black, phthalocyanine blue, and navy blue. Examples of inorganic pigments include, for example, titanium white, red iron oxide, barite powder, silica, tankal, talc, chalk,
Neutral and non-reactive substances such as iron oxide powder;
nO, zinc oxide), lead white, red lead, zinc dust, lead oxide powder, and the like (active pigments) which are basic and reactive with acidic substances in the paint. Note that various colorants such as dyes may be included. Such various pigments may be contained in the curable composition, particularly the curable coating composition, for example, in a total of 0.1.
It is blended in an amount of about 5 to 45% by weight.

<Other coating film-forming components> As the coating film-forming components, coating film-forming components other than the above-mentioned organopolysiloxane (A) may be contained within a range not inconsistent with the object of the present invention. Such "other coating film forming components"
Examples include acrylic resin, acrylic silicone resin, unsaturated polyester resin, fluorine resin, polybutene resin, silicone rubber, urethane resin (rubber), polyamide resin, vinyl chloride copolymer resin, chlorinated rubber (resin), chlorinated Difficult or non-olefin resins such as olefin resins, styrene / butadiene copolymer resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, cumarone resins, trialkylsilyl acrylate (co) polymers (silyl resins), and petroleum resins A water-soluble resin (hereinafter also referred to as a difficult / water-insoluble resin) can be used.

<Other Fillers, Flame Retardants, Thixotropic Agents, Thermal Conductivity Improvers, Adhesive Components, etc.> As fillers other than those described above, diatomaceous earth, iron oxide, zinc oxide,
Metal oxides such as titanium oxide and alumina or those whose surfaces have been surface-treated with a silane compound; metal carbonates such as calcium carbonate, magnesium carbonate and zinc carbonate; other asbestos, glass fibers, carbon black, quartz powder, water Examples include aluminum oxide, gold powder, silver powder, surface-treated calcium carbonate, and glass balloon. These fillers may be used alone or in combination of two or more.

Examples of the thixotropic agent include polyethylene glycol, polypropylene glycol and derivatives thereof. Examples of the flame retardant include antimony oxide and paraffin oxide. Examples of the heat conduction improver include boron nitride and aluminum oxide. Examples of the adhesive component include a substance containing one or more groups such as an alkoxysilyl group, an epoxy group, a hydrosilyl group, an acryl group, and a hydroxysilyl group, or a mixture of these substances.

<Solvent> The curable composition such as the curable coating composition of the present invention may or may not contain a solvent. Can be used by dissolving or dispersing in a solvent according to the above. As the solvent used here, for example, various solvents such as an aliphatic type, an aromatic type, a ketone type, an ester type, an ether type, and an alcohol type which are usually blended in an antifouling paint are used. Examples of the aromatic solvent include xylene and toluene, and examples of the ketone solvent include MIBK and cyclohexanone. Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl. Ether acetate (PMAC) and the like can be mentioned, and as the alcohol-based solvent, for example, isopropyl alcohol and the like can be mentioned.

Such a solvent can be used in any amount. For example, 100 parts by weight of the component (A)
It is used in an amount of 0.1 to 9999 parts by weight, preferably in an amount of 1 to 50 parts by weight. Further, it is used in an amount of 1 to 99% by weight, preferably 5 to 50% by weight in the curable composition of the present invention. The viscosity (2) of a curable composition such as a curable coating composition diluted as necessary with such a solvent.
5 ° C., B-type viscometer, No. 3 rotor) is, for example, 0.01 to 500 poise / 25 ° C., and preferably 0, in consideration of coatability (sagging property), film thickness obtained by single coating, and the like. .
It is about 1 to 200 poise / 25 ° C. In other words,
0.001 to 50 Pa · s, preferably 0.01 to 20
It is about Pa · s.

The curable composition of the present invention can be used as a coating material (coating composition) for covering the surface of various substrates such as electric parts, electronic parts, building materials, craft supplies, garment industrial supplies, and medical supplies. It is suitably used as an antifouling paint for antifouling the surface of substrates that come into contact with seawater or fresh water, for example, substrates such as underwater structures, ship outer panels, fishing nets and fishing gear. In addition, it is also used as an anti-icing paint, a water repellent and the like.
As described above, the curable composition of the present invention can be used for electric and electronic devices, building materials and crafts, the clothing industry, medical care, agriculture, forestry and fisheries, power generation,
It is used in a wide range of industrial fields such as civil engineering, shipbuilding or ship repair, especially ship painting.

In particular, the above curable composition is used as a coating composition for electrical parts, electronic supplies, building materials, craft supplies,
When applied and cured on the surface of base materials such as apparel industry supplies and medical supplies, the composition has an excellent balance between low viscosity and high thixotropy, so that a single coating can be used to make a thick film. The composition has good properties, and by coating and curing such a composition, for example, a coated substrate having excellent flame retardancy, rubber strength, surface smoothness, and the like can be obtained.

In particular, the curable composition as described above is coated with a paint,
In particular, antifouling paints (antifouling paint compositions) include, for example, underwater structures such as water supply / drainage ports of thermal and nuclear power plants, seawater utilization equipment (eg, seawater pumps, etc.), mega floats, bay roads, submarine tunnels, Sludge diffusion prevention membrane for various marine civil engineering works such as port facilities, canals and waterways, ships, especially ship outer panels,
It is applied to the surface of various molded products such as fishery materials (eg, ropes, fishing nets, floats, buoys) once or multiple times in accordance with ordinary methods and cured, and is excellent in antifouling properties. An antifouling base material such as a ship or an underwater structure coated with an antifouling coating film which can be gradually released over a long period of time, has an appropriate flexibility even when thickly coated, and has excellent crack resistance can be obtained. In the case of such coating, conventionally known coating means such as a brush, a roll, a spray, a dip coater and the like are widely used.

The antifouling coating film obtained by applying and curing the curable antifouling coating composition according to the present invention on the surface of various molded articles (substrates) is Aosa, Barnacle, Aonori, Serpula, Oyster, Fusakokeshi It is excellent in antifouling properties such as the ability to continuously prevent the attachment of aquatic organisms such as water. In particular, the curable antifouling paint composition can be used on the surface of a base material (material) even when the material of a water supply / drain port, mega float, ship, etc. of a nuclear power plant is FRP, steel, wood, aluminum alloy, or the like. Good adhesion to Further, the curable antifouling paint composition may be overcoated on the surface of an existing antifouling coating film.

For example, if the curable antifouling paint composition is applied to the surface of a marine structure and cured, the adhesion of marine organisms can be prevented, and the function of the structure can be maintained for a long time. If applied to, can prevent the blockage of the fishing net,
Moreover, there is little risk of environmental pollution. The curable antifouling paint composition according to the present invention may be directly applied to a fishing net, or applied to a surface of a ship or an underwater structure or the like to which a base material such as a rust inhibitor and a primer has been applied in advance. May be.
Furthermore, the surface of a ship, particularly an FRP ship or an underwater structure, which has already been coated with a conventional antifouling paint or has been coated with the curable antifouling paint composition of the present invention, is used for repair. Alternatively, the curable antifouling paint composition of the present invention may be overcoated. The thickness of the antifouling coating film formed on the surface of a ship, an underwater structure or the like in this manner is not particularly limited, but is, for example, about 30 to 150 μm / time.

The antifouling coating film of the present invention obtained as described above or the coating film on the surface of the water-contacting portion of a ship / underwater structure is formed from the above-mentioned curable antifouling coating composition. It has a low risk of environmental pollution and has excellent long-term antifouling properties against a wide range of organisms attached to ships and underwater structures.

[0098]

When the curable composition according to the present invention is used as a coating composition, in particular, a paint, an antifouling paint composition, etc., it exhibits low viscosity and high thixotropy in a well-balanced manner.
Excellent spray coating properties, such as no nozzle clogging and turbulence, enables a thicker film to be formed by a single coating, shortens the coating period, and allows uniform coating surface uniformity (uniform film thickness or surface smoothness) A cured product such as a coating film having excellent properties is obtained, and the obtained coating film has a coating film strength (rubber strength),
Excellent coating film hardness, and when used as an antifouling paint, the resulting coating film can exhibit excellent antifouling performance for a long time, and also has excellent storage stability before coating, and therefore, a coating composition In particular, a curable composition suitable as a curable paint composition, an antifouling paint composition and the like is provided.

Further, according to the present invention, various cured products such as a coating film and a cured coating material exhibiting excellent coating film strength and coating film hardness and exhibiting excellent antifouling performance for a long period of time as described above. In particular, an antifouling coating film, and an underwater structure, a ship outer panel, etc., coated with the coating film and provided with these characteristics are provided. Furthermore, according to the present invention, a coating film having the above-mentioned excellent properties can be efficiently formed on the surface of various substrates such as the surface of an underwater structure, safely for an operator, and without fear of environmental pollution. It is possible to provide a method for forming a coating film on the surface of a substrate such as an electronic component, and a method for preventing the surface of a substrate such as an underwater structure from being stained.

[0100]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples and Comparative Examples. The composition values and the like described in the following Synthesis Examples, Examples, and Comparative Examples are expressed in parts by weight.

(Synthesis of Silicone Oil (D))

[0102]

[Synthesis Example 1] The following formula:

[0103]

Embedded image

193 g of an organopolysiloxane containing an alcoholic hydroxyl group represented by the following formula and 60 g of methyltri (methylethylketoxime) silane are mixed and reacted at room temperature.

[0105]

Embedded image

A silicone oil (D) represented by the following formula was obtained. This silicone oil contained unreacted raw material methyltri (methylethylketoxime) silane.

[Preparation of Organopolysiloxane Coating Compositions (A) to (F) described in Table 1] Both ends of the molecule are blocked with silanol groups and have a viscosity of 20,000 cst (2
A mixture of 50 parts by weight of dimethylpolysiloxane (10,000 cst) and 10 parts by weight of hydrophobic fumed silica surface-treated with hexamethyldisilazane was mixed and stirred at 150 ° C. for 2 hours and heat-treated (see * 2). The same hydrophobic silica described above was mixed and stirred at room temperature with 50 parts by weight of an organopolysiloxane (see * 3), and 10 parts by weight of the hydrophilic silica described in Table 1 was mixed with 50 parts by weight of an organopolysiloxane. The mixture was mixed and stirred at 150 ° C. for 2 hours, and heat-treated (see * 4) was blended in the blending amount shown in Table 1, and was sufficiently mixed and dispersed by a stirring device so as to be uniform. Further, a crosslinking agent and a catalyst were added in the amounts shown in Table 1 and uniformly mixed to obtain a room-temperature-curable organopolysiloxane-based coating composition having the compositions shown in (A) to (F).

Table 1 shows these property values. * 1, 2, 3, 4 and the test method in Table 1 are as follows. In the table, various silicas are the amount (parts by weight) of silica based on 100 parts by weight of the organopolysiloxane (A). * 1: Organopolysiloxane: manufactured by Shin-Etsu Chemical Co., Ltd. Chemical formula: “HO (CH ₃ .CH ₃ .SiO) _m H” (25
* 2: Heat-treated hydrophobic fumed silica: Silica obtained by mixing and heating the hydrophobic fumed silica shown in Table 1 and the above organopolysiloxane at 150 ° C. for 2 hours with stirring, Shin-Etsu Chemical Co., Ltd. Made, silica water content 0.05
%, Bulk density 50 g / L, primary particle diameter 10 mμ, and specific surface area (BET surface area) 180 m ² / g. * 3: hydrophobic fumed silica treated at room temperature: silica obtained by mixing and stirring the hydrophobic fumed silica shown in Table 1 and the above organopolysiloxane at room temperature for 2 hours, manufactured by Shin-Etsu Chemical Co., Ltd., water content 0.2% , Bulk density 50 g / L, primary particle diameter 10 mμ, specific surface area (BET surface area) 180 m ² /
g. * 4: Heat-treated hydrophilic silica: the hydrophilic silica described in Table 1 and the above-mentioned organopolysiloxane were treated at 150 ° C. for 2 hours.
Silica mixed and stirred for hours, manufactured by Shin-Etsu Chemical Co., Ltd., having a water content of 1.0%, a bulk density of 60 g / L, a primary particle diameter of 12 mμ, and a specific surface area (BET surface area) of 190 m ² / g.

[Test Method] (a) Viscosity: The viscosity was measured by a B-type viscometer (No. 3 rotor) of the viscosity (Pa · s / 25 ° C.) of the organopolysiloxane coating composition obtained in Table 1. I asked. (B) Coating physical properties: The coating physical properties were determined by applying each of the organopolysiloxane coating compositions (A) to (F) on a stainless steel plate,
Leave it at 25 ° C and 55% RH for 7 days to cure and make it 2m thick
m were prepared and examined.

Table 1 shows the results.

[0111]

[Table 1]

[0112]

Examples 1 to 4 and Comparative Examples 1 and 2 To 100 parts by weight of each of the organopolysiloxane coating compositions (A) to (F) obtained in Table 1 were added silicone oil and xylene in the composition shown in Table 2. The mixture was added and stirred until it became uniform to obtain each antifouling paint composition. The properties and coating workability of each paint were examined.

Table 2 shows the results. Further, an antifouling test was performed on each antifouling paint immediately after preparation. Table 3 shows the results.
Note that * 5, 6, 7, 8 and the test method in Table 2 are as follows. In addition, the parentheses for the amounts of various silicone oils and the like are those of organopolysiloxane (A) 10
It is a blending amount (parts by weight) based on 0 parts by weight. * 5: "SH550": dimethylphenyl silicone oil, viscosity: 130 centistokes, manufactured by Toray Dow Corning Silicone Co., Ltd. * 6: "TSF431": dimethylphenyl silicone oil, viscosity: 100 centistokes, manufactured by Toshiba Silicone Co., Ltd. * 7: "KF50": dimethylphenyl silicone oil, viscosity: 100 centistokes, manufactured by Shin-Etsu Chemical Co., Ltd. * 8: “KF6016”: polyether-modified silicone oil, viscosity: 150 centistokes, manufactured by Shin-Etsu Chemical Co., Ltd.

[0114]

[Table 2]

[0115]

[Table 3]

[Test Method] (A) Paint property value: The paint property value was measured in the same manner as in Example (A). The coating workability and antifouling test are as follows. (B) Painting workability: size 1000 mm x 1000 mm x
In the center of a 1 mm (thick) tin plate, 70 mm x 150 mm
Airless spray coating with a 1mm (thick) mild steel plate attached, and a tin plate standing upright, confirming the presence or absence of clogging of the equipment at the time of spraying and drying the limit film thickness at which film sagging occurs It was measured afterwards. (C) Antifouling test: 100 mm x 300 mm x 5 mm (thickness)
A 200 μm-thick epoxy-based undercoat is applied to the PVC plate, and each antifouling paint is brush-coated on the coating so that the dry film thickness becomes 150 μm, and dried for 3 days.
The sample was immersed for 0 month, and the antifouling property was evaluated by visual observation. (D) Evaluation of paint stability and coating workability: Also, after preparing each antifouling paint, the paint state (stability) after 3 months at 50 ° C.
A test was conducted on the coating workability.

The results are shown in Table 2 above. (E) Antifouling test: After preparing an antifouling paint, an antifouling test was performed on the antifouling paint after 3 months at 50 ° C. Table 4 shows the results.

The test method is as follows. [Test method] Paint state (stability): Put each antifouling paint shown in Table 2 in a can, leave it in a sealed state in a thermostat at 50 ° C for 3 months, and carefully paint after opening the can. The mixture was stirred and inspected with a tub gauge.

[0119]

[Table 4]

[0120]

Example 5 25 ° C. having 5 mol% of diphenylsiloxy units (—Ph ₂ SiO—, Ph: phenyl group) in one molecule and both ends of a molecular chain (molecule) blocked with a hydroxyl group
Dimethylpolysiloxane 50 parts by weight, hydrophilic silica 10 parts by weight of a BET specific surface area of 200 meters ² / g, the surface of hydrophobic silica treated with hexamethyldisilazane having a BET specific surface area of 130m ² / g viscosity of 20,000cS in 10
The parts by weight were stirred and mixed at 150 ° C. for 2 hours. afterwards,
Having 5 mol% of diphenylsiloxy groups in one molecule,
Viscosity at 25 ° C with both molecular ends blocked with hydroxyl groups is 2
The mixture was diluted with 50 parts by weight of dimethylpolysiloxane of 000 cS, and 10 parts by weight of methyltributanoxime silane, 0.1 part by weight of dibutyltin dioctoate, and 1.0 part by weight of aminopropyltrimethoxysilane were degassed and mixed. To this composition was further added 40 parts by weight of xylene, and 20 m
A Pa · s curable silicone solution was used. When this was applied to an aluminum wall surface with a coating roll, a coating thickness of 400 microns could be obtained. This composition is
When cured at 70 ° C./55% RH / 7 days, a rubber having a glossy surface, good transparency, a durometer type A hardness of 60, and a tensile strength of 4.0 MPa was obtained. A cured coating having the above was obtained.

[0121]

Comparative Example 3 A molecule having 5 mol% of diphenylsiloxy units in one molecule and having both ends of a molecular chain blocked with hydroxyl groups 25
50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS at 20 ° C. and 20 parts by weight of hydrophilic silica having a BET specific surface area of 200 m ² / g were stirred and mixed at 150 ° C. for 2 hours. Then, at 25 ° C. having 5 mol% of diphenylsiloxy groups in one molecule and both ends of the molecular chain blocked with hydroxyl groups.
Diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS in methyltributanoxime silane 1
0 parts by weight, 0.1 parts by weight of dibutyltin dioctoate,
1.0 part by weight of aminopropyltrimethoxysilane was defoamed and mixed. To this composition was further added 40 parts by weight of xylene to obtain a curable silicone solution of 13 mPa · s. When this was painted on an aluminum wall with a painting roll,
The limit is to obtain a coating thickness of 100 microns, and if an attempt is made to obtain a coating thickness of more than 100 microns, sagging occurs.

[0122]

Example 6 25 ° C. in which both ends of a molecular chain are blocked with hydroxyl groups
Weight of dimethyl polysiloxane having a viscosity of 20,000 cS (20,000 cS) at a BET specific surface area of 200 m ² /
g of 5 parts by weight of hydrophilic silica and 10 parts by weight of hydrophobic silica having a BET specific surface area of 130 m ² / g whose surface was treated with hexamethyldisilazane were stirred and mixed at 150 ° C. for 2 hours. Then, both ends of the molecular chain were blocked with hydroxyl groups at 25 ° C.
Diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS (20,000 cS), 10 parts by weight of methyltributanoxime silane, 0.1 part by weight of dibutyltin dioctoate, and aminopropyltrimethoxysilane.
0 parts by weight were defoamed and mixed, and the viscosity was adjusted by adding 20 parts by weight of methyl ethyl ketone to obtain a curable silicone composition having a viscosity of 60 mPa · s. This composition was coated on an electronic substrate with a dispenser, and was heated at 23 ° C./55% R
When cured under the condition of H / 7 days, a glossy silicone film having a very good appearance was formed on the substrate. This film had good physical properties such as a durometer type A hardness of 50 and a tensile strength of 3.5 MPa.

[0123]

Comparative Example 4 Both ends of a molecular chain were blocked with hydroxyl groups at 25 ° C.
Was mixed at room temperature with 50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS (20,000 cS) and 15 parts by weight of hydrophobic silica having a BET specific surface area of 130 m ² / g whose surface was treated with dimethyldichlorosilane.

Thereafter, the mixture was diluted with 50 parts by weight of dimethyl polysiloxane having a viscosity of 20,000 cS at 25 ° C., both ends of which were blocked with hydroxyl groups, and 10 parts by weight of methyltributanoxime silane and 0.1 part by weight of dibutyltin dioctoate. 1
By weight, 1.0 part by weight of aminopropyltrimethoxysilane was degassed and mixed, and the viscosity was adjusted by adding 20 parts by weight of methyl ethyl ketone to obtain a curable silicone composition having a viscosity of 80 mPa · s.

This composition was coated on an electronic substrate with a dispenser. The composition was inferior in dischargeability from a nozzle and was cured at 23 ° C./55% RH / 7 days. A matte silicone film was formed.

[0126]

Example 7: Both ends of a molecular chain were blocked with hydroxyl groups at 25 ° C.
Dimethylpolysiloxane 5 with a viscosity of 5,000 cS
0 parts by weight, a BET specific surface area of 200 meters ² / g hydrophilic silica 5 parts by weight, hydrophobic silica 5 parts by weight of hexamethyldisilazane treated with a BET specific surface area of 130m ² / g to the surface, for 2 hours at 0.99 ° C. Stir and mix. Thereafter, the viscosity at 25 ° C. at which both ends of the molecular chain were blocked with hydroxyl groups was 5,000.
Diluted with 50 parts by weight of 0 cS dimethylpolysiloxane,
Then, 2.0 parts by weight of zinc carbonate, 10 parts by weight of vinyltributanoxime silane, 1.5 parts by weight of aminopropyltrimethoxysilane, and a platinum catalyst having a platinum atom concentration of 300 parts by weight.
The resulting mixture was mixed to give a curable silicone composition having a viscosity of 10 mPa · s. This composition was dip-coated on a glass fiber and cured under the conditions of 23 ° C./55% RH / 7 days. As a result, a good flame-retardant coat film having a substantially uniform thickness of about 1 mm was obtained.

[0127]

Comparative Example 5 25 ° C. in which both ends of a molecular chain are blocked with hydroxyl groups
Dimethylpolysiloxane 5 with a viscosity of 5,000 cS
0 parts by weight and 10 parts by weight of a hydrophilic silica having a BET specific surface area of 200 m ² / g were stirred and mixed at 150 ° C. for 2 hours. Thereafter, the mixture was diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity of 5,000 cS at 25 ° C. in which both ends of the molecular chain were blocked with hydroxyl groups, and then 2.0 parts by weight of zinc carbonate and 10 parts by weight of vinyltributanoxime silane. 1.5 parts by weight of aminopropyltrimethoxysilane and a platinum catalyst were mixed so that the concentration of platinum atoms was 300 ppm, and the viscosity was 4 Pa · s.
A curable silicone composition was obtained. This composition was dip-coated on glass fiber and heated at 23 ° C./55% RH /
When the composition was cured under the conditions for 7 days, sagging and drips were generated during the curing, and a flame-retardant cured product having a uniform film thickness could not be obtained.

[0128]

Example 8: Both ends of a molecular chain are blocked with hydroxyl groups at 25 ° C.
Viscosity dimethylpolysiloxane 100 parts by weight of 1,000,000CS, hydrophilic silica 30 parts by weight of a BET specific surface area of 200 meters ² / g, a BET specific and treated with dimethyldichlorosilane surface area 130m ² / g hydrophobic in 15 parts by weight of silica, 10 parts by weight of dimethylpolysiloxane having an average degree of polymerization of 13 in which both molecular chain terminals are blocked with hydroxyl groups,
The mixture was stirred and mixed at 50 ° C. for 2 hours. When 10 parts by weight of vinyltributanoxime silane, 1.5 parts by weight of aminopropyltrimethoxysilane, and 65 parts by weight of xylene were further added to this composition, the viscosity measured with a BL rotational viscometer at 4 rotations was 60 Pa · s, 20 parts by weight. By rotation, a composition having a high thixotropy of 4 Pa · s was obtained. This composition is heated at 23 ° C /
When cured at 55% RH / 7 days, it has a glossy surface,
Good transparency, Durometer type A hardness: 6
5. A cured coating having good rubber properties and a tensile strength of 8.0 MPa was obtained.

[0129]

Comparative Example 6 25 ° C. in which both ends of a molecular chain are blocked with hydroxyl groups
Weight: 100 parts by weight of dimethylpolysiloxane having a viscosity of 1,000,000 cS, 45 parts by weight of hydrophilic silica having a BET specific surface area of 200 m ² / g, and dimethylpolysiloxane having an average degree of polymerization of 13 and having both molecular chains terminated by hydroxyl groups. 10 parts by weight were stirred and mixed at 150 ° C. for 2 hours. When 10 parts by weight of vinyltributanoxime silane, 1.5 parts by weight of aminopropyltrimethoxysilane, and 65 parts by weight of xylene were further added to this composition, the viscosity measured with a BL rotational viscometer at 4 rotations was 12 Pa · s, 20 parts by weight. 9Pa · s for rotation
And the thixotropy was quite low.

[0130]

[Comparative Example 7] 25 ° C. in which both ends of a molecular chain are blocked with hydroxyl groups
Weight of 100,000,000 parts by weight of dimethylpolysiloxane having a viscosity of 1,000,000 cS, 45 parts by weight of hydrophobic silica having a BET specific surface area of 200 m ² / g whose surface was treated with dimethyldichlorosilane, and both ends of molecular chains were blocked with hydroxyl groups. 10 parts by weight of dimethylpolysiloxane having an average degree of polymerization of 13 was stirred and mixed at room temperature for 2 hours. When 10 parts by weight of vinyltributanoxime silane, 1.5 parts by weight of aminopropyltrimethoxysilane, and 65 parts by weight of xylene were further added to this composition, the viscosity measured with a BM rotational viscometer was 85 at 4 rotations.
The thixotropy was high at 180 Pa · s at 0 Pa · s and 20 rotations, but the viscosity was extremely high.

[0131]

Example 9 50% by weight of dimethylpolysiloxane having a viscosity of 20,000 cS (20,000 cS) at 25 ° C. and both ends of a molecular chain blocked with a trimethoxysiloxy group (—O—Si— (OCH ₃ ) ₃ ). Part, BET specific surface area 200 m ² / g
5 parts by weight of hydrophilic silica (fumed silica) having a BET specific surface area of 1 treated with hexamethyldisilazane
5 parts by weight of 30 m ² / g hydrophobic fumed silica
The mixture was stirred and mixed at 150 ° C. for 2 hours. Thereafter, the mixture was diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS (20,000 cS) at 25 ° C. in which both terminals of the molecular chain were blocked with trimethoxysiloxy groups, 5 parts by weight of methyltrimethoxysilane, 0.1 part by weight of octoate and 1.0 part by weight of aminopropyltrimethoxysilane are defoamed and mixed, and the viscosity is adjusted by adding 20 parts by weight of methyl ethyl ketone, and the curable silicone composition having a viscosity of 200 mPa · s (L ) (Curable composition L) was obtained. When this composition was cured under the conditions of 23 ° C./55% RH / 7 days, a glossy silicone film having a very good appearance was formed on the substrate. The cured product had good rubber properties with a durometer type A hardness of 40 and a tensile strength of 2.7 MPa. (According to JIS 6249)

[0132]

Comparative Example 8 The viscosity at 25 ° C. of both ends of a molecular chain blocked with a trimethoxysiloxy group was 20,000 cS (20,000 cS).
50 parts by weight of the dimethylpolysiloxane of S) and 10 parts by weight of hydrophobic fumed silica having a BET specific surface area of 200 m ² / g were stirred and mixed at room temperature for 2 hours. Then, both ends of the molecular chain are blocked with trimethoxysiloxy groups, and dimethylpolysiloxane having a viscosity of 20,000 cS at 25 ° C.
The mixture was diluted with 50 parts by weight, degassed and mixed with 5 parts by weight of methyltrimethoxysilane, 0.1 part by weight of dibutyltin dioctoate, and 1.0 part by weight of aminopropyltrimethoxysilane, and added with 20 parts by weight of methyl ethyl ketone. The viscosity was adjusted to obtain a curable silicone composition (M) having a viscosity of 480 mPa · s. The composition (M) was coated on an electronic substrate with a dispenser. However, the composition was inferior to the composition of Example 9 in terms of dischargeability from a nozzle.
When cured under the condition of RH / 7 days, an emulsified surface matte silicone coating was formed on the substrate. The cured product has a durometer type A hardness of 35,
The tensile strength was 2.0 MPa. (According to JIS 6249) Thus, according to Examples 5 to 9 and Comparative Examples 3 to 8, the curable composition of the present invention has a low viscosity and a high thixotropy, and the workability during coating. It is clear that the coating film strength and the surface smoothness are excellent.

[0133]

Examples 10 to 13 and Comparative Examples 9 to 12 The curable silicone compositions described in Example 9 above (Examples 10 to 13) were used in place of the organopolysiloxane composition (A). L), and in Comparative Examples 9 to 12, the curable silicone composition (M) described in Comparative Example 8 was used.
An antifouling paint composition was prepared in the same manner as in Example 1 except that silicone oil and xylene were used in the amounts shown in Table 5, respectively, and various physical properties were evaluated in the same manner as in Example 1.

Tables 5 to 8 show the results. Table 5 shows that
Table 2 shows the properties and the paint workability when the paint was formed in the same manner as in Table 2. Table 6 shows the antifouling properties after the paint was formed in the same manner as in Table 3. Table 7 shows the properties of the paint after storage for a predetermined period. Table 8 shows the values.
The stain resistance of the paint after storage is shown in the same manner as in Table 4.

[0135]

[Table 5]

[0136]

[Table 6]

[0137]

[Table 7]

[0138]

[Table 8]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/04 C08L 83/04 C09D 5/16 C09D 5/16 183/04 183/04 (72) Inventor Toshiharu Yamamoto 1 in 1 Meiji-Shinkai, Otake-shi, Hiroshima Pref. Inside China Coating Co., Ltd. (72) Inventor Hironobu Muramatsu 1-10, Hitomi, Matsuida-cho, Usui-gun, Gunma 1-10 F term in the laboratory (reference) 4J002 CP03X CP05W CP06W DJ016 EX037 EX047 FB096 FB266 GH00 4J038 DL031 DL081 HA446 KA08 KA20 LA02 NA05 NA11 NA23 NA26 PA06 PA19 PB05 PB07

Claims (22)

[Claims] 1. A curable composition comprising (A) an organopolysiloxane in which both terminals of a molecule are condensation-reactive functional groups, and (B) hydrophobic silica and hydrophilic silica. 2. The method according to claim 1, wherein the organopolysiloxane (A) has the following formula [α]: (In the formula [α], W represents a hydroxyl group or a hydrolyzable group;
¹ and R each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a plurality of R ¹ and R may be the same or different from each other, and n is 5 or more. A represents an integer, and a represents 0, 1 or 2. The curable composition according to claim 1, wherein (3) W in the above formula [α] is a hydroxyl group, and
In addition to the component (A) and the component (B), which are 2, C) Formula [I]: R ¹ _a SiX _4-a (in the formula [I], R ¹ has ¹ carbon atom. ~
8 represents an unsubstituted or substituted monovalent hydrocarbon group, X represents a hydrolyzable group, and a represents 0 or 1. 3. The curable composition according to claim 2, which contains the organosilane represented by the formula (1) or a partial hydrolyzate thereof. 4. The method according to claim 1, wherein the hydrophilic silica comprises the component (A)
4. A heat treatment at a temperature of 100 [deg.] C. or more.
The curable composition according to any one of the above. 5. The above component (B) is replaced with the above component (A) 100
The curable composition according to any one of claims 1 to 4, which is contained in an amount of 1 to 100 parts by weight based on part by weight. 6. The component (C) is replaced with the component (A) 100
4. The composition according to claim 3, which is contained in an amount of 1 to 20 parts by weight based on parts by weight.
3. The curable composition according to item 1. 7. The method according to claim 1, wherein the hydrophobic silica (a) and the hydrophilic silica (b) are contained in a weight ratio ((a) / (b)) = 1/99 to 99/1. A curable composition according to any one of the above. 8. The silicone oil (D) is added in a total amount of 0.1 to 2 parts by weight based on 100 parts by weight of the component (A).
It is contained in an amount of 00 parts by weight.
8. The curable composition according to any one of 7. 9. The curable composition according to claim 1, further comprising a catalyst, an antifouling agent and / or a colorant. 10. The method for producing the curable composition,
The method according to any one of claims 1 to 9, further comprising a step of heating the component (A) and at least the hydrophilic silica of the component (B) at a temperature of 100 ° C or higher. A method for producing a curable composition. 11. A coating composition comprising the curable composition according to claim 1. 12. The composition according to claim 11, wherein said coating composition is a paint. 13. The paint according to claim 12, wherein said paint is an antifouling paint.
A composition according to claim 1. 14. A cured product obtained by curing the curable composition according to claim 1. 15. A coating film comprising the curable composition according to claim 1. 16. An antifouling coating film comprising the curable composition according to claim 1. 17. A substrate with a coating film, wherein the surface of the substrate is coated with a coating film obtained by curing the curable composition according to claim 1. 18. A surface of a base material which comes into contact with seawater or fresh water is coated with a coating film obtained by curing the curable composition according to any one of claims 1 to 9. Antifouling substrate. 19. The antifouling substrate according to claim 18, wherein the substrate is any of an underwater structure, a ship outer panel, a fishing net, and fishing gear. 20. A method of applying or impregnating a coating material comprising the curable composition according to claim 1 on the surface of a substrate, and then curing the coating material to form a coating film. A method for forming a coating film on the surface of a substrate, characterized by the following. 21. An antifouling paint comprising the curable composition according to any one of claims 1 to 9 applied or impregnated on the surface of the substrate, and then the antifouling paint is cured to obtain an antifouling coating film. A method for preventing soiling of a substrate, characterized by forming 22. The method according to claim 21, wherein the substrate is any of an underwater structure, a ship outer panel, a fishing net, and fishing gear.