JPH09100362A - Room temperature foam-curable silicone composition - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: To provide a room-temperature-curable organopolysiloxane composition which is free from environmental pollution and has a long-lasting antifouling effect of preventing adhesion of marine organisms such as barnacles and is useful as an antifouling paint. provide. SOLUTION: The room temperature foam-curable silicone composition comprises (A) a vehicle mainly composed of organopolysiloxane and having foam-curing properties, and (B) a silicone oil which is incompatible with the organopolysiloxane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a room temperature foam-curable silicone composition, and more specifically, it is applied to a place that is in contact with seawater for a long period of time, such as a seawater introduction pipe, a marine structure or a ship, to pollute the environment. The present invention relates to a room temperature foam-curable silicone composition which is useful as an antifouling paint capable of preventing marine organisms such as barnacles from adhering for a long period of time.

[0002]

2. Description of the Related Art For example, marine organisms such as barnacles adhere to places that have been in contact with seawater for a long period of time, such as seawater introduction pipes, marine structures, and ships, and cause various harmful effects. Conventionally, in order to prevent such marine organisms from attaching,
At locations where seawater comes into contact, paints containing cuprous oxide, tributyltin, triphenyltin, etc. were applied, but since these additives cause environmental pollution such as contaminating seafood, In recent years, use of these has been a concern. Also,
Paints that do not use additives that cause such environmental pollution include those that form a coating film that lowers the surface energy of the contact area of seawater, and coating films that have a hydrophobic hydrophilic microphase separation structure on the surface. There are those which are formed and those which form a coating film capable of bleeding incompatible oil on the surface. Specifically, a vehicle mainly composed of a curable silicone composition to which an organic compound such as liquid paraffin is added (see JP-A-53-79980), a vehicle mainly composed of a curable silicone composition Those containing an organic compound that lowers the surface energy such as petrolatum obtained from petroleum fractions (see Japanese Patent Application Laid-Open No. 60-3433), and those containing polyvinyl butyral in a vehicle mainly composed of a curable silicone composition. (JP-A-54-2
No. 6826, Japanese Patent Publication No. 57-16868), a vehicle mainly composed of a curable silicone composition, to which a phenyl-modified silicone oil which is incompatible with the silicone vehicle is added (Japanese Patent Publication No. 56-262).
No. 72) is known. However, the coating film formed by using these paints can prevent the adhesion of marine organisms for about two years, and no further effect of preventing the adhesion can be obtained. In particular, paints containing phenyl-modified silicone oils that are incompatible with the silicone vehicle must be added in large amounts in order to prolong the service life, and therefore the physical properties of the paint film itself and the base paint Adhesion becomes insufficient.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to use room-temperature-curable organoorganic compounds which are useful as an antifouling paint which has no environmental pollution and has a long-lasting antifouling effect of preventing adhesion of marine organisms such as barnacles. A polysiloxane composition is provided.

[0004]

Means for Solving the Problems The present inventor has found that the effect of preventing the adhesion of marine organisms is improved if the coating film formed at the portion in contact with seawater is continuously vibrated by the movement of seawater. Has reached the present invention.

The present invention is a room temperature foam-curable silicone composition containing (A) a vehicle mainly composed of organopolysiloxane and having foam-curing properties, and (B) a silicone oil which is not compatible with the organopolysiloxane. .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

(A) Mainly composed of organopolysiloxane
Vehicle having foam-curing property The foam-curing vehicle of the component (A) used in the present invention includes, for example, an organopolysiloxane and a curing agent, and hydrogen gas is generated by mixing these components to form a sponge-like foam. It can be used without particular limitation as long as it can be cured. Examples of such a foam-curable vehicle include a known room-temperature foam-curable organopolysiloxane composition, and a typical example thereof is an organopolysiloxane having at least two silanol groups in one molecule, Examples thereof include compositions containing an organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule and a catalyst.

Organopolysiloxane having silanol group
The organopolysiloxane having at least two silanol groups in hexane per molecule, for example, the following general formula _{(1): R i (OH} ) j SiO [4- (i + j)] / 2 (1) ( In the formula, R is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and i and j are 0 to 3 provided that i + j is 1 to 3. Is an integer of 1 and j is an integer of 1 to 3).

The component organopolysiloxane is the base component of the foam-curable organopolysiloxane composition, and the silanol group undergoes a dehydrogenation reaction with a hydrogen atom bonded to a silicon atom of the component organopolysiloxane to give a hydrogen atom. It cures while generating hydrogen gas, which is a foaming source, and becomes a sponge-like cured product.

Examples of the substituted or unsubstituted monovalent hydrocarbon having no aliphatic unsaturated bond represented by R in the general formula (1) include, for example, methyl group, ethyl group, propyl group, and the like. An alkyl group having 1 to 6; a cycloalkyl group having 6 to 10 carbon atoms such as cyclohexyl group; an aryl group having 6 to 10 carbon atoms such as phenyl group, tolyl group; benzyl group, 2-phenylethyl group, 2- Aralkyl groups having 7 to 12 carbon atoms such as phenylpropyl group; and groups in which at least a part of hydrogen atoms of these groups are substituted with halogen atoms, for example, 3,3,3-trifluoropropyl group and the like. .

The unit represented by the above formula (1) may be present at the end of the molecular chain or may be present in the middle of the molecular chain.

The component organopolysiloxane may have any other organosiloxane unit as long as it has at least two units of the formula (1) in one molecule. Examples of such other organosiloxane units include the following general formula (2): R _e SiO _{(4-e) / 2} (2) (wherein R has the same meaning as described above, and e is 1 to 3). Units that are integers).

R in the above formula (2) is defined as the above formula (1).
Examples of the same as those exemplified in.

The molecular structure of the component organopolysiloxane may be linear, branched, cyclic, or net-like, but a linear one is usually used. These organopolysiloxanes may be used alone or in combination of two or more. Furthermore, the viscosity of this organopolysiloxane is not particularly limited, and at 25 ° C.
It can be used from low viscosity of about 100 centipoise to high viscosity called silicone raw rubber.

A typical organopolysiloxane as a component is, for example, the following general formula (3): HO (R ⁴ R ⁵ SiO) _L H (3), wherein R ⁴ and R ⁵ are the same. Can be different,
An organopolysiloxane represented by the following formula, which is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and L is an integer of 20 to 3,000, and the following general formula (4): (R ⁶ ) ₃ SiO (R ⁴ R ⁵ SiO) _M [R ⁴ Si (OH) O] _N Si (R ⁶ ) ₃ (4) [In the formula, R ⁴ and R ⁵ are the same as defined above, and R ⁶ is independently a fat. It is a substituted or unsubstituted monovalent hydrocarbon group having no group unsaturated bond, M is an integer of 2 to 20, and N is 3 to 20.
Is an integer of], and the like.

R ⁴ , R ^{5 of the} above formulas (3) and (4) or
Examples of the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond represented by R ⁶ include the same as those exemplified in the above formula (1).

A particularly suitable component of the organopolysiloxane is dimethylorganopolysiloxane terminated at both ends with silanol groups.

Having a hydrogen atom bonded to a silicon atom
The organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms in the organopolysiloxane per molecule, for example,
A unit represented by the following general formula (5): R _i (H) _j SiO _{[4- (i + j)] / 2} (5) (wherein R, i and j have the same meanings as described above) Organopolysiloxanes having at least two in one molecule are mentioned.

The component organopolysiloxane functions as a so-called cross-linking agent, and a hydrogen atom bonded to a silicon atom undergoes a dehydrogenation reaction with a silanol group of the component organopolysiloxane to form a cured product. Moreover,
Hydrogen gas, which is a foaming source, is generated by the dehydrogenation reaction, so that foaming occurs at the same time as curing, and the resulting cured product becomes a sponge-like foam.

The group R in the general formula (5) is the same as R in the general formula (1), and examples thereof include the same groups as those exemplified for the general formula (1).

The unit represented by the general formula (5) may be present at the end of the molecular chain or may be present in the middle of the molecular chain. It may be present in both of them.

Further, examples of the unit other than the general formula (5) include the unit represented by the general formula (2).

The molecular structure of the component organopolysiloxane may be linear, branched, cyclic, or net-like, but a linear or cyclic one is usually used.
Further, the organopolysiloxane may be used alone or in combination of 2
A combination of more than one species may be used. Further, the viscosity is not particularly limited, but generally 1 to 1000 at 25 ° C.
It is preferably 0 centipoise.

Specific examples of the organopolysiloxane of the component include, for example, the formula: R ⁷ (R ⁷ R ⁷ SiO) _q (R ⁷ HSiO) _r Si (R ⁷ ) ₃ [wherein R ⁷ is independently a fat An organopolysiloxane represented by the formula (1) is a substituted or unsubstituted monovalent hydrocarbon group having no group unsaturated bond, q is an integer of 0 to 100, and r is an integer of 2 to 100].

The substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond represented by R ⁷ in the above formula is
The same thing as what was illustrated about R of the said General formula (1) is mentioned.

It is generally preferable to use such a component in an amount such that the hydrogen atom bonded to the silicon atom of the component is 1 to 50 equivalents per equivalent of the silanol group of the component, and more preferably 5 to 20 equivalents. It is an amount. If the number of hydrogen atoms bonded to the silicon atom of the component contained in the composition of the present invention is too small, the composition may not sufficiently foam. On the other hand, if the amount is too large, problems may occur such as deterioration of physical properties of the cured product (foam) or hardening of the foam over time. Generally, the blending amount of the component is within the range of satisfying the above quantitative condition for the hydrogen atom bonded to the silicon atom.
0.1 to 50 parts by weight, particularly 2 to 30 parts by weight are suitable per 0 parts by weight.

Catalyst As the catalyst, a platinum compound, a tin compound, or an amine compound is usually used. These catalysts are for promoting the dehydrogenative curing reaction of the composition of the present invention by the silanol group and the hydrogen atom bonded to the silicon atom described above. The platinum compound is, for example, a complex of fine-particle platinum metal adsorbed on a carrier such as silica, alumina, or silica gel, platinum chloride, chloroplatinic acid, chloroplatinic acid hexahydrate, and olefin or divinyldimethylpolysiloxane. , An alcohol solution of chloroplatinic acid hexahydrate, and the like. As the tin compound, for example, a divalent tin compound such as dioctate tin, or a tetravalent tin compound such as dibutyltin dimethoxide or dibutyltin dilaurate can be used. Examples of the amine compound include hydroxyamines such as dimethylhydroxyamine and diethylhydroxyamine; and guadinyl compounds.

In the case of a platinum compound, the amount of the catalyst added is usually 1 to 500 ppm in terms of platinum weight with respect to the components.
Particularly, it is preferably used in an amount of 10 to 100 ppm. In the case of tin compounds or amine compounds, component 10
It is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 0 parts by weight. If the addition amount is too small, the curing reaction is not effectively promoted,
Curing and foaming of the composition of the present invention may be insufficient. On the other hand, if the amount is too large, the curing reaction is not promoted to the extent commensurate with it, which is not economical.

(B) Incompatible Silicone Oil The silicone oil of the component (B) used in the present invention is a component in which the composition of the present invention bleeds out on the surface of a sponge-like cured product after foaming and curing. It is a component that prevents the colonization of living things. Therefore, the silicone oil as the component (B) used in the present invention is not compatible with the organopolysiloxane component (in the above-mentioned examples, the components and components) in the foam-curable vehicle of the above (A). There is no particular limitation as long as it is a silicone oil.

The silicone oil as the component (B) is represented by the following general formula (6):

[0031]

Embedded image (In the formula, R ¹ is independently an unsubstituted or unsubstituted monovalent hydrocarbon group, and p is an integer of 2 to 1500, preferably 10
Is an integer of 500) and the following general formula (7):

[0032]

Embedded image [In the formula, R ¹ is the same as defined above, Z is the following general formula ^{(8): - (R 2} O) c - (C 3 H 6 O) d -X (8) ( wherein, R ² Is an alkylene group, X is a hydrogen atom, an alkyl group, an acetyl group or an allyl group, and c is 2-1.
00 is an integer, group or the following formula represented by d is an integer of 0~100) (9): - ( OR 2) c - (OC 3 H 6) d -Q (9) ( wherein , R ² , c and d are the same as above, Q is a group represented by a hydroxyl group, an alkoxy group, an acetoxy group or an allyloxy group, and Y is an unsubstituted or substituted monovalent hydrocarbon group, It is a group represented by the general formula (8) or a group represented by the general formula (9), and m is 2 to 1,500.
Is an integer of 5 to 500, and n is 1 to
An integer of 100, preferably an integer of 1 to 80] is preferred, and one or more kinds of organopolysiloxane selected from the group consisting of organopolysiloxanes are preferable.

The unsubstituted or substituted monovalent hydrocarbon group represented by R ¹ in the above general formulas (6) and (7) is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Alkyl groups such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group An alkenyl group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a hexenyl group or a cyclohexenyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a biphenyl group; Aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group and methylbenzyl group; and Part or all of the hydrogen atoms bonded to the carbon atoms of these groups are fluorine, chlorine, a halogen atom such as bromine, a group substituted with a cyano group, for example, a chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, etc. A non-substituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms is preferable, one having 1 to 10 carbon atoms is preferable, and a carbon having no aliphatic unsaturated bond is more preferable. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 atoms, and the like, and particularly preferably a methyl group, a phenyl group, a 3,3,3-trifluoropropyl group, 3,3,4,4 , 5, 5, 6, 6, 6, 6- Is a Na-fluoro-hexyl group.

[0034] As non-substituted or unsubstituted monovalent hydrocarbon group represented by R ¹ in the general formula (7) include the same as R ¹ in the formula (6).

Examples of the alkylene group represented by R ² in the general formula (8) include alkylene groups such as methylene, ethylene, trimethylene, methylethylene, tetramethylene, hexamethylene and methylpropylene groups. Possible and preferred alkylene groups have 1 to 1 carbon atoms.
6 is a straight-chain or branched alkylene group, more preferably a straight-chain or branched alkylene group having 2 to 4 carbon atoms, and particularly preferably trimethylene group, ethylene group, tetra group. It is a methylene group.

Examples of the alkyl group represented by X in the general formula (8) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-group.
Butyl group, pentyl group, neopentyl group, hexyl group,
Examples thereof include a heptyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group, and among them, a methyl group, an ethyl group and a butyl group are preferable.

Specific examples of the group represented by the general formula (8) include, for example, —C ₃ H ₆ —O— (C ₂ H ₄ O) _t —H—C ₃ H ₆ —O— (C _{3 H 6 O) t -H -C 3} H 6 -O- (C 4 H 8 O) t -H -C 3 H 6 -O- (C 2 H 4 O) t -CH 3 -C 3 H 6 - _{O- (C 3 H 6 O)} t -CH 3 -C 3 H 6 -O- (C 4 H 8 O) t -CH 3 -C 3 H 6 -O- (C 2 H 4 O) t -COCH _{3 -C 3 H 6 -O- (C} 3 H 6 O) t -COCH 3 -C 3 H 6 -O- (C 4 H 8 O) t -COCH 3 - (C 2 H 4 O) c - ( _{C 3 H 6 O) d -H} - (C 2 H 4 O) c - (C 3 H 6 O) d -CH 3 - (C 2 H 4 O) c - (C 3 H 6 O) d -COCH ₃ (in the above formula, t is an integer of 1 to 99, and c and d are the same as above) and the like.

Examples of the alkoxy group represented by Q in the general formula (9) include a methoxy group, an ethoxy group and a butoxy group.

[0039] Specific examples of a group represented by general formula (9), for _{example, - (OC 2 H 4)} c -OH - (OC 3 H 6) c -OH - (OC 4 H 8) c - _{OH - (OC 2 H 4)} c -OCH 3 - (OC 3 H 6) c -OCH 3 - (OC 4 H 8) c -OCH 3 - (OC 2 H 4) c -OCOCH 3 - (OC 3 H _{6) c -OCOCH 3 - (OC} 4 H 8) c -OCOCH 3 - (OC 2 H 4) c -OCH 2 -CH = CH 2 - (OC 3 H 6) c -OCH 2 -CH = CH 2 - _{(OC 4 H 8) c -OCH} 2 -CH = CH 2 - (OC 2 H 4) c - (OC 3 H 6) d -OH - (OC 2 H 4) c - (OC 3 H 6) d - _{OCH 3 - (OC 2 H 4} ) c - (OC 3 H 6) d -OCOCH 3 - (OC 2 H 4) c - (OC 3 H 6) d -OCH 2 -C
H = CH ₂ (in the above formula, c and d are same as that defined above), and the like.

Specific examples of the organopolysiloxane represented by the general formula (6) include, for example, Me ₃ SiO 2.
(SiMe ₂ O) ₁₀ (SiMe (C ₈ H ₁₇ ) O) ₅ Si
Me ₃ Me ₃ SiO (SiMe ₂ O) ₄₀ (SiMePhO) ₄
SiMe ₃ , Me ₃ SiO (SiMe ₂ O) ₄₀ (SiM
ePhO) ₈ SiMe ₃ , Me ₃ SiO (SiMe
₂ O) ₄₀ (SiMePhO) ₁₀ SiMe ₃ , Me ₃ Si
O (SiMe ₂ O) ₄₀ (SiPh ₂ O) ₂ SiMe ₃ ,
Me ₃ SiO (SiMe ₂ O) ₄₀ (SiPh ₂ O) ₄ S
iMe ₃ , Me ₃ SiO (SiMe ₂ O) ₄₀ (SiPh
₂ O) ₅ SiMe ₃ , Me ₃ SiO (SiMe ₂ O) ₄₀
(SiMe (C ₈ H ₁₇ ) O) ₁₀ SiMe ₃ (in the above formula,
Me is a methyl group and Ph is a phenyl group).

Specific examples of the organopolysiloxane represented by the general formula (7) include, for example, Me ₃ Si (S
iMe ₂ O) ₁₀ (SiMeR ⁸ O) ₄ SiMe ₃ , Me
₃ Si (SiMe ₂ O) ₁₀ (SiMeR ⁹ O) ₅ SiM
e ₃ , Me ₃ Si (SiMe ₂ O) ₃₀ (SiMeR
¹⁰ O) ₅ SiMe ₃ , Me ₃ Si (SiMe ₂ O)
₆₀ (SiMeR ⁹ O) ₅ SiMe ₃ , PhMe ₂ Si
(SiMe ₂ O) ₆₀ (SiMeR ¹⁰ O) ₅ SiMe ₂ P
h (in the above formula, Me is a methyl group, Ph is a phenyl group, R ⁸ is a group —C ₃ H ₆ —O (C ₂ H ₄ O) ₁₀ —
Is H, R ⁹ is a group _{-C 3 H 6 -O (C 2} H 4 O) 10 -
Is Me, R ¹⁰ is a group _{-C 3 H 6 -O (C 2} H 4 O) 20
(C ₃ H ₆ O) is ₂₀ -COCH _3), and the like.

The organopolysiloxane represented by the general formula (6) is used alone as the silicone oil as the component (B), and the general formula (1) is used as the component (A).
Alternatively, when the organopolysiloxane in which R in (2) is a methyl group is used, it is more preferable to select one in which R ^{1 in the} general formula (6) is a monovalent hydrocarbon group other than a methyl group. It is preferable because it is not compatible with the component (A).

The silicone oil as the component (B) generally has a viscosity at 25 ° C. of 25 to 5 from the viewpoint of workability sustainability.
0,000 cSt, preferably 1,000-100,
000 cSt. If this viscosity is too low, all may bleed out in a short time, and if it is too high, the desired bleedout may be small and it may not be possible to suppress the establishment of organisms.

Component (B) is a blended amount of silicone oil
In the component (A), it is usually 1 to 200 parts by weight, preferably 20 to 100 parts by weight with respect to 100 parts by weight of the organopolysiloxane component.
It is 150 parts by weight.

Other Components The room-temperature foam-curable organopolysiloxane composition of the present invention may be used as a plasticizer, an anti-sagging agent, or a known antifouling agent, if necessary, so long as it does not affect the curing. Silicone oil, petrolatum, solid paraffin, liquid paraffin, wax, oils and fats, as well as bacterial agents and fungicides can be added.

In addition to these components, various additives that have been conventionally compounded in a known foamable silicone rubber composition can be compounded as required. For example, a vinyl group-containing organopolysiloxane can be blended to increase the reinforcing property of the sponge-like cured product, and fumed silica, precipitated silica, diatomaceous earth, quartz fine powder, iron oxide,
Titanium oxide, aluminum oxide, aluminum silicate,
Inorganic fillers such as zinc white and carbon black; antistatic agents; heat-resistant agents; flame retardants; pigments; glass fibers; carbon fibers and the like can be appropriately mixed. In particular, the inorganic filler may be untreated, or may be surface-treated with an organosilicon compound such as organochlorosilane, organopolysiloxane, or hexaorganosilazane.

In addition to the above-mentioned components, it is preferable to add a pot life adjusting agent to the composition of the present invention. Examples of the pot life adjusting agent include vinyl group-containing polysiloxane, peroxide, acetylene alcohol compound, amine compound, amide compound and the like. The addition amount of the pot life adjusting agent is such that the pot life of the composition is 10 seconds to 2 hours,
The amount is preferably about 2 to 20 minutes.

Preparation of room temperature foam-curable silicone composition,
Further, the room-temperature foam-curable silicone composition is usually divided into a main agent and a curing agent before foaming and curing (two-component type). For example, as the component (A), an organopolysiloxane having at least two silanol groups in one molecule of the above component, and an organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule of the component, When a composition containing a catalyst is used, the composition of the present invention can be divided into two parts as follows.
That is, for example, when the component (A) is divided into two liquids, that is, a mixture of the component and the component, at least one liquid (B)
The component silicone oil may be blended. Of course 2
You may mix | blend the silicone oil of (B) component with each of the liquids. Also, when the component (A) is divided into two liquids of a component and a mixture of the component and the component, the silicone oil of the component (B) may be blended in at least one of the liquids as described above.

The two-liquid type composition of the present invention is used by mixing so that the two liquids become uniform just before the construction. The mixing may be performed by hand or by using an automatic stirrer. In addition, the composition of the present invention, even if it is not divided into two liquids as described above, is treated with the component (A) immediately before the construction.
It may be prepared by mixing with the component (B).

As a construction method using the composition of the present invention,
For example, a method may be mentioned in which the composition is directly applied to the construction surface by a flow coating method or a spray method and then cured at room temperature. In addition, as another construction method, the composition is foamed and cured into a sheet shape, and a silicone-based RT is applied to the construction surface.
A method of bonding using V rubber or the like can be mentioned.

The sponge-like cured product obtained from the composition of the present invention provided on the construction surface as described above constantly vibrates slightly due to the movement of seawater, and the silicone oil bleeds out on the surface of the cured product. Effectively prevent the attachment of organisms for a long time.

[0052]

Example 1 80 parts by weight of dimethylpolysiloxane having a viscosity of 5000 cP at 25 ° C. and terminated with hydroxy groups at both ends of a molecular chain, 15 parts by weight of atomized silica whose surface is treated with dichlorodimethylsilane, at 25 ° C. 7 parts by weight of methyl hydrogen siloxane having both ends of the molecular chain with a viscosity of 30 cP stopped by trimethylsilyl groups, 0.5 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyltetracyclosiloxane Part, viscosity at 25 ° C is 50 cP
5 parts by weight of dimethylpolysiloxane in which both ends of its molecular chain are terminated with hydroxy groups and the following formula: Me ₃ SiO (SiMe ₂ O) ₄₀ (SiPh ₂ O) ₂ S
15 parts by weight of silicone oil represented by iMe ₃ (wherein Me is a methyl group and Ph is a phenyl group) was charged into a universal mixer and uniformly mixed. 0.5 parts by weight of a 1% isopropanol solution of chloroplatinic acid was added to this mixture and stirred for 3 minutes to uniformly mix. Next, this mixture was poured into a mold of 50 cm × 50 cm × 1 cm to obtain a sheet-shaped foamed cured product. This sheet-form foamed cured product was attached to an iron plate coated with a rust preventive coating with an epoxy resin using a room temperature curable resin composition [KE44 (deoxime type RTV) manufactured by Shin-Etsu Chemical Co., Ltd.]. Then, the sheet-like foamed cured product thus attached to the iron plate was immersed in seawater for 2 years, and the state of adhesion of marine organisms on the surface of the cured product was observed every 6 months from the start of the impregnation. Table 1 shows the results. Example 2 In Example 1, Me ₃ SiO (SiMe ₂ O)
Instead of the silicone oil represented by ₄₀ (SiPh ₂ O) ₂ SiMe ₃ , the following formula: Me ₃ SiO (SiMe ₂ O) ₁₀ [SiMe (-C ₃ H ₆ O (C ₂ H ₄ O) ₁₀
-H) O] ₅ SiMe ₃ (wherein Me is a methyl group) 15 parts by weight of silicone oil is used, and 5 parts by weight of diethylhydroxyamine is used instead of a 1% isopropanol solution of chloroplatinic acid. A sheet-shaped foamed and cured product was obtained in the same manner as in Example 1 except that it was immersed in seawater for 2 years, and the surface of the cured product was replenished every 6 months from the start of soaking. The state of adhesion of marine organisms was observed. Table 1 shows the results. Example 3 80 parts by weight of methylphenylpolysiloxane having a viscosity of 10,000 cP at 25 ° C. and terminated with hydroxy groups at both ends of a molecular chain (phenyl group content: 10 mol%), 30 parts by weight of pulverized silica, and a viscosity of 30 cP at 25 ° C. 10 parts by weight of methyl hydrogen siloxane whose both ends of the molecular chain are terminated by trimethylsilyl groups, 0.5 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-tetracyclosiloxane, 25 Viscosity at 5 ℃
7 parts by weight of dimethylpolysiloxane in which both ends of the molecular chain of 0 cP are terminated with hydroxy groups and the following formula: Me ₃ SiO (SiMe ₂ O) ₁₀ (SiMe (C
20 parts by weight of silicone oil represented by ₈ H ₁₇ ) O) ₅ SiMe ₃ (where Me is a methyl group) was charged into a universal mixer and uniformly mixed. To this mixture was added 7 parts by weight of tin dioctylate, and the mixture was stirred for 3 minutes and uniformly mixed. Next, this mixture was poured into a mold in the same manner as in Example 1 to obtain a sheet-shaped foamed and cured product. Then, the sheet-shaped foamed cured product attached to the iron plate was immersed in seawater for 2 years, and the state of adhesion of marine organisms on the surface of the cured product was observed every 6 months from the start of impregnation. Table 1 shows the results. Example 4 In Example 1, Me ₃ SiO (SiMe ₂ O)
Instead of the silicone oil represented by ₄₀ (SiPh ₂ O) ₂ SiMe ₃ , the following formula: PhMe ₂ SiO (SiMe ₂ O) ₆₀ (SiMeR
¹⁰ O) ₅ SiMe ₂ Ph (in the above formula, Me is a methyl group, Ph is a phenyl group, and R ¹⁰ is a group —C ₃ H ₆ —O (C ₂ H ₄ O) ₂₀ (C
₃ H ₆ O) ₂₀ —COCH ₃ ) and used 5 parts by weight of diethylhydroxyamine instead of 1% isopropanol solution of chloroplatinic acid. A sheet-shaped foamed cured product was obtained in the same manner as in 1, and the sheet-shaped foamed cured product attached to an iron plate was immersed in seawater for 2 years, and the state of adhesion of marine organisms on the surface of the cured product was monitored every 6 months from the start of impregnation. I observed. Table 1 shows the results
Shown in Comparative Example 1 80 parts by weight of dimethylpolysiloxane in which both ends of a molecular chain having a viscosity of 5000 cP at 25 ° C. were terminated by hydroxy groups, 15 parts by weight of sprayed silica whose surface was treated with dichlorodimethylsilane, and methyltri (methylethylketooxyimino) silane. 7 parts by weight, dibutyltin laurate 0.2
Parts by weight and the following formula: Me ₃ SiO (SiMe ₂ O) ₄₀ (SiPh ₂ O) ₂ S
15 parts by weight of silicone oil represented by iMe ₃ (wherein Me is a methyl group and Ph is a phenyl group) was charged into a universal mixer and uniformly mixed. Then mix this mixture with 5
It was poured into a 0 cm × 50 cm × 1 cm mold to obtain a sheet-shaped cured product (non-foamed product). This sheet-shaped cured product was attached to an iron plate in the same manner as in Example 1, immersed in seawater for 2 years, and the state of adhesion of marine organisms on the surface of the cured product was observed every 6 months from the start of impregnation. Table 1 shows the results. Comparative Example 2 In Example 1, the following formula: Me ₃ SiO (SiMe ₂ O) ₄₀ (SiPh ₂ O) ₂ S
A sheet-shaped foamed / cured product was obtained in the same manner as in Example 1 except that the silicone oil represented by iMe ₃ was not used, and the sheet-shaped foamed / cured product attached to the iron plate was immersed in seawater for 2 years to be immersed. The state of adhesion of marine organisms on the surface of the cured product was observed every 6 months from the start. Table 1 shows the results. Comparative Example 3 In Example 2, the following formula: Me ₃ SiO (SiMe ₂ O) ₁₀ [SiMe (-C ₃ H ₆ O (C ₂ H ₄ O) ₁₀
-H) O] ₅ SiMe ₃ was used, except that the silicone oil represented by SiMe ₃ was not used, and a sheet-shaped foamed / cured product was obtained in the same manner as in Example 2, and the sheet-shaped foamed / cured product attached to an iron plate was added to seawater. It was soaked for one year, and the state of adhesion of marine organisms on the surface of the cured product was observed every 6 months after the start of the soaking. Table 1 shows the results. Comparative Example 4 In Example 3, the following formula: Me ₃ SiO (SiMe ₂ O) ₁₀ (SiMe (C
₈ H ₁₇ ) O) ₅ SiMe ₃ was used in the same manner as in Example 3 except that the silicone oil was not used, and the sheet-shaped foamed and cured product attached to an iron plate was added to seawater. It was soaked for 2 years, and the state of adhesion of marine organisms on the surface of the cured product was observed every 6 months after the start of the soaking. Table 1 shows the results.

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[Table 1]

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EFFECTS OF THE INVENTION According to the present invention, a room temperature curable organopolysiloxane composition having no environmental pollution and capable of sustaining an antifouling effect for preventing adhesion of marine organisms such as barnacles for a long time and useful as an antifouling paint. And a cured product thereof.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C09D 5/00 PPH C09D 5/00 PPH 5/16 PQJ 5/16 PQJ 183/04 PMV 183/04 PMV 183/05 183/05 183/06 183/06 183/12 183/12

Claims (2)

[Claims] 1. A room-temperature foam-curable silicone composition comprising (A) a vehicle mainly composed of organopolysiloxane and having foam-curing properties, and (B) a silicone oil which is incompatible with the organopolysiloxane. 2. The silicone oil of (B) is represented by the following general formula (6): (In the formula, R ¹ is independently an unsubstituted or unsubstituted monovalent hydrocarbon group, and p is an integer of 2-1500) and an organopolysiloxane represented by the following general formula (7): ] [In the formula, R ¹ is the same as above, Z is the following general formula (8):-(R ² O) _c -X (8) (In the formula, R ² is an alkylene group, and X is hydrogen. An atom, an alkyl group or an acetyl group, and c is an integer of 2 to 100), or a group represented by the following general formula (9):-(OR ² ) _c -Q (9) (in the formula, R ² and c is the same as above, Q is a hydroxyl group,
An alkoxy group, an acetoxy group or an allyl group), Y is an unsubstituted or substituted monovalent hydrocarbon group, a group represented by the general formula (8) or a general formula (9). And m is an integer of 2 to 1500 and n is an integer of 1 to 100], or 1 or 2 selected from the group consisting of organopolysiloxanes
The room temperature foam-curable silicone composition according to claim 1, which is one or more kinds.