JP3179005B2 - Room temperature foaming-curable silicone composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a room-temperature foaming-curable silicone composition, and more particularly to polluting the environment by applying it to a long-term contact with seawater such as a seawater introduction pipe, a marine structure or a ship. The present invention relates to a room-temperature foaming-curable silicone composition useful as an antifouling paint capable of preventing marine organisms such as barnacles from adhering for a long time without performing.

[0002]

2. Description of the Related Art Underwater 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, ships, etc., causing various adverse effects. Conventionally, to prevent such marine organisms from attaching,
Paints added with cuprous oxide, tributyltin, triphenyltin, etc. were applied to the places where seawater comes in contact.However, these additives cause environmental pollution such as polluting fish and shellfish, In recent years, their use has been concerned. Also,
Such paints that do not use additives that cause environmental pollution include those that form a coating that reduces the surface energy of the seawater contact area, and those that have a hydrophobic hydrophilic microphase separation structure on the surface. Some of them are formed, and others are those that form a coating film on the surface that can bleed incompatible oil. Specifically, a vehicle containing a curable silicone composition as a main component and an organic compound such as liquid paraffin added thereto (see JP-A-53-79980). One 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 one obtained by blending polyvinyl butyral with a vehicle mainly comprising a curable silicone composition (Japanese Patent Laid-Open No. 54-2
No. 6826, Japanese Patent Publication No. 57-16868), a vehicle comprising a curable silicone composition as a main component and a phenyl-modified silicone oil incompatible with the silicone vehicle added thereto (Japanese Patent Publication No. 56-262).
No. 72) is known. However, a coating film formed using these paints can prevent the adhesion of marine organisms for about two years, and no further effect of preventing adhesion can be obtained. In particular, paints containing phenyl-modified silicone oil, which is incompatible with the silicone vehicle, have to be added in large quantities to extend the life of the paint. Adhesion becomes insufficient.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a room-temperature-curable organo-organic composition useful as an antifouling paint which is free of environmental pollution and has a long-lasting antifouling effect for preventing the adhesion of marine organisms such as barnacles. It is to provide a polysiloxane composition.

[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 place in contact with seawater is constantly vibrated minutely by the movement of seawater. Reached the present invention.

The present invention is a room temperature foam-curable silicone composition comprising (A) a foam-curable vehicle mainly composed of an organopolysiloxane, and (B) a silicone oil incompatible 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 properties 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. Any hardening material can be used without particular limitation. Such foam-curable vehicles include, for example, known room-temperature foam-curable organopolysiloxane compositions, typical examples of which include an organopolysiloxane having at least two silanol groups in one molecule; A composition including an organopolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule, and a catalyst, and the like are given.

[0008] Organopolysilo having silanol groups
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 each 0 to 3 provided that i + j is 1 to 3. And j is an integer of 1 to 3). An organopolysiloxane having at least two units in one molecule represented by the following formula:

The organopolysiloxane component is a base component of the foam-curable organopolysiloxane composition. The silanol group undergoes a dehydrogenation reaction with a hydrogen atom bonded to a silicon atom contained in the organopolysiloxane component. It is cured while generating hydrogen gas as 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, a methyl group, an ethyl group and a propyl group. An alkyl group having 1 to 6 carbon atoms; 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 and tolyl group; benzyl group, 2-phenylethyl group, 2- An aralkyl group having 7 to 12 carbon atoms such as a phenylpropyl group; and a group in which at least a part of hydrogen atoms of these groups is substituted with a halogen atom or the like, for example, a 3,3,3-trifluoropropyl group or the like. .

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

The organopolysiloxane of the component may have any other organosiloxane unit as long as it has at least two units of the above formula (1) in one molecule. Examples of such other organosiloxane units include, for example, the following general formula (2): R _e SiO _{(4-e) / 2} (2) (wherein R is as defined above, and e is Which is an integer).

In the above formula (2), R is the above formula (1)
And the same as those exemplified above.

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

Typical examples of the organopolysiloxane of the component include the following general formula (3): HO (R ⁴ R ⁵ SiO) _L H (3) wherein, even if R ⁴ and R ⁵ are the same, May be different,
A substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and L is an integer of from 20 to 3,000], an organopolysiloxane represented by 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) wherein R ⁴ and R ⁵ are the same as above, and R ⁶ is independently fat 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;
And an organopolysiloxane represented by the following formula:

In the above formulas (3) and (4), R ⁴ , R ⁵ or
As the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond represented by R ⁶ , the same as those exemplified in the above formula (1) can be mentioned.

A particularly preferred 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} (where R, i and j have the same meanings as above) An organopolysiloxane having at least two in one molecule is exemplified.

The component organopolysiloxane functions as a so-called crosslinking agent, and a hydrogen atom bonded to a silicon atom dehydrogenates with a silanol group of the component organopolysiloxane to form a cured product. Moreover,
Hydrogen gas serving as 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 includes the same groups as those exemplified for the general formula (1).

The unit represented by the general formula (5) may be present at the terminal of the molecular chain, or may be present in the middle of the molecular chain. Also, they may be present in both of them.

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

The molecular structure of the organopolysiloxane of the component may be any of linear, branched, cyclic, network and the like, but usually a linear or cyclic one is used.
The organopolysiloxane may be used singly or as a mixture of two or more.
A combination of more than one species may be used. Furthermore, although the viscosity is not particularly limited, it is generally 1 to 1000 at 25 ° C.
It is preferably 0 centipoise.

Specific examples of the organopolysiloxane of the component include, for example, a compound represented by the formula: R ⁷ (R ⁷ R ⁷ SiO) _q (R ⁷ HSiO) _r Si (R ⁷ ) ₃ [wherein R ⁷ is independently a fatty acid 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 includes:
The same as those exemplified for R in the general formula (1) can be used.

In general, the component is preferably used in an amount of 1 to 50 equivalents, more preferably 5 to 20 equivalents, per 1 equivalent of the silanol group of the component. Amount. In addition, when 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 foam sufficiently. On the other hand, if the amount is too large, problems such as deterioration of physical properties of the cured product (foam) and hardening of the foam over time may occur. In general, the compounding amount of the component is within a range that satisfies the above-described 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, per 0 parts by weight is suitable.

Catalyst As a catalyst, a platinum compound, a tin compound and an amine compound are usually used. These catalysts are for accelerating the dehydrogenation curing reaction of the composition of the present invention by the aforementioned silanol group and the hydrogen atom bonded to the silicon atom. Examples of the platinum compound include fine particles of platinum metal adsorbed on a carrier such as silica, alumina or silica gel, platinum chloride, chloroplatinic acid, a complex of chloroplatinic acid hexahydrate with an olefin or divinyldimethylpolysiloxane. And chloroplatinic acid hexahydrate in alcohol. As the tin compound, for example, a divalent tin compound such as dioctoate 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 guanidinyl compounds.

In the case of a platinum compound, the amount of the catalyst to be added is usually 1 to 500 ppm, in terms of platinum weight, relative to the component.
It is particularly preferred to use it in an amount of from 10 to 100 ppm. In the case of a tin compound or an amine compound, component 10
The amount is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 0 parts by weight. If the addition amount is too small, the curing reaction is not effectively promoted,
The 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 accelerated to a corresponding degree and is not economical.

(B) Silicone oil having no compatibility The silicone oil (B) used in the present invention is a component that causes the composition of the present invention to bleed out to the surface of a sponge-like cured product after foaming and curing. And is a component that prevents the settlement of living things. Therefore, the silicone oil of the component (B) used in the present invention is not compatible with the organopolysiloxane component (the component and the component in the case of the above example) 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 of the component (B) is represented by the following general formula (6):

[0031]

Embedded image (Wherein R ¹ is independently an unsubstituted or unsubstituted monovalent hydrocarbon group, and p is an integer of 2 to 1500, preferably 10 to
An organopolysiloxane represented by 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 to 1
A group represented by the following general formula (9):-(OR ² ) _c- (OC ₃ H ₆ ) _d -Q (9) (wherein d is an integer of 0 to 100) , R ² , c and d are the same as described above, Q is a hydroxyl group, an alkoxy group, an acetoxy group or an allyloxy group), Y is an unsubstituted or substituted monovalent hydrocarbon group, A group represented by the general formula (8) or a group represented by the general formula (9), wherein m is 2 to 1500
, Preferably an integer of 5 to 500, n is 1 to
An integer of 100, and preferably an integer of 1 to 80]. The organopolysiloxane is preferably one or more selected from the group consisting of organopolysiloxanes.

Examples of the unsubstituted or substituted monovalent hydrocarbon group represented by R ¹ in the general formulas (6) and (7) include 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 and dodecyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and 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 and a cyclohexenyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and 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, halogen atoms such as bromine, a group substituted with a cyano group, for example, a chloromethyl group, a 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. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably having 1 to 10 carbon atoms, and more preferably a carbon having no aliphatic unsaturated bond. Examples thereof include an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 atoms, and particularly preferred are a methyl group, a phenyl group, a 3,3,3-trifluoropropyl group, a 3,3,4,4 , 5,5,6,6,6- Is a Na-fluoro-hexyl group.

As the unsubstituted or unsubstituted monovalent hydrocarbon group represented by R ¹ in the general formula (7), those similar to R ^{1 in the} above formula (6) can be mentioned.

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. Preferred and preferred alkylene groups are those having 1 to
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 a trimethylene group, an ethylene group, or a tetra-alkylene group. It is a methylene group.

The alkyl group represented by X in the general formula (8) includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-
Butyl group, pentyl group, neopentyl group, hexyl group,
Examples include a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. Of these, 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 described above).

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

Specific examples of the group represented by the general formula (9) include, 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 the same as above) and the like.

Specific examples of the organopolysiloxane represented by the general formula (6) include, for example, Me ₃ SiO
(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).

As a specific example of the organopolysiloxane represented by the general formula (7), 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 (where Me is a methyl group, Ph is a phenyl group, and R ⁸ is a group —C ₃ H ₆ —O (C ₂ H ₄ O) ₁₀ —
H and R ⁹ is a group —C ₃ H ₆ —O (C ₂ H ₄ O) ₁₀ —
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 ).

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

The silicone oil of the component (B) has a viscosity at 25 ° C. of usually from 25 to 5 from the viewpoint of sustainability of workability.
00,000 cSt, preferably 1,000 to 100,
000 cSt. If the viscosity is too low, all may bleed out in a short time, and if the viscosity is too high, bleeding out at the intended stage may be so small that colonization of organisms may not be suppressed.

The component (B) has a silicone oil content of:
In the component (A), 1 to 200 parts by weight, preferably 20 to 200 parts by weight, based on 100 parts by weight of the organopolysiloxane component is used.
It is 150 parts by weight.

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

In addition to these components, various additives which are blended in conventionally known foamable silicone rubber compositions can be blended 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; In particular, the inorganic filler may be untreated, or may be surface-treated with an organosilicon compound such as organochlorosilane, organopolysiloxane, or hexaorganosilazane.

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

Preparation of a room temperature foam-curable silicone composition,
And the formation of a coating film using the same The room-temperature foaming-curable silicone composition is usually divided into a main agent and a curing agent before foaming and curing (two-pack type). For example, as the component (A), an organopolysiloxane having at least two silanol groups in one molecule of the above component, an organopolysiloxane having at least two hydrogen atoms bonded to a silicon atom 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 liquids as follows.
That is, for example, when the component (A) is divided into two liquids of the mixture of the component and the component, at least one of the liquids (B)
What is necessary is just to mix | blend the silicone oil of a component. Of course 2
You may mix | blend the silicone oil of (B) component with each of liquids. Also, when the component (A) is divided into two liquids of the component and the mixture of the component, the silicone oil of the component (B) may be blended into at least one of the liquids as described above.

The two-pack type composition of the present invention is used by mixing it just before the application so that the two-package becomes uniform. Mixing may be by manual stirring or by using an automatic stirrer. Further, the composition of the present invention, even if not divided into two liquids as described above, immediately before the construction and the component (A)
It may be one prepared by mixing the component (B) with an errand.

The construction method using the composition of the present invention includes:
For example, there is a method in which the composition is directly applied to a construction surface by a flow coating method or a spray method, and then cured at room temperature. Further, as another construction method, a composition obtained by foaming and curing the composition into a sheet shape is used as a silicone RT.
A method of bonding using V rubber or the like may be used.

The sponge-like cured product obtained from the composition of the present invention provided on the working surface as described above constantly vibrates minutely due to the movement of seawater, and the silicone oil bleeds out on the surface of the cured product. It effectively prevents organisms from attaching for a long time.

[0052]

EXAMPLES Example 1 80 parts by weight of dimethylpolysiloxane having a viscosity of 5000 cP at 25 ° C. and both ends of the molecular chain terminated with a hydroxy group, 15 parts by weight of sprayed silica whose surface was treated with dichlorodimethylsilane at 25 ° C. 7 parts by weight of methyl hydrogen siloxane having both ends of a molecular chain having a viscosity of 30 cP terminated by a trimethylsilyl group, 0.5 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyltetracyclosiloxane Parts, viscosity at 25 ° C is 50 cP
5 parts by weight of dimethylpolysiloxane terminated with hydroxy groups at both molecular chain terminals of: and Me ₃ SiO (SiMe ₂ O) ₄₀ (SiPh ₂ O) ₂ S
15 parts by weight of silicone oil represented by iMe ₃ (where Me is a methyl group and Ph is a phenyl group) were charged into a universal mixer and uniformly mixed. To this mixture, 0.5 part by weight of a 1% solution of chloroplatinic acid in isopropanol was added, and the mixture was stirred for 3 minutes to mix uniformly. Next, this mixture was poured into a mold frame of 50 cm × 50 cm × 1 cm to obtain a sheet-like foamed cured product. This sheet-shaped foamed cured product was affixed to an iron plate coated 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 six months from the start of impregnation. Table 1 shows the results. Example 2 In Example 1, Me ₃ SiO (SiMe ₂ O)
₄₀ Instead of the silicone oil represented by (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 (where, Me is a silicone oil 15 parts by weight, represented by a methyl group), in place of the 1% isopropanol solution of chloroplatinic acid, use the 5 parts by weight diethylhydroxylamine Except for the above, a sheet-like foamed cured product was obtained in the same manner as in Example 1, and the sheet-shaped foamed cured product attached to an iron plate was immersed in seawater for 2 years, and the surface of the cured product was removed every 6 months from the start of impregnation. The state of attachment of marine organisms was observed. Table 1 shows the results. Example 3 Viscosity at 25 ° C. of 10,000 cP 80 parts by weight of methylphenylpolysiloxane terminated at both molecular chains with hydroxy groups (phenyl group content: 10 mol%), 30 parts by weight of pulverized silica, viscosity at 25 ° C. of 30 cP 10 parts by weight of methyl hydrogen siloxane terminated at both molecular chain terminals with a trimethylsilyl group, 0.5 part by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-tetracyclosiloxane, 25 5 ° C viscosity
7 parts by weight of dimethylpolysiloxane in which both ends of the 0cP molecular chain 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, 7 parts by weight of tin dioctylate was added, 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-like foamed cured product. Then, the sheet-like foamed cured product attached to the iron plate was immersed in seawater for two years, and the state of adhesion of marine organisms to the surface of the cured product was observed every six 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 (where 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 a ₃₎ a silicone oil 30 parts by weight represented by, instead of 1% isopropanol solution of chloroplatinic acid, except for using 5 parts by weight of diethyl hydroxylamine, Example In the same manner as in Example 1, a sheet-like foamed cured product was obtained, and the sheet-shaped foamed cured product attached to an iron plate was immersed in seawater for 2 years. Observed. Table 1 shows the results
Shown in COMPARATIVE EXAMPLE 1 80 parts by weight of dimethylpolysiloxane having a viscosity of 5000 cP at 25 ° C. at both molecular chains terminated by hydroxy groups, 15 parts by weight of sprayed silica whose surface was treated with dichlorodimethylsilane, 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 (where Me is a methyl group and Ph is a phenyl group) were charged into a universal mixer and uniformly mixed. The mixture is then
It was poured into a mold having a size of 0 cm × 50 cm × 1 cm to obtain a sheet-like cured product (non-foamed product). This cured sheet was adhered to an iron plate in the same manner as in Example 1 and immersed in seawater for 2 years, and the state of adhesion of marine organisms to 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
except for using no silicone oil represented by IME ₃ may obtain a sheet-like foam cured in the same manner as in Example 1, and the sheet-like foam cured product was adhered to the iron plate was immersed for two years in seawater, impregnation Every six months from the start, the state of adhesion of marine organisms to the surface of the cured product was observed. 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 except for using no silicone oil represented by SiMe ₃ may obtain a sheet-like foam cured in the same manner as in Example 2, and the sheet-like foam cured product was adhered to the iron plate seawater 2 It was immersed every year, and the state of adhesion of marine organisms to the surface of the cured product was observed every six months from the start of impregnation. 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 except for using no silicone oil represented by SiMe ₃ may obtain a sheet-like foam cured in the same manner as in Example 3, and the sheet-like foam cured product was adhered to the iron plate seawater It was immersed for 2 years, and the state of adhesion of marine organisms to the surface of the cured product was observed every 6 months from the start of impregnation. Table 1 shows the results.

[0053]

[Table 1]

[0054]

According to the present invention, a room-temperature-curable organopolysiloxane composition which is free of environmental pollution and has a long-lasting antifouling effect for preventing the adhesion of marine organisms such as barnacles, and is useful as an antifouling paint. And a cured product thereof.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-225154 (JP, A) JP-A-62-84166 (JP, A) JP-A-6-25559 (JP, A) JP-A-1- 201377 (JP, A) JP-A-1-207365 (JP, A) JP-A-3-255169 (JP, A) JP-A-4-106156 (JP, A) JP-A-4-142373 (JP, A) JP-A-8-231898 (JP, A) JP-A-9-12413 (JP, A) JP-B-56-26272 (JP, B2) JP-A-7-506599 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 9/00-9/42 C08L 1/00-101/16 C09D 1/00-201/10

Claims (2)

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