JP3091506B2 - Cold-curable marine biofouling preventing silicone rubber composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention
The present invention relates to a silicone rubber composition useful as a jointing agent or a sealant, which becomes an antifouling silicone rubber exhibiting an effect of preventing the adhesion of marine organisms for a long time without polluting the environment.

[0002]

2. Description of the Related Art Rubber parts such as rubber domes and acoustic materials are attached to the outside of a ship. These are usually
A plurality of rubber parts are used, and joints or seal materials such as polyurethane rubber or polysulfide resin are buried between the plurality of rubber parts for rectification.

By the way, such rubber domes and acoustic materials include so-called antifouling rubbers which exhibit an effect of preventing the adhesion of marine organisms such as barnacles, bryozoans, serpula and seaweed (hereinafter also referred to as antifouling effect). in use. Further, it is preferable that the joint material and the sealing material also exhibit the same effect.

Conventionally, the effective components of such antifouling rubbers have been mainly tributyltin fluoride, tributyltin oxide, phenyltin compounds, triphenyltin dimethyl, dithiocarbamate, tributyltin oxide, and phenyltin compounds. Organotin compounds such as phenyltin fluoride, triphenyltin oxide, triphenyltin acetate, and triphenyltin chloride have been used. However,
Organotin compounds pollute the sea, accumulate in fish, and eventually affect the human body. Therefore, in view of such a social situation, various antifouling components replacing organic tin compounds are being developed.

[0005] One of such newly developed antifouling components is N-arylmaleimides. However, a rubber or resin composition for a joint material or a sealing material of polyurethane rubber or polysulfide resin has N-
When an arylmaleimide was added, the maleimide ring portion was opened, and a phenomenon was observed in which the antifouling effect was no longer exhibited or the curing of the rubber or resin composition was inhibited.

[0006] Until now, N-arylmaleimides can be used effectively, and despite the presence of N-arylmaleimides, the basic physical properties required for jointing materials or sealing materials have been improved. The rubber or resin composition to be the cured product shown is not known.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and shows basic physical properties required for a joint material or a sealing material, and is safe (has no environmental pollution). The present invention aims to provide a room-temperature-curable silicone rubber composition which is a cured product that releases an antifouling component having a high antifouling effect over a long period of time.

[0008]

Means for Solving the Problems In order to develop a joint material or a seal material containing N-arylmaleimides, the present inventors screened a polymer constituting the matrix. As a result, they found that a room temperature-curable silicone rubber was suitable for it, and completed the present invention.

That is, the present invention relates to a diorganopolysiloxane (A) represented by the following formula I, a cyclic organopolysiloxane (B) represented by the following formula II, and an N-arylmaleimide (C) represented by the following formula III: ), And the content of the N-arylmaleimides (C) is 5 to 1 when the total of the diorganopolysiloxane (A) and the cyclic organopolysiloxane (B) is 100 parts by weight.
The diorganopolysiloxane (A) and the cyclic organopolysiloxane (B) are separately stored, and are a room-temperature-curable marine biofouling-preventing silicone rubber composition.

Embedded image (In the above formula I, R ¹ , R ² , R ³ , and R ⁴ independently represent a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a vinyl group, an allyl group, a phenyl group, a β-phenyl (Selected from an ethyl group, a β-phenylpropyl group, a 3,3,3-trifluoropropyl group, a 3,3,3-trichloropropyl group, a chloromethyl group, and a β-cyanoethyl group.)

Embedded image (In the above formula II, five R ⁵ 's are independently selected from a methyl group, an ethyl group, a propyl group and a butyl group, and R ⁶ is a methyl group, an ethyl group, a propyl group, a butyl group and a dialkylamino group. An oxy group (however, the two alkyl groups are independently selected from a methyl group, an ethyl group, a propyl group, and a butyl group)

Embedded image (In the above formula III, X ¹ and X ² are independently selected from a hydrogen atom and a halogen atom, and Y ¹ is a hydrogen atom, a halogen atom, an alkyl group, a lower alkoxy group, a nitro group, a hydroxyl group, an alkoxycarbonyl Group, carboxyl group, phenyl group, phenylamino group, alkenyl group,
Selected from a thiocyano group, a sulfone group, an acetylamino group and a sulfamoyl group, Y ² is selected from a hydrogen atom, a halogen atom, an alkyl group, a lower alkoxy group, a nitro group and a hydroxyl group, and Y ³ is a hydrogen atom, a halogen atom And a dialkylamino group. )

Hereinafter, the present invention will be described in detail.

The diorganopolysiloxane (A) used in the present invention is represented by the above formula (I). There are various diorganopolysiloxanes (A) represented by the formula (I). The diorganopolysiloxane (A) has the lowest viscosity for the degree of polymerization of the siloxane, and has a workability of extruding the composition before curing and a silicone after curing. Preferably, 85% or more of all the organic groups (R ¹ , R ² , R ³ and R ⁴ ) are methyl groups, since substantially all the organic groups (R ¹ , R ² , R ³ and R ⁴ ) are methyl groups. Is more preferable. However, when the cured silicone rubber is required to have cold resistance and heat resistance, those having a phenyl group as a part of the organic group are preferred.

The diorganopolysiloxane (A) of the formula I is known to have various degrees of polymerization, but has a viscosity at 25 ° C. of 100 to 200,000.
Those within the range of cSt are preferred. 100 cSt viscosity
If it is less than 200, the elongation of the silicone rubber after curing is not sufficient. On the other hand, if it exceeds 200,000 cSt, a uniform composition cannot be obtained, and workability deteriorates. A particularly preferred range is between 500 and 50,000 cSt.

The cyclic organopolysiloxane (B) used in the present invention is represented by the above formula II. And
In the composition of the present invention, it acts as a curing agent. That is, the composition of the present invention comprises dehydroxylated amine between the terminal silanol group of the diorganopolysiloxane (A) capped with a silanol group and the dialkylaminooxy group of the cyclic organopolysiloxane (B). As a result of the reaction, the diorganopolysiloxane (A) is cross-linked and chain-lengthened, and is cured.

The cyclic organopolysiloxane (B) represented by the formula II contains various compounds, but the dialkylaminooxy group of the cyclic organopolysiloxane (B) has a dialkylaminooxy group because of its reactivity and easy release of the released organohydroxylamine. Preferred is a diethylaminooxy group, and particularly preferred is a cyclic diethylaminoxysiloxane represented by the following formula IIa.

[0015]

Embedded image

The amount ratio of the diorganopolysiloxane (A) to the cyclic organopolysiloxane (B) in the composition of the present invention is not particularly limited, but is based on 100 parts by weight of the diorganopolysiloxane (A). The amount of the cyclic organopolysiloxane (B) is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight. When the content of the cyclic organopolysiloxane (B) is less than 0.1 part by weight or more than 30 parts by weight, a cured product having rubber elasticity may not be obtained.

The N-arylmaleimides (C) used in the present invention are those represented by the above formula III. These N-arylmaleimides (C) have an effect of repelling aquatic organisms, but have extremely low toxicity, hardly act on humans and birds, and do not pollute the environment. It is a component that does not fall under the law, the Poisonous and Deleterious Substances Control Law, and the Chemical Substances Control Law (Law Concerning the Examination and Manufacture of Chemical Substances). Further, it does not inhibit the reaction (curing) between the diorganopolysiloxane (A) and the cyclic organopolysiloxane (B), nor does it cause an addition reaction thereto.

Specific compounds included in the N-arylmaleimides (C) represented by the above formula III include N-arylmaleimides.
(2,4,6-trichlorophenyl) maleimide, N-
(3,5-dichlorophenyl) maleimide, N- (4-
Anilinophenyl) maleimide, N- (2,5-xylyl) -2,3-dichloromaleimide and the like are exemplified.
In the present invention, N- (2,4,6-trichlorophenyl) maleimide is particularly preferably used.

In addition, other than the above, N represented by the above formula III
Specific compounds contained in the arylmaleimides (C) and the method for producing the N-arylmaleimides (C) represented by the formula III are described in detail in JP-A-53-9320.

In the composition of the present invention, the N-arylmaleimide (C) is used in an amount of 100 times the sum of the diorganopolysiloxane (A) and the cyclic organopolysiloxane (B).
When used as parts by weight, the content is 5 to 100 parts by weight. If the amount is less than 5 parts by weight, the effect of preventing the adhesion of marine organisms will not be maintained for a long period of time, while if it exceeds 100 parts by weight, the surface condition of the cured product will deteriorate and the adhesion to the adherend will decrease.

The essential components of the composition of the present invention are as described above. Usually, a curing accelerator, fumed silica, precipitated silica, silica aerosil, diatomaceous earth, calcium carbonate, and other fillers are used. contains. In addition, as long as the gist of the present invention is not impaired, generally used plasticizers, antiaging agents, organic bentonite, thixotropy imparting agents such as hydrogenated castor oil, bengara, coloring agents such as titanium white, and other fungicides It may also contain an agent or a flame retardant.

The composition of the present invention is of a two-pack type, wherein the diorganopolysiloxane (A) and the cyclic organopolysiloxane (B) are stored separately.

Other components include diorganopolysiloxane (A) and cyclic organopolysiloxane (B)
, Or both of them. Alternatively, it may be stored separately from these. However, usually, all of the other components are stored together with the diorganopolysiloxane (A) to constitute the base liquid, and the curing agent liquid is composed solely of the cyclic organopolysiloxane (B).

It is preferable that the N-arylmaleimides (C) are stored together with the diorganopolysiloxane (A). In general, since the amount of the cyclic organopolysiloxane (B) used is small, it is difficult to uniformly mix it with the N-arylmaleimides (C).

When the composition of the present invention is used, the base liquid and the hardener liquid (or further the third constituent liquid) are mixed and applied to a predetermined position by a method such as coating, embedding, or coating. Later, it can be cured at room temperature.

The long-lasting effect of the silicone rubber obtained by curing the composition of the present invention on the marine organism adhesion is considered to be due to the following mechanism of action.

The cured product (silicone rubber) of the composition of the present invention has a water-permeable silicone network structure, and the N-arylmaleimides (C) have a chemical structure having an underwater biological repellent effect. As is, it is held in its silicone network. Therefore, the N-arylmaleimides (C) included in the silicone network structure are always diffused and moved to the surface of the cured product that comes into contact with seawater by the seawater that has penetrated into the network structure. . As a result, from the initial stage of immersion of the cured product in water, until the N-arylmaleimides (C) are all diffused and consumed, the effect of repelling the adhesion of underwater organisms is uniformly exerted.

The composition of the present invention can be used to mold a thick-film cured product. Therefore, by adjusting the thickness of the cured product, it can be prevented for a desired period including a long period. A cured product exhibiting a fouling effect (silicone rubber joint material, sealing material, etc.) can be obtained.

[0029]

The present invention will be specifically described below with reference to examples.

Example A silicone rubber composition having the composition shown in Table A was prepared. The following test evaluation was performed about them. The results are shown in Table B.

1) Shear bond strength test According to JIS K6830, the adherend is a rolled steel material SS4
1. The surface treatment was carried out on ten test pieces under the condition of cleaning with toluene. All (100%) test pieces broken at the material (silicone rubber) part, ○, 80% or more of test pieces broken at the material part (the remainder was peeled off at the interface), Δ broken at the material part When the test piece was less than 80%, it was evaluated as x.

2) Underwater immersion test Each silicone rubber composition was kneaded, processed on a sheet, and then cured and cured at room temperature for one week. Then, 100x
A 200 × 6 mm test piece was obtained. The specimens were taken off the coast of Uranagama, Numazu City, Shizuoka Prefecture (in Suruga Bay, about 10 m from the quay).
Was immersed in a place at a water depth of about 1 m, pulled up at predetermined intervals, and the slime and marine organism attachment areas were measured.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

According to the present invention, there is provided a silicone rubber composition which contains a safe (having no environmental pollution) and high antifouling effect antifouling component and is a cured product which is released over a long period of time. You. Since the silicone rubber composition of the present invention is suitable for producing a joint material between ship parts such as a rubber dome and an acoustic material and a sealant, a joint material, a sealant and the like can be produced using the silicone rubber composition of the present invention. If manufactured, marine organisms can be prevented from attaching to the hull for a long period of time.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification code FI C09D 183/06 C09D 183/06 C09K 3/10 C09K 3/10 G (58) Investigated field (Int.Cl. ⁷ , DB name) ) C08L 83/06 C08L 83/08 C08L 83/04 C09D 5/14 C09D 183/06 C09D 183/04

Claims (2)

(57) [Claims] 1. It comprises a diorganopolysiloxane (A) represented by the following formula I, a cyclic organopolysiloxane (B) represented by the following formula II, and an N-arylmaleimide (C) represented by the following formula III: The N-arylmaleimide (C) content is 5 to 100 parts by weight when the total of the diorganopolysiloxane (A) and the cyclic organopolysiloxane (B) is 100 parts by weight;
A room temperature curing type marine biofouling preventing silicone rubber composition, wherein the diorganopolysiloxane (A) and the cyclic organopolysiloxane (B) are separately stored. Embedded image (In the above formula I, R ¹ , R ² , R ³ , and R ⁴ independently represent a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a vinyl group, an allyl group, a phenyl group, a β-phenyl (Selected from an ethyl group, a β-phenylpropyl group, a 3,3,3-trifluoropropyl group, a 3,3,3-trichloropropyl group, a chloromethyl group, and a β-cyanoethyl group.) (In the above formula II, five R ⁵ 's are independently selected from a methyl group, an ethyl group, a propyl group and a butyl group, and R ⁶ is a methyl group, an ethyl group, a propyl group, a butyl group and a dialkylamino group. An oxy group (provided that the two alkyl groups are each independently selected from a methyl group, an ethyl group, a propyl group and a butyl group). (In the above formula III, X ¹ and X ² are independently selected from a hydrogen atom and a halogen atom, and Y ¹ is a hydrogen atom, a halogen atom, an alkyl group, a lower alkoxy group, a nitro group, a hydroxyl group, an alkoxycarbonyl Group, carboxyl group, phenyl group, phenylamino group, alkenyl group,
Selected from a thiocyano group, a sulfone group, an acetylamino group and a sulfamoyl group, Y ² is selected from a hydrogen atom, a halogen atom, an alkyl group, a lower alkoxy group, a nitro group and a hydroxyl group, and Y ³ is a hydrogen atom, a halogen atom And a dialkylamino group. ) 2. The silicone rubber composition of claim 1, wherein said N-arylmaleimide (C) is stored together with said diorganopolysiloxane (A).