JP3103605B2 - Rubber composition for preventing adhesion of marine organisms - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition which provides an antifouling rubber exhibiting an effect of preventing the adhesion of marine organisms for a long period of time without polluting the environment, and an antifouling rubber obtained by vulcanizing the rubber composition.
About dirty rubber .

[0002]

2. Description of the Related Art At present, so-called antifouling rubbers having an effect of preventing the adhesion of marine organisms such as barnacles, bryozoans, serpula, and seaweeds are used for rubber domes, acoustic materials and the like.

[0003] Conventionally, as an active ingredient of such antifouling rubber, tributyltin chloride (TBT),
Organotin compounds such as triphenyltin (TPT) have been used. However, organotin compounds are polluting the sea and accumulating in fish bodies, which may affect the human body.

[0004] In view of such a social situation, various antifouling components replacing organic tin compounds are being developed. Further, if the type of the antifouling component changes, the specific method of using the antifouling component also changes. Therefore, research is also being conducted on a specific method of using a new antifouling component.

[0005] Nevertheless, a rubber composition containing a newly developed antifouling component and providing an antifouling rubber capable of effectively utilizing it has not yet been known.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a rubber composition which contains an antifouling component which is safe (has no environmental pollution) and has a high antifouling effect, and which is an antifouling rubber which releases it over a long period of time. It is an object of the present invention to provide a product and an antifouling rubber obtained by vulcanizing the product.

[0007]

Means for Solving the Problems The present invention comprises a raw rubber,
N -arylmaleimides represented by the following formula I, wherein the content of the N -arylmaleimides is 3 parts by weight or more based on 100 parts by weight of the raw rubber. Rubber composition for preventing marine organisms from adhering to rubber for rubber molding (hereinafter simply referred to as rubber composition), and then vulcanized
A molded antifouling rubber is provided.

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

Hereinafter, the present invention will be described in detail. The raw rubber used in the present invention is not particularly limited as long as the rubber exhibits weather resistance and seawater resistance after vulcanization.

For example, natural rubber (NR), isoprene rubber (IR), polybutadiene rubber ((BR), styrene-butadiene rubber (SBR), ethylene-propylene rubber (EPM, EPDM), butyl rubber (IIR), chlorinated butyl rubber (Cl-IIR), brominated butyl rubber (B
r-IIR), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), nitrile rubber (NB
R), urethane rubber (U), acrylic rubber (ACM, A
NM), polysulfide rubber (T), fluorine rubber (F
PM), chlorinated polyethylene rubber (CPE), ethylene-vinyl acetate rubber (EVA), epichlorohydrin rubber, and the like. EPM, EPDM, IIR, Cl-
IIR, Br-IIR, CR and the like are preferred.

The antifouling component in the rubber composition of the present invention is an N-arylmaleimide represented by the above formula I. These N-arylmaleimides have an effect of repelling aquatic organisms, but have extremely low toxicity, hardly act on humans and birds, and do not pollute the environment.

Specific compounds contained in the N-arylmaleimides represented by the formula I include N- (2,4,
6-trichlorophenyl) maleimide, N- (3,5-
Dichlorophenyl) maleimide, N- (4-anilinophenyl) maleimide, N- (2,5-xylyl) -2,
Examples thereof include 3-dichloromaleimide. In the present invention, N- (2,4,6-trichlorophenyl) maleimide is particularly preferably used.

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

The rubber composition of the present invention comprises the raw rubber 10
It contains 3 parts by weight or more of the N-arylmaleimide per 0 parts by weight. If the amount is less than 3 parts by weight, the effect of preventing adhesion of marine organisms cannot be exhibited.

The content of N-arylmaleimides in the rubber composition of the present invention is in a range of 3 parts by weight or more based on 100 parts by weight of the raw rubber, depending on the period during which the effect of preventing the adhesion of marine organisms is required. It is determined. In addition, what is necessary is just to refer to the Example mentioned later for determination of content.

The rubber composition of the present invention contains the above-mentioned raw rubber and the above-mentioned N-arylmaleimides as essential components. The rubber composition further contains copper suboxide (Cu ₂ O).
Is contained in an amount of 450 parts by weight or less, preferably 20 to 300 parts by weight, based on 100 parts by weight of the raw material rubber, the duration of the effect of preventing the antifouling rubber obtained by vulcanizing the rubber composition from sticking to the marine organism is reduced. become longer.

In addition, the cuprous oxide content was adjusted to
450 parts by weight or less with respect to 0 parts by weight
When the content is more than part by weight, the physical properties of the antifouling rubber may be out of an allowable range.

Similarly, the rubber composition of the present invention further comprises
Even when the thiuram-based vulcanization accelerator is contained in an amount of 5 parts by weight or less, preferably 1 to 2.5 parts by weight, based on 100 parts by weight of the raw rubber, an antifouling rubber obtained by vulcanizing the rubber composition. , The duration of the effect of preventing marine organisms from adhering becomes longer.

The reason why the content of the thiuram-based vulcanization accelerator is set to 5 parts by weight or less based on 100 parts by weight of the raw rubber is that if the content exceeds 5 parts by weight, the physical properties of the antifouling rubber will be out of the allowable range. Because there is.

As the thiuram-based vulcanization accelerator, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide,
Tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide and the like are exemplified.

Of course, the cuprous oxide and the thiuram-based vulcanization accelerator may be used in combination.

The rubber composition of the present invention further contains a vulcanizing agent. The type and content of the vulcanizing agent are determined according to the type of the raw rubber.

Further, the rubber composition of the present invention may contain carbon, generally used, within a range not to impair the purpose of the present invention.
Fillers such as calcium carbonate and clay, DOA, DBP,
Plasticizers such as TCP, antioxidants such as p-phenylenediamine, diphenylamine, and phenol; vulcanization accelerators such as thiazole and sulfenamide; zinc oxide;
It may contain stearic acid, process oil and the like.

The rubber composition of the present invention is kneaded with its constituent components, processed into a sheet shape, a block shape, a cylindrical shape or the like, and vulcanized under ordinary conditions to obtain an antifouling rubber.

The effect of the antifouling rubber obtained by vulcanizing the rubber composition of the present invention to prevent the marine organisms from adhering to the sea for a long time is as follows.
It seems to be due to the following mechanism of action.

That is, the N-arylmaleimides are held in the antifouling rubber, but when the antifouling rubber is immersed in seawater, the N-arylmaleimides on the surface layer are eluted first. . As a result, in antifouling rubber,
A concentration gradient of N-arylmaleimides occurs. Then, according to this gradient, the internal N-arylmaleimides migrate to the surface layer. This transition is due to the thermal motion of rubber molecules, and is generally known as a substance transfer phenomenon in rubber. The speed of this transition is affected by the degree of thermal motion of the molecule.

By the above mechanism, the N-arylmaleimides in the antifouling rubber are gradually released, so that the effect of preventing the adhesion of marine organisms is exhibited for a long time.

[0027]

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

Example A rubber composition was prepared by adding the compounds shown in Table C to the basic rubber compound shown in Table B. The following test evaluation was performed about them. The results are shown in Table C.

1) Normal physical property test Each rubber composition was kneaded and processed into a sheet, and then 148.
Vulcanized at 45 ° C. for 45 minutes. For those vulcanized rubbers, J
A tensile test is performed according to IS K6301 (JIS 3
No. dumbbell-shaped test piece), tensile strength (T _B ) and elongation (E _B ) were calculated. Further, a spring hardness test (A type) was performed according to JIS K6301. Further, a tear test (A type) was performed according to JIS K6301.

2) Underwater immersion test Each rubber composition was kneaded and processed into a sheet, and then 148.
Vulcanized at 45 ° C. for 45 minutes. Then 300x300x3
mm test pieces were obtained. The test specimens were taken at a depth of about 1 m at Uranagama beach (in Suruga Bay, about 10 m from the quay) in Numazu City, Shizuoka Prefecture.
, And was raised every predetermined period, and the presence or absence of marine organisms was evaluated according to the criteria shown in Table A below.

[0031]

[0032]

[Table 1]

[0033]

[Table 2]

[0034] * 1 IT-354 manufactured by Ihara Chemical Industries * 2 Sanshin Chemical * 3 Not implemented

[0035]

According to the present invention, there is provided a rubber composition serving as an antifouling rubber which contains an antifouling component which is safe (has no environmental pollution) and has a high antifouling effect, and which releases it over a long period of time. . Since the rubber composition of the present invention is suitable for manufacturing marine parts such as rubber domes and acoustic materials, the use of the rubber domes and acoustic materials manufactured using the rubber composition of the present invention for a long period of time. Thus, the adhesion of marine organisms to the hull can be prevented.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A01N 37/32 A01N 25/10 A01N 59/20

Claims (5)

(57) [Claims] 1. A rubber composition comprising a raw rubber and an N-arylmaleimide represented by the following formula I, wherein the content of the N-arylmaleimide is 3 to 100 parts by weight of the raw rubber.
A rubber composition for molding a vulcanized antifouling rubber, which is not less than part by weight. Embedded image (In the above formula I, X ¹ and X ² are each independently a hydrogen atom or 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. , A carboxyl group, a phenyl group, a phenylamino group, an alkenyl group, a thiocyano group, a sulfone group, an acetylamino group or a sulfamoyl group, and Y ² is a hydrogen atom, a halogen atom, an alkyl group, a lower alkoxy group, a nitro group or a hydroxyl group. And Y ³ is a hydrogen atom, a halogen atom or a dialkylamino group.) 2. The vulcanized antifouling rubber molding according to claim 1, wherein the rubber composition further contains 450 parts by weight or less of cuprous oxide based on 100 parts by weight of the raw rubber.
A rubber composition for preventing the adhesion of marine organisms. 3. The rubber composition according to claim 1, wherein the rubber composition further contains 5 parts by weight or less of a thiuram vulcanization accelerator based on 100 parts by weight of the raw rubber.
A rubber composition for preventing the adhesion of marine organisms for vulcanized antifouling rubber molding . 4. An antifouling rubber obtained by vulcanizing and molding the rubber composition according to claim 1. 5. The antifouling rubber according to claim 4, wherein the antifouling rubber is a rubber dome or an acoustic material.