JPH06256586A - Rubbre composition for preventing adhesion of aquatic organism and its structure - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of continuously releasing an active component free from danger of environmental pollution and having high antifouling effect for a long period by blending a rubber with a specific isothiazolone derivative. CONSTITUTION:This rubber composition contains (A) 100 pts.wt. rubber and (B) 3-80 pts.wt. 3-isothiazolone derivative (preferably 4,5-dichloro-2-n- octylisothiazolin-3-one) of the formula (X<1> and X<2> are H, halogen, etc.; Y is straight-chain or branched chain 1-14C alkyl, 1-9C aryl, etc.). Furthermore, as the component A, chloroprene rubber, natural gum, nitrile rubber, etc., is preferably used and number-average molecular weight thereof is preferably 50000-1000000. Furthermore, vulcanization accelerator, vulcanizer, etc., may preferably be blended with this composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition for preventing adhesion of aquatic organisms to rubber components such as underwater structures and ships.

[0002]

2. Description of the Related Art At present, an antifouling rubber which can be made thick as a rubber composition for preventing adhesion of aquatic organisms, has an adjustable thickness, and has a long life compared to paints is used in rubber members for ships and underwater structures. There is. As the component having the antifouling property, those having organic tin such as tributyltin (TBT) and tripropyltin (TPT) are most effective, and the other components are remarkably inferior in performance and cannot be used.

[0003]

However, since organic tin contaminates seawater and freshwater, and even affects the human body, antifouling materials such as structures and members containing organic tin are used in water. That was totally banned.
Therefore, there is a demand for the development of a rubber which is a non-tin antifouling agent and which is less likely to cause water pollution and which can prevent adhesion of aquatic organisms.

[0004]

Means for Solving the Problems The inventors have incorporated a 3-isothiazolone derivative into a rubber as a non-tin antifouling material with little risk of water pollution, and utilize the migration phenomenon of this derivative in the rubber. Sequentially, by migrating a compound having an antifouling function from the inside to the surface, it was found that a rubber composition for antifouling of aquatic organisms can be obtained with a long life of antifouling performance of aquatic organisms, leading to the present invention. It was

That is, the present invention comprises (1) 100 parts by weight of rubber and (2) formula 1

[Chemical 2]

(Where X is¹And X²Are each alone
To hydrogen, halogen, or C₁~ C _FourStraight chain or minutes
A branched chain alkyl group, Y is a straight chain having no substituent
Or branched chain C₁~ C₁₄As an alkyl group or substituent
Has halogen or lower alkyl, or is unsubstituted
C₁~ C ₉Aralkyl group of or as a substituent
Enoxy, hydroxy, trihalomethyl, halogen, low
With primary alkyl or lower alkoxy, or non-
Substitution C₁~ C₉Is an aryl group. ) Represented by 3
Water containing 3 to 80 parts by weight of isothiazolone derivative
Provided is a rubber composition for preventing adherence of metabolites. further,
Adhesion of aquatic organisms that have been cured by the addition of a vulcanizing agent
A cured product of a rubber composition for prevention is provided. Rubber composition
The thickness of the cured product is preferably 1 mm or more. Well
In addition, the underwater rubber member that uses such a cured product for the surface layer
And underwater structures.

The present invention will be described in detail below.

The rubber used in the present invention is not particularly limited as long as it shows weather resistance and seawater resistance after vulcanization. For example, natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), ethylene-propylene rubber (EPM), ethylene-propylene-diene terpolymer rubber (EPDM), isobutylene isoprene rubber (IIR). ), Brominated isobutylene isoprene rubber (Br-IIR), chlorinated isobutylene isoprene rubber (Cl-IIR), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), nitrile rubber (NBR), and the like. Chloroprene rubber (C
R), natural rubber (NR), brominated isobutylene isoprene rubber (Br-IIR), nitrile rubber (NBR), chlorosulfonated polyethylene (CSM) and the like are preferable.

The rubber used in the rubber composition of the present invention preferably has a number average molecular weight of 50,000 to 1,000,000.

In the present invention, the compound used to prevent the attachment of aquatic organisms has the formula 1

[0011]

[Chemical 3] It is a 3-isothiazolone derivative represented by.

Where X¹And X²Are each alone
To hydrogen, halogen, or C₁~ C _FourWith an alkyl group of
Yes, X¹Or X²At least one of
It's a gen. Y is a linear or branched chain having no substituent
C of the chain₁~ C₁₄Alkyl group, halogen or
Or C₁~ C₃With lower alkyl, or non-substituted
Replacement C₁~ C₉As an aralkyl group or a substituent
Phenoxy, hydroxy, trihalomethyl, halogen,
C₁~ C_FourLower alkyl or C₁~ C₃Lower Al
C with or without substitution₁~ C₉Ally
It is a ru basis. However, having a substituent containing a carbon atom
The number of carbon atoms in the aralkyl group and aryl group is
It is defined by the number including carbon atoms in the substituent.

Specific examples of X ¹ include hydrogen, chloro, bromo, iodo, methyl, ethyl, propyl, isopropyl, butyl, t-butyl and the like. Specific examples of X ² include hydrogen, chloro, bromo, iodo, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, chloromethyl, chloropropyl, bromomethyl, bromoethyl, bromopropyl and the like. Specific examples of Y include methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, pentadecyl, octadecyl, cyclopropyl, cyclohexyl, benzyl, 3,4-dichlorobenzyl, 4-methoxybenzyl, 4-chlorobenzyl. , 3,4-dichlorophenyl,
Hydroxymethyl, chloromethyl, chloropropyl, diethylaminoethyl, cyanoethyl, carbomethoxyethyl, ethoxyethyl, 2-methoxy-1-bromomethyl, 3,3,5-trimethylcyclohexyl, phenoxyethyl, p-chloroanilinomethyl, phenylcarba Moxymethyl, allyl, propynyl, vinyl, carboxyethyl, 1-isothiazolonylethyl, and 1,
2,2-trichlorovinyl etc. are mentioned.

Among them, X ¹ and X ² are Cl, and Y is C
Unsubstituted aralkyl group or aryl group ₁ -C _9, it is preferable in particular C ₈ H _17. Examples of such a 3-isothiazolone derivative include, for example, 4,5-dichloro-
2-n-octylisothiazolin-3-one is available and is available from Rohm and Haas. Further, such a 3-isothiazolone derivative does not have toxicity that pollutes the surrounding environment. For example, 4,5-
The LD ₅₀ of dichloro-2-n-octylisothiazolin-3-one was 1700 mg / kg (male rat), 28
00 mg / kg (female rat).

The content of such a 3-isothiazolone derivative is 3 to 80 parts by weight based on 100 parts by weight of rubber,
Particularly, it is preferably 5 to 55 parts by weight. The content is
If it is less than 5 parts by weight, sufficient antifouling property cannot be maintained.
On the other hand, if it exceeds 55 parts by weight, the crosslinking of the rubber is inhibited and the molecular network structure becomes rough. Therefore, the antifouling property does not last.

A vulcanization accelerator, a vulcanizing agent, a vulcanization retarder, an antiaging agent and the like may be added to the rubber used in the present invention. Specific examples of the vulcanization accelerator include tetramethylthiuram monosulfide (TS), dibenzothiazyl disulfide (DM), ZnO, MgO, stearic acid, N-cyclohexyl-2-benzothiazylsulfenamide (CZ), Tetramethylthiuram disulfide (TT), 2-mercaptoimidazoline (Na22)
Etc. The addition amount of the vulcanization accelerator is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of rubber.

Specific examples of the vulcanizing agent include sulfur, 4,4-
Dithiomorpholine (R), ZnO, MgO, PbO,
Pb ₃ O ₄ and the like. The amount of vulcanizing agent added is 1
It is preferably 0.1 to 10 parts by weight with respect to 00 parts by weight.

Specific examples of the vulcanization retarder include N-cyclohexylthiophthalimide (PVI) and the like.
The addition amount of the vulcanization retarder is 100 parts by weight of rubber,
It is preferably 0.1 to 5 parts by weight.

Specific examples of the antiaging agent include N-phenyl-N '-(isopropyl-p-phenylenediamine).
(3C), N-phenyl-N '-(1,3-dimethylbutyl-p-phenylenediamine) (6C), octylated diphenylamine (OD3), poly (2,2,4-trimethyl-1,2-di) Hydroquinoline) (RD), 2-
Examples include mercaptobenzimidazoline (MB).
The amount of antioxidant added is 100 parts by weight of rubber,
It is preferably 0.1 to 10 parts by weight.

In the rubber composition of the present invention, in addition to the above-mentioned components, fillers such as carbon, calcium carbonate, silica, talc and clay, colorants such as disazo red and disazo yellow, DOA, DBP, TCP and the like. Additives such as plasticizers, aroma type, naphthene type and paraffin type softeners may be added.

(Production Method of Rubber Composition) The production method of the rubber composition of the present invention is not particularly limited. For example, 100 parts by weight of the above-mentioned rubber and 3-isothiazolone derivative 3 to 3 are used.
It is obtained by adding 80 parts by weight and, if necessary, other additives and kneading. Furthermore, a composition to which a vulcanizing agent has been added can be produced.

(Production Method of Cured Product) The production method of the cured product of the rubber composition of the present invention is not particularly limited. For example, in the case of chloroprene rubber (CR) or natural rubber (NR), sulfur or ZnO, Using MgO, Pb ₃ O ₄ or the like as a vulcanizing agent, at a temperature of 100 ° C. to 180 ° C., a pressure of 4 kgf /
It is obtained by reacting for 10 minutes to 24 hours at a cm ² or more.

The obtained rubber composition or a cured product thereof can be appropriately molded, and the rubber composition for preventing adhesion of aquatic organisms can be used as an underwater rubber member or an underwater structure.

Here, aquatic organisms attach to organisms attached to underwater parts such as ships, buoys and artificial structures on the bottom of the water, and to parts that may be temporarily exposed to the sea due to low tide. Includes organisms (adherent organisms). Specifically, examples thereof include aquatic animals such as barnacles, bryozoans, and serpras, or aquatic plants such as seaweeds.

As the underwater member using the rubber composition containing the 3-isothiazolone derivative of the present invention for preventing the adhesion of aquatic organisms or a cured product thereof, the bottom of a ship, a member used on the side of a ship, a barge, a pier, Examples include rubber buoys, fenders, marine hoses, and floating and sinking type airbags used for floating parts. These underwater members can be produced, for example, by using the rubber composition itself of the present invention or by obtaining a cured product of the composition and adhering the cured product to a required portion of the underwater member.

Further, as an underwater structure using the rubber composition containing the 3-isothiazolone derivative of the present invention for preventing adhesion of aquatic organisms or a cured product thereof, a submarine cable surface layer material or a facility installed on the seabed can be used. Examples include vessels that are fixed on the seabed such as surface materials, quays, and oil rigs, or that artificially store seawater or freshwater such as ikesu.

The rubber composition for preventing adhesion of aquatic organisms and the cured product thereof containing the 3-isothiazolone derivative of the present invention can maintain the effect of preventing adhesion of aquatic organisms for a long period of time. As its mechanism of action, a molded article (antifouling layer) of an antifouling rubber composition containing a 3-isothiazolone derivative, which is a component having an antifouling effect used in the present invention, or a vulcanized molded article (antifouling layer) thereof is treated with seawater. When immersed in, the antifouling component of the surface layer is eluted into the sea. As a result, a concentration gradient of the antifouling component is generated in the antifouling layer. It is considered that due to this concentration gradient, the antifouling component inside the antifouling layer migrates to the surface and is eluted from the surface of the antifouling layer into seawater.

When the rubber composition for preventing adhesion of aquatic organisms containing the 3-isothiazolone derivative of the present invention is molded into an underwater member or an underwater structure, a preferable antifouling layer thickness is 1
It is preferably at least mm, especially at least 3 mm. 1 mm
If it is less than the above range, long-term release of the antifouling component cannot be expected, which is not suitable for practical use. When it is 1 mm or more, the antifouling effect is effective for a long period of time, and therefore it is considered that the 3-isothiazolone derivative as the antifouling component is sequentially transferred from the inside of the cured product of the rubber composition to the outside.

[0029]

EXAMPLES The present invention will be described in detail below with reference to examples.

(Examples 1 to 9 and Comparative Examples 1 to 3) (1) Polymers having the following compounding ratios were produced. (I) CR basic composition (unit is parts by weight) CR 100 carbon SRF 50 MgO 4 stearic acid 3 old-proof 6C 1 ZnO 5 vulcanization accelerator (Na22) 1 (ii) NR basic composition (unit is parts by weight) NR 100 carbon HAF 35 ZnO 3 stearic acid 2 old protective 6C 1.5 sulfur 2.5 vulcanization accelerator (CZ) 1

(Iii) IIR basic composition (unit is parts by weight) IIR 100 carbon HAF 50 ZnO 3 stearic acid 1 sulfur 1.75 vulcanization accelerator (TT) 1

Note) Na22: Sansera-22 manufactured by Sanshin Chemical Co., Ltd. 6C: Nocrac 6C manufactured by Ouchi Shinko Chemical Co., Ltd. Vulcanization accelerator (CZ): Sansera-CM vulcanization retarder manufactured by Sanshin Chemical Co., Ltd. (PVI): Sunguard P manufactured by Monsanto
VI Vulcanization accelerator (DM): Noxera-D manufactured by Ouchi Shinko Chemical Co., Ltd.
M Vulcanization accelerator (CZ): Noxera-C manufactured by Ouchi Shinko Chemical Co., Ltd.
Z vulcanization accelerator (TT): Noxera-T manufactured by Ouchi Shinko Chemical Co., Ltd.
T

Various components were added to the above-mentioned polymers in the mixing ratios (i) to (iii) at the mixing ratios shown in Table 1, and the mixture was kneaded for 4 to 6 minutes with an internal laboratory mixer to give the rubber composition of the present invention. Was manufactured. The physical properties of the obtained rubber composition and the immersion test in the sea were measured. The results are shown in Table 1.
Shown in. Also for Comparative Examples 1 to 3, at the compounding ratio of Table 1,
With respect to the composition obtained in the same manner as in Example 1, the physical properties in the normal state and the immersion test in the sea were measured. The results are shown in Table 1. In Example 9, the rubber composition of Example 4 was used as a marine hose-shaped test piece (inner diameter φ30 mm, outer diameter φ50 mm, length 1).
The one molded into 50 mm) was used. In Comparative Example 2, the test piece of Comparative Example 1 to which the silicon-based paint was applied once was used.

(2) Normal State Physical Property Test The above rubber compositions (i) to (iii) were kneaded, processed into a sheet, and then vulcanized at 148 ° C. for 45 minutes. These vulcanized rubber, (using the dumbbell-shaped test piece of JIS 3 No.) subjected to a tensile test according to JIS K6301, to calculate the tensile strength (T _B) and elongation (E _B). In addition, a spring hardness test (A type) was performed according to JIS K6301. Furthermore, JIS K630
A tear test (type A) was performed according to 1. Table 1 shows the measurement results of the above-mentioned normal physical properties.

(3) Immersion test in sea Each rubber composition was molded in the same manner as in the preparation of the test piece for a physical property test in (2) using a mold to obtain 300 × 300 × 3 mm.
The test piece of was obtained. The test pieces were dropped into the sea at a depth of about 1 m from the sea surface of about 400 m from the shore of Uranagahama quay in Numazu City, Shizuoka Prefecture, and after 2 months, 4 months, and 8 months, sheets were placed. The degree of slime adhered on the top and the amount of organisms were measured and evaluated according to the criteria described in Table 2. The adherence rate (%) of the organism was shown by the ratio of the area of the part of the sheet to which the organism adheres to the total area of the sheet. Based on this, it is determined whether the composition can be used or not as the marine rubber member or the undersea structure of the present invention by 1 to 5
It evaluated with the whole number. The evaluation results are listed in Table 1.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[0039]

EFFECTS OF THE INVENTION By using the rubber composition for preventing adhesion of aquatic organisms or the vulcanized product thereof containing the 3-isothiazolone derivative of the present invention, an antifouling component having no risk of environmental pollution can be continued for a long period of time. It is now possible to manufacture products that prevent the adhesion of aquatic organisms that are released by

Claims (5)

[Claims] (1) 100 parts by weight of rubber and (2) formula 1(In the formula, X¹And X²Are hydrogen, ha
Rogen or C₁~ C _FourA straight or branched chain alky
And Y is a linear or branched chain having no substituent.
C₁~ C₁₄Alkyl group, halogen as a substituent or
Is a lower alkyl or unsubstituted C₁~ C ₉
Aralkyl group of or phenoxy,
Droxy, trihalomethyl, halogen, lower alkyl or
Or having lower alkoxy or unsubstituted C₁~
C₉Is an aryl group. ) 3-isothiazo
Ron derivative 3 to 80 parts by weight
A rubber composition for preventing adhesion of aquatic organisms. 2. A composition obtained by further adding a vulcanizing agent to the rubber composition for preventing adhesion of aquatic organisms according to claim 1. 3. The cured product of the rubber composition has a thickness of 1 mm.
The cured product of the rubber composition according to claim 2, which is for preventing adhesion of aquatic organisms. 4. A water-in-water rubber member, wherein the cured product of the composition according to claim 2 or the cured product according to claim 3 is used for a surface layer. 5. An underwater structure using the cured product of the composition according to claim 2 or the cured product according to claim 3 for the surface layer.