JPS61250049A - Antifouling gelatinous composition - Google Patents

Abstract

PURPOSE:To provide the titled composition of high stress dispersibility, free from fouling-in-water, outstanding long-term prevention of aqueous organisms from latching, suitable for application to vessels, etc., constituted by dispersion medium made up of specific copolymer elastomer and oil component and W/O type emulsion consisting of aqueous disperse phase. CONSTITUTION:An A-B-A type tereblock copolymer elastomer (A is rigid polymer from vinyl compound such as styrene; B is flexible polymer from conjugated diene compound such as butadiene) is dissolved in an excess amount of oil component (e.g. machine oil) on heating followed by adding emulsifier (a nonionic surfactant) and slowly dropping water to effect emulsification thus forming a W/O type emulsion with a weight ratio of the aqueous disperse phase to dispersion medium falling between 85/15 and 5/95. This emulsion is then cooled to effect gelation, thus obtaining the objective composition.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention provides an antifouling gel composition that is applied to submerged parts of ships and the like to prevent the adhesion and growth of aquatic organisms such as algae, barnacles, and shellfish. It is related to.

[Conventional technology]

Ships such as yachts, boats, cargo ships, fishing boats, marine and undersea structures such as light buoys, buoys, oil storage structures, and fishing nets;
Regarding fishing equipment such as octopus, aquatic organisms such as algae, barnacles, bryozoans, and shellfish grow attached to the submerged parts of the equipment, causing various harmful effects. For example, in marine structures, the structure itself begins to corrode due to attached growth of aquatic organisms, and the attached pipes become clogged due to growth of aquatic organisms in attached pipes. In addition, in ships, the weight of the ship increases due to the attachment of the above-mentioned aquatic organisms to the bottom of the ship, and the resistance to water increases, resulting in a reduction in sailing speed and problems such as increased fuel costs. ing. Furthermore, if fishing equipment such as fishing nets is left immersed in water for a long period of time, the above-mentioned aquatic organisms will attach and grow, clogging the mesh of the fishing net and causing damage such as mass mortality of fish. ing.

In order to prevent various harmful effects caused by the adhesion and growth of aquatic organisms, the conventional method has been to apply paint to the submerged parts of the above-mentioned ships, marine/undersea structures, etc., and to mix poisonous substances into the paint. Various proposals have been made. For example, antifouling paints are made by mixing toxic substances such as cuprous oxide and organic tin compounds with paints whose main components are synthetic resins and rosin.
It has been proposed to paint this on the submerged areas. In addition, in order to maintain the antifouling properties of the paint for a long period of time, proposals have also been made to cover the painted surface with a plastic sheet or a film made of water-insoluble hydrophilic resin. (Unexamined Japanese Patent Publication No. 49-606
(See No. 0).

Recently, organotin-based compounds have been combined with high-molecular polymers and used as a component of antifouling paints.The high-molecular polymers are hydrolyzed and the organic tin-based compounds are gradually eluted. Attempts have also been made to prolong the effect.

[Problem that the invention seeks to solve]

In this way, conventionally proposed methods have focused on incorporating toxic substances into antifouling paints, etc., to prevent aquatic organisms, especially marine organisms, from adhering to submerged parts of ships, etc. It is intended to prevent However, the inclusion of poisonous substances in the paint is not only for preventing the adhesion of aquatic organisms, but also poses a serious problem in that the poisonous substances eluted into the water cause contamination of water such as seawater. In particular, water contamination with such toxic substances has a negative impact on fish and shellfish living in the water, and in severe cases, it may even lead to their death. It also has an adverse effect on humans who ingest the fish.

In addition, as mentioned above, the various proposed methods described above gradually elute toxic substances into water to prevent attachment of aquatic organisms (antifouling).
Therefore, once the toxic substances are eluted and exhausted, the antifouling effect on aquatic organisms disappears, and aquatic organisms begin to attach and grow again. Therefore, in order to maintain the antifouling property, it is necessary to perform re-application, which requires a huge amount of expense.

As described above, there is a strong demand for a method for preventing the attachment and growth of aquatic organisms without using poisonous substances from the viewpoint of cost and prevention of seawater contamination caused by poisonous substances.

The present invention was made in view of the above circumstances, and its purpose is to provide an antifouling gel composition that can prevent the adhesion of aquatic organisms over a long period of time without contaminating the water with toxic substances. It is something.

[Means for solving problems]

In order to achieve the above object, the antifouling gel composition of the present invention is produced by using a dispersion medium consisting of an A-B-A type teleblock copolymer elastomer and an oil component, and an emulsifier to make water into fine particles. The mutual ratio of the dispersion medium and the aqueous dispersed phase (water dispersed phase)/(dispersion medium) is 8 on a weight basis.
It is constructed by cooling and gelling a W/O emulsion set from 5/15 to 5/95, and the gel structure has a structure in which the water dispersed phase is held in a dispersed state in the form of particles. .

In order to find a method for preventing the attached growth of aquatic organisms without using poisonous substances, the present inventors first conducted repeated research on the attached growth mechanism of aquatic organisms. As a result, when the above-mentioned aquatic organisms attach to the submerged parts of ships, etc., first, the larvae of the aquatic organisms, such as the larvae of Fujibbo and the seeds of algae, attach to the submerged part and then move from there. I discovered that I can grow. Therefore, if the adhesion of such larvae of aquatic organisms can be prevented, the various adverse effects described above can be eliminated. As a result of further research on preventing the adhesion of such larvae, the present inventors found that the larvae easily adhere to fixed surfaces, but have difficulty adhering to physically unstable surfaces. In particular, the inventors have discovered that remarkable effects can be obtained by constructing the physically unstable surface with a gel-like composition having excellent stress dispersion ability, and have thus arrived at the present invention.

In the gel structure of the antifouling gel composition of the present invention,
The aqueous dispersed phase is not kept in a continuous state but in a particulate dispersed state, and is easily deformed when external force is applied.
During this deformation, the water contained in the gel in a dispersed state acts to absorb or disperse stress, and when the external force is removed, the gel has stress dispersion properties such that the deformation gradually recovers and returns to its original shape. Therefore, the larval bodies of aquatic organisms attach 1
Even if one tries to do so, due to the physical instability caused by the stress dispersion ability and the action of the oily substance on the gel surface, adhesion is not possible. In addition, in this antifouling gel composition, the water particles are stabilized by the action of the emulsifier, so even if it is left at room temperature for a long period of time, the weight loss is minimal. Moreover, it does not freeze even at low temperatures of about -20°C, maintains flexibility, and exhibits excellent stain resistance. This antifouling gel composition can be adjusted over a wide range from a very flexible gel to a relatively tough gel depending on the type, amount, water content, etc. of the teleblock copolymer elastomer and oil component. The above-mentioned antifouling gel composition can be prepared, for example, by dissolving an A-B-A type teleblock copolymer elastomer and appropriate additives in an excess amount of an oil component by heating, and then dissolving this dissolved system. It can be obtained by adding an emulsifier to the mixture, and then gradually adding water to emulsify the mixture to form a W/O emulsion, which is then cooled to form a water-containing gel containing water in the form of emulsion particles.

The above A-B-A type teleblock copolymer elastomer (hereinafter abbreviated as [teleblock elastomer]) is an elastomer with an A-B-A type structure consisting of a hard polymer A and a soft polymer B, For example, the A block is styrene,
A hard polymer of vinyl compounds such as methylstyrene, whose glass transition temperature is 70°C or higher, and about /O0
Polymers having an average molecular weight of 0 to 1 ooooo are effective. The B block is, for example, a soft polymer of a conjugated diene compound such as butadiene or isoprene, and its glass transition temperature is within the range of 150 to 30°C, and is approximately 450°C.
Polymers having an average molecular weight in the range 0 to /O00000 are useful.

The terminal A block of the teleblock elastomer consists of approximately 15 to 65 weight percent (hereinafter abbreviated as "%") of the teleblock elastomer.

The oil component that forms the dispersion medium together with the Teleblock elastomer includes oily substances that are liquid at room temperature and are compatible with the B block of the Teleblock elastomer and incompatible with the A block, such as machine oil, cylinder oil, Examples include transformer oil, rosin oil, and various liquid paraffins. These may be used alone or in combination. Note that a mixture in which a substance that becomes oily when heated, such as paraffin wax with a melting point of 120° C. or less or waxy low molecular weight polyethylene with a melting point of 150° C. or less, is added to the above oily substance can also be used as the oil component of the present invention.

The amount of the oil component to be used is within the range of /O0 parts based on 5 to 30 parts by weight (hereinafter abbreviated as "parts") of the teleblock elastomer, which is effective for forming a dispersion medium of the hydrogel.
The amount of teleblock elastomer used is determined primarily by the relationship between the water content of the final hydrogel product and its desired flexibility.

In addition, in order to increase the toughness of the final hydrogel, a crosslinking agent effective for the teleblock elastomer may be used in combination, if necessary. In this case, the crosslinking agents that can be used are effective vulcanizing agents and vulcanization accelerators that are used for the vulcanization of general rubbers, such as peroxides such as benzoyl peroxide, sulfur, and tetramethylthiuram. Disulfite, etc. The appropriate amount of the vulcanizing agent and vulcanization accelerator to be used is 0.01 to 2 parts based on 0 parts of Teleblock elastomer/O.
The optimum amount to be used is determined based on the relationship between the toughness and flexibility of the final hydrogel. Furthermore, anti-aging agents, antioxidants, or reinforcing fillers 9 are added to the teleblock elastomer or oil component to prevent thermal deterioration, oxidative deterioration, photodegradation, etc.
Coloring pigments, dyes, etc. can be added.

Dissolution of the teleblock elastomer and oil component.

The emulsifier added to the solution system has the property of stably maintaining the form of a W/O emulsion by forming a dispersed phase of countless emulsified water molecules in the dispersion medium consisting of the teleblock elastomer and oil component. Nonionic surfactants are particularly effective as this type of emulsifier. As an example, polyethylene glycol oleyl ether.

Examples include polyethylene glycol nonylphenyl ether, polyethylene glycol decylphenyl ether, sorbitan laurate, etc. Commercially available products include, for example, Noigen EA, Noigen ET, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Sorgen and the like are preferred.

The water that is emulsified by the emulsifier and becomes a dispersed phase may be pure water or may contain ions such as certain metal ions and halogen ions, such as tap water and natural water. In addition, water-soluble organic materials such as fragrances, dyes, and carbonic acid may be added to this water to the extent that they do not affect the emulsification of the water or the stability of the final gel, for the purpose of coloring the hydrogel, improving flame retardancy, and other purposes. calcium,
Inorganic materials such as sodium carbonate, etc. can be added. The amount of emulsifier to be used varies depending on the amount and type of water contained in the final hydrogel, but in general, it is appropriate to use 1 to 20 parts, preferably 5 to 10 parts, based on 0 parts of water/O.
Department.

The method for producing the antifouling gel composition of the present invention is not particularly limited, but a preferred method is to first dissolve the above-mentioned teleblock elastomer and appropriate additives in an excess amount of oil component under heating. A nonionic surfactant is added as an emulsifier to this dissolved system, and water is gradually added dropwise to emulsify it to form a W/O emulsion. the result,
A stable heterogeneous system is formed in which the oil component in which the teleblock elastomer is dissolved is the dispersion medium and the water particles are the dispersed phase. Next, this heterogeneous system is cooled to room temperature to induce gelation, thereby obtaining a hydrogel containing water in the form of emulsion particles.

In this production example, a mixture of teleblock elastomer and oil component in a predetermined ratio is heated to about 80-170°C to dissolve. This melting system is a fluid having a viscosity in the range of 10 to 500 voids in the temperature range of about 80°C or higher, and the viscosity increases rapidly as the temperature falls, and
It becomes an oily gel with no fluidity in the temperature range from °C to room temperature. Emulsification of water in the above-mentioned dissolution system is carried out at a temperature range of about 80 to 00C under atmospheric pressure, and in a temperature range of about 00 to 1300C under pressure such as in an autoclave. After the emulsifier is added in this manner, water is gradually added dropwise to form a W/O emulsion. This W
When cooling and gelling the /O type emulsion, gel products of various shapes can be obtained by using a mold or the like. For example, after adding a vulcanizing agent etc. to the W/O emulsion as necessary, it is poured into a mold, extruded with an extruder, or coated with a coating device while maintaining fluidity in the temperature range of 70 to 90°C. Use 1 paper of cloth.

Hydrous gel products in various shapes can be obtained by applying it to the surface of release paper or the like and then cooling it to room temperature.

In addition, in this invention, the aspect of each process of the said manufacturing example can be changed suitably. For example, if a thermally stable emulsifier can be used, it can be added in advance to the mixture of the Teleblock elastomer and the oil component, or water in which the emulsifier is dissolved or dispersed can be added to the Teleblock elastomer. It can also be added to a heated melt system of elastomer and oil component. In addition, the amount of water used as the dispersed phase is
The weight ratio of (water dispersed phase)/(dispersion medium) is 85/15 to 5/
It is necessary to set it within the range of 95. If the amount of water used exceeds 85% of the total amount of both, the amount of the mixture of the teleblock elastomer and the oil component will decrease relatively, and the stability of the hydrogel will deteriorate, or the W2O type will undergo phase inversion. This results in an O/W type emulsion, and gelation becomes impossible.

Conversely, if the amount of water used is less than 5% of the total amount of both,
The amount of the mixture of the teleblock elastomer and the oil component increases significantly, making it impossible to obtain a hydrogel with sufficient functionality.

Therefore, the antifouling gel composition of the present invention obtained by cooling and gelling the emulsion has an aqueous dispersed phase of 85 to 85%.
The content of the dispersion medium consisting of the teleblock elastomer and the oil component is within the range of 15 to 95%.

The antifouling gel composition of the present invention obtained in this manner can be adjusted over a wide range from a very soft gel to a relatively tough gel depending on the type and amount of the teleblock elastomer and oil component used, water content, etc. In either state, the particulate water dispersed phase in the gel exhibits excellent stress dispersion properties and prevents aquatic organisms from adhering to the gel. The above stress dispersion characteristics are
Unlike the rubber-like elasticity of conventional oil-based gels (easily deformed when stress is applied, but instantly restored when stress is removed),
When stress is applied, the stress is absorbed or diffused by the dispersed phase of water particles, and after the stress is removed, it gradually recovers to its original shape, making it extremely effective in preventing the attachment of aquatic organisms.

〔Effect of the invention〕

As described above, the antifouling gel composition of the present invention has stress dispersion properties that are extremely effective for preventing the adhesion of aquatic organisms, so it can be applied to submerged parts of ships, etc. Demonstrates outstanding effectiveness in preventing adhesion of aquatic organisms. Moreover, since this product does not contain any toxic substances, there is no risk of contamination of the water (and it maintains its antifouling effect for a long time without losing its antifouling effect due to the disappearance of toxic substances).
Significant cost savings can be achieved.

Next, examples will be described together with comparative examples.

[Example 1] IIi? equipped with an efficient stirrer, reflux condenser and nitrogen gas inlet. In a three-necked flask, machine oil with a viscosity of 330 centipoise (20°C) (manufactured by Idemitsu Kosan Co., Ltd., Daphne Mechanic Oil-Mechanic 75) /0 parts and styrene-butadiene-styrene teleblock elastomer (manufactured by Shell Chemical Co., Ltd., Califlex TR- 1/O1)/
Add part O and heat to approximately 130°C while stirring in a nitrogen gas stream.
It was heated to dissolve. After adding and dissolving 5 parts of an emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neugen EA-50) to this solution, 0 parts of distilled water/O was added while keeping the temperature inside the flask at 80-90'C and stirring well. Gradually drip over about 2 hours,
A W/O emulsion was produced.

The obtained white emulsion was heated to about 80'C to give it fluidity, poured into a mold with a depth of 50 m, and then cooled to room temperature to have a volume of 300X/O0X50.
A flexible hydrogel of m was obtained.

This water-containing gel did not show any deformation even in a water resistance test where it was left in water for 12 hours.
The gel weight reduction rate when left for days was as small as 1.7%.

Next, in order to measure the stress dispersion properties of this hydrogel,
Transmission stress measuring device rheometer (manufactured by Fuji Rika Kogyo Co., Ltd., R
The results of measurements using the UD-J type will be explained with reference to FIG. A rod (B) on which a steel metal ball (A) with a diameter of 18 m and a weight of 34.5 g is connected is linked to a rheometer body (not shown), and the metal ball (A) is inserted into the gel (C). The relationship between the penetration distance (H) of the metal ball (A) and the stress applied to the rod (B) is measured. As a result of measurement in this way, the penetration distance (H) was 30 mm and the metal ball (A
) was buried in the gel (C), the repulsive stress applied to the (B) portion was as small as about 3QOg.

Furthermore, when this metal ball was removed, it completely recovered to its original shape in about 1.5 minutes.

The above properties indicate that the hydrogel of the present invention is flexible, tough, and has excellent stress dispersion properties. This stress dispersion property appears as a result of the water particles in the gel deforming easily in response to external force and absorbing or dispersing the external force.

[Comparative Example 1] In a beaker, 0 parts of machine oil (manufactured by Idemitsu Kosan Co., Ltd., Daphne Mechanic Oil-Mechanic 75) and styrene-butadiene-styrene teleblock elastomer (
Shell Chemical Co., Ltd., CARIFLEX TR-1/O1)
/O part was added and heated to about 130°C to dissolve. This melt was poured into the same mold as in Example 1 and then cooled to obtain an oily gel with a volume of 300x/00x50.

As a result of measuring the stress dispersion properties of this oil-based gel in the same manner as in Example 1, the repulsive stress applied to the part (B) at a penetration distance of 301 m from the metal ball was approximately 1800 g, which showed extremely high repulsive resiliency. Ta. In addition, metals ■, y from the gel
was removed (and the gel instantly recovered to its original shape, exhibiting the properties of a highly elastic gel).

[Example 2] Cylinder oil (manufactured by Idemitsu Kosan Co., Ltd., MC-500) with viscosity FJj of 240 centiboise (20°C) / 0 parts of 0 and styrene-butadiene-styrene teleblock elastomer (
Manufactured by Shell Chemical Co., Ltd., CARIFLEX TR-1/O7) 20
A portion of the mixture was placed in the same flask as in Example 1, and heated to about 140° C. with stirring in a nitrogen gas stream to dissolve. An emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neugen ET-80) is added to this solution.
Ion-exchanged water 3 was prepared in the same manner as in Example 1 by adding /O part.
00 parts were emulsified to produce a W/O emulsion.

Next, this white emulsion is heated to about 80°C to give it fluidity, poured into a mold, and then cooled to a volume of 30°C.
A hydrous gel of 0xlOOx50 Tsuru was obtained.

[Example 3] Liquid paraffin with a viscosity of 170 centiboise (20°C)
An emulsifier (Daiichi Kogyo Seiyaku Co., Ltd.) was added to a solution of 15 parts of styrene-butadiene-styrene teleblock elastomer (Califlex TR-1/O7, made by Shell Chemical Co., Ltd.) and 15 parts of styrene-butadiene-styrene teleblock elastomer (Califlex TR-1/O7, made by Shell Chemical Company). Manufactured by Neugen EA-7
3) Add 250% of tap water in the same manner as in Example 1, adding part O.
A W/O type emulsion was produced by emulsifying the mixture. Next, this emulsion was heated to about 80°C, poured into a mold, and then cooled to obtain a hydrogel pad having a volume of 300X/O0X/O11.

This gel pad did not show any deformation in the water resistance test when it was left in water for 12 hours.
The gel weight reduction rate when left in the sun was 2.4%.

[Example 4] 60 parts of liquid paraffin (same as that of Example 3), softened fish with an average molecular weight of about 2000/low molecular weight polyethylene (manufactured by Sanyo Kasei Co., Ltd., Sunwax 151-P) 40
and styrene-butadiene-styrene teleblock elastomer (manufactured by M Kasei Co., Ltd., Turprene-411) 20
Add an emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neugen E
A-83) Add 7 parts of 25% sodium carbonate aqueous solution/
Part O0 is emulsified in the same manner as in Example 1 to produce a W/O emulsion. Next, this emulsion was heated to about 90°C.
A water-containing gel sheet was obtained by coating the gel on a silicone resin-treated release paper in the form of a sheet with a thickness of 2 mm at a temperature of 100 mL, and cooling it to room temperature.

This water-containing gel sheet exhibited strong adhesion to glass, wood-based materials, and paper-based materials. For example, the surface of crepe paper could be directly coated with this hydrogel sheet.

[Example 5] Styrene-butadiene-styrene teleblock elastomer (Shell Chemical Co., Ltd., Kaliflex TR) was added to 0 parts of liquid paraffin (Kyodo Oil Liquid Paraffin-350, manufactured by Kyodo Oil Co., Ltd.) with a viscosity of 400 boids (20°C). -1/O7)
/O part was heated and dissolved in the same manner as in Example 1. After adding 5 parts of an emulsifier (Solgen-50, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) to this solution, 15 parts of distilled water was gradually added in the same manner as in Example 1 to emulsify. The obtained W/O emulsion was poured into a mold at about 80°C and cooled to a volume of 30°C.
A hydrogel sheet of 0X/O0X2m was obtained.

[Comparative Example 2.3] A conventional coating composition shown in Table 1 (Comparative Example 2) and a coating composition to which cuprous oxide was added as an antifouling agent (
Comparative Example 3) was applied with a brush to a thickness of 3 fins on a glass fiber reinforced polyester panel (300X/O0x5 Tsuru), and air-dried for 7 days to obtain Comparative Samples 2 and 3.

(Left below) (Antifouling test) Glass fiber reinforced polyester board (300X/OX/O0X) to which the gel sheets of Examples 1 to 5 and Comparative Example 1 were fixed
Glass fiber-reinforced polyester plates coated with the paints of 5 and Comparative Example 2.3 were suspended 1.5 m below the water surface from a test raft installed at Akashi Port, Hyogo Prefecture, and the state of contamination by marine organisms was observed for 2 years. .

The results are shown in Table 2. The numerical value is the ratio (%) of the area covered by marine organisms to the area of the polyester board.

From the results in Table 2, in Comparative Example 1 using oil-based gel, 12
Adhesion of aquatic organisms was observed after 24 months had passed, and the adhesion state had reached 75% after 24 months had passed. Further, in Comparative Example 2 in which a simple coating film was formed, adhesion of aquatic organisms was already observed after 6 months had passed, and the adhesion state had reached /O0% after 18 months had passed.

Also, in Comparative Example 2, in which an antifouling agent was added, adhesion of aquatic organisms was observed after 18 months, and the amount had increased to 50% after 24 months. In contrast, Example 1
- 4, after 24 months had passed, only 5% of the adhesion was observed in Example 2 and 2% in Example 5, and the other Examples showed no adhesion of aquatic organisms. It can be seen that an extremely excellent adhesion prevention effect can be obtained.

[Brief explanation of drawings]

The drawing is an explanatory diagram of an apparatus for measuring stress dispersion properties of an antifouling gel composition. - A... Steel metal ball B... Rod C... Gel 1st
figure

Claims (1)

[Claims] (1) Equipped with a dispersion medium consisting of an A-B-A type teleblock copolymer elastomer and an oil component, and an aqueous dispersed phase formed by finely distributing water with an emulsifier. Ratio (water dispersed phase)/(dispersion medium) is 85 on a weight basis
Constructed by cooling gelation of W/O type emulsion set at /15 to 5/95, in the gel structure,
An antifouling gel composition characterized in that the aqueous dispersed phase is maintained in a dispersed state in the form of particles.