KR970006493B1 - Composite and method for prevention of hydroides elegans adhesion - Google Patents

Abstract

None.

Description

[Name of invention]

Anti-adhesion agent and anti-adhesion method of Hydroid Elegance

Detailed description of the invention

The present invention relates to an anti-adhesion agent and an anti-adhesion method of one species of living creatures in the sea, particularly by adding it to an intake of sea water or applying it to an underwater structure such as a fishing net or the bottom of a ship. The present invention relates to a biofouling agent and coating composition inhabiting the sea effective for preventing contamination by Lloyd's elegance and a method thereof.

In recent years, hydrophilic elegance, which is one of the fouling organisms in a closed port and aquaculture, has increased, and in factories where seawater is used as cooling water, it has become a cause of corrosion by attaching and drilling holes in cooling tubing of heat exchangers.

On the other hand, aquaculture farms have caused great damage to oyster farming, attached to fish nets in large quantities, hampered the distribution of seawater, caused dissolved oxygen in farming nets, and killed broilers.

In addition, when attached to the shelf floor, the navigation speed of the ship is lowered, and therefore, there are obstacles such as having to put it in a dock to remove it.

Therefore, organic tin compounds and copper oxide have been widely used as biofouling agents for bottom coatings and fishing nets, that is, antifouling agents in seawater.

However, these antifouling agents are restricted in their use for environmental pollution prevention due to their poor degradability in nature and bioconcentration.

Accordingly, the urgent development of highly stable alternative antifouling agents and the pursuit of the stability of the compounds have resulted in strong selectivity of effects on individual contaminants.

In this regard, high aliphatic amine compounds (Japanese Patent Application Laid-Open No. 57-29441, Japanese Patent Application Laid-Open No. 55-55101) or dialkyl, together with many effective medicines, are safe and prevent the adhesion of living organisms in these seas. Dithiocarbamic acid compounds (Japanese Unexamined Patent Application Publication No. 48-8816) have already been limited and widely known.

In addition, the present inventors have already proposed an invention (Japanese Patent Application No. 62-189645) relating to a higher aliphatic amine-containing polymer having various desired properties as a safe coating composition.

However, conventionally proposed antifouling agents such as higher aliphatic amine compounds and dialkyldithiolacbamic acid compounds are known to exhibit strong antifouling effects against Mytilus edulis or Barnacle. The hydrophilic elegance described above cannot exhibit sufficient antifouling effect, and particularly has a drawback that the effect is remarkably lowered in a sea area with a lot of organic matter and bacteria.

On the other hand, it is preferable that the coating antifouling agent dissolves the active ingredient by a predetermined amount from the coated surface, and the effect is maintained for a longer period of time.

In addition, when applied to an underwater structure such as a ship bottom or a seawater intake wall or the like, various conditions to be provided as roads, that is, coating film properties such as strength or adhesion as a coating film, and other active ingredients are contained in the road It must also satisfy the fact that there is no reactivity with the component and that it does not greatly affect the drying property.

Here, the hydroid elegance is a creature that lives in the marine species belonging to the group of ring-shaped animal gates, polymorphs, and Serpulidae, and the organisms swim in the sea and adhere to the attachment base. It grows by secreting the calcareous habitat.

These creatures have been known for a long time with barnacles as the fouling organisms at the bottom of the ship, but according to the findings obtained by past experiences of the inventors, the fouling organisms of these seawater systems such as Hydroids Elegance, Mytileus Edulis, Barnacles, etc. The growth of these organisms and their attachment to the waterway walls are special, by the environment of the sea area and by the adaptation of each organism.

In other words, if the organisms of any of these organisms adhere to the coffin walls or their waters, then the formation of the organisms of other organisms will be inhibited, and only the first organisms that have produced their first attachment will grow. In addition, in the case of hydrolyzed elegance, it is not surprising that only this covers the entire attachment base in a specific sea area, and the thickness of the adhesion layer reaches 10 cm in about two months.

In view of such phenomena and perceptions, the present invention is particularly effective for hydrodes having low toxicity to livestock and fish, and less environmental pollution to fishing nets, facilities and waterways in areas where hydroid elegance attaches preferentially. It is to provide an elegance adhesion agent and coating composition and a method thereof.

Thus, according to this invention, general formula (I) or (II)

[Wherein R ¹ is a saturated or unsaturated straight chain aliphatic hydrocarbon group having 12 to 18 carbon atoms, R ² is a hydrogen atom or a methyl group, R ³ is a hydrogen atom, a methyl group,

(CH ₂ ) ₂ -NH ₂ or (CH ₂ ) ₃ -NH ₂

Is a group represented by the formula (wherein R ² represents a methyl group, R ³ represents a methyl group).

[Wherein, R ⁴ represents an alkyl group having 10 to 28 carbon atoms, R ⁵ represents an amino group, a C ₁ to ₂ alkyl group substituted amino group (however, these alkyl groups may be substituted with an amino group) or C ₁ to ₂ alkyl group substituted Means an amino group] 0.01-1 parts by weight of the general formula (III) or (IV) with respect to the amine component consisting of at least one of the higher aliphatic amine compound and salts thereof and 1 part by weight of the amine component;

In the formula, each of R ⁶ -R ⁹ represents a lower alkyl group, and X represents -S-,-SS- or -S-Zn-S-.

[Wherein, R ¹¹ and R ¹² each represent a lower alkyl group, and Z represents a monovalent alkali metal or ammonium. Provided that at least one of the dialkyldithiocarbamic acid compounds represented by R ¹¹ and R ¹² may form a cyclic group at the mutual bond] as an active ingredient. Invention (1)] is provided.

Furthermore, according to the present invention, 0.01-1 part by weight of general formula (III) or 1 part by weight of the amine component and one part of the amine component of the general formula (I), or the general formula (II) or their salts, Preventing the adhesion of hydrolyzed elegance by adding at least one of the dialkyldithiocarbamic acid compounds of (IV) to the seawater channel and preventing or inhibiting the adhesion of the hydrolyzed elegance in the seawater channel. [Invention (2)] is provided.

The anti-adhesion agent according to the invention (1) achieves its purpose by generating a small amount of the hydride elegance larvae or afterwards by joining a small amount in the seawater cooling system.

In the inventions (1) and (2), as the higher aliphatic amine compound represented by the general formula (I), dodecylamine, tetradecylamine, nucleodecylamine, oxadedecylamine, oleylamine, ujialkylamine and palm alkyl Primary amines such as amines: secondary amines such as dodecylmethylamine, hexadecylmethylamine, octadecylmethylamine, ujialkylmethylamine, cured ujialkylmethylamine and palm alkylmethylamine; Tertiary amines such as dodecyl dimethyl amine, hexadecyl dimethyl amine, octadecyl dimethyl amine, palm alkyl dimethyl amine, uji alkyl dimethyl amine and hardened uji alkyl dimethyl amine; N-monosubstituted ethyledamines, such as dodecylethylenediamine, hexadecylethyleneamine, octadecylethylenediamine, oleylethylenediamine, and ujialkylethylenediamine: dodecyltrimethylenediamine, hexadecyltrimethylenediamine, octadecyltrimethylene N-monosubstituted trimethylenediamine, such as a diamine, an oleyl trimethylene diamine, a palm alkyl trimethylene diamine, a uji alkyl trimethylene diamine, and a hardened | denatured trimester alkyl trimethylene, etc. are mentioned.

Palm alkyl in these amines; … Amine Ujialkyl… … Amine Cured Wood Alkyl ... … In the above-mentioned (III, IV), in which the amine is produced by palm oil or palm oil, Uji, and the like widely known, R ¹ is a saturated or unsaturated hard chain of 12 to 18 carbon atoms. It is meant that the aliphatic hydrocarbon group is a mixture of amines (mixed alkylamines) occupying its main components.

Moreover, as a specific example of the higher aliphatic amine compound represented by general formula (II), N, N- dimethyl- (beta) -hydroxy- dodecylamine, N, N-dimethyl- (beta) -hydroxy- hexadecylamine, N, N Dimethyl-β-hydroxy-octadecylamine, N, N-dimethyl- β-hydroxy-eicosylamine, N, N-dimethyl-β-hydroxy-triacacylamine, N, Ndimethyl-β-hydr Hydroxy-eicosyleneamine, β-hydroxydodecylamine, β-hydroxy-tetradecylamine, β-hydroxyhexadecylamine, N, N-diethyl-β-hydroxyhexadecylamine, β-hydroxy -Hexadecylethylenediamine, (beta) -hydroxy-octadecylethylenediamine, etc. are mentioned.

When using these higher aliphatic amine compounds represented by general formula (I) or (II) together with dialkyldithiocarbamic acid compounds and using them in seawater channels such as seawater cooling water, Preferably, the addition salt with the inorganic acid or organic acid of the compound of General formula (I) and (II) which were mentioned above can be mentioned.

Specific examples thereof include addition salts such as hydrochloric acid, nitric acid, nitrous acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, butyric acid, oleic acid, naphthenic acid, adipic acid, lactic acid, or citric acid.

As the dialkyldithiocarbamic acid compound represented by the following general formula (III), zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc diisopropyldithiocarbamate and diphthyldithio Zinc carbamate, tetramethylthiuram disulfide, tetraisopropylthiuram disulfide, tetra-η-propylthiuram disulfide, tetra-η-butylthiuram disulfide, tetramethylthiuram monosulfide, tetraethylthiuram monosulfide, etc. Among these, tetraeryldiuram disulfide is most preferred in the formulation of the formulation, solubility in solvents, and weakly effective phase.

As the dialkyldithiocarbamic acid compound represented by the following general formula (IV), sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, N-piperidine Sodium dithioate, sodium N-fulolidinedithiroate, and the like, and their potassium salts, ammonium salts, and the like may be mentioned instead of the above sodium salts.

The blending ratio of the higher aliphatic amine compound represented by the general formula (I) or (II) and the dialkyldithiocarbamic acid compound represented by the general formula (III) or the general formula (IV) in order to exhibit a sufficient synergistic effect It is suitable to mix | blend the higher aliphatic amine compound 1 (weight part) in the ratio of the dialkyl dithiocarbamic acid compound 0.01-1 (weight part), and 0.1-0,8 (weight part) is more preferable.

In general, the amount of the antifouling agent added to the seawater cooling system may be injected in a total amount of the active ingredient in the amount of 0.1 ppm to 1-24 hours per day relative to the seawater flow rate.

The amount of addition is slightly increased or decreased depending on the situation of the sea area, but when the amount of generation of hydroid elegance is particularly large, it is preferable to be 0.005 ppm or more.

In any situation, however, an amount of up to 0.1 ppm is sufficient and more is economically undesirable.

In addition, in the case of adding the compound of the present invention of the seawater cooling system, a predetermined amount of each compound is added individually, or a suitable solvent (water or alcohol, isetone, xylene, dimethylformamide, methyl In an organic solvent such as cellsolve) or by emulsifying and adding a surfactant, if necessary, can be used as a formulation of a suitable concentration.

Examples of the surfactant at this time include higher fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene polyoxypropylene interpolymers, alkyltrimethylammonium alkyl betaines, and the like. have.

Further, according to the findings of the present inventors, the higher aliphatic amine compound represented by the general formula (II) (β-hydroxy higher alkyl amine), the dialkyldithiocatbamic acid compound represented by the general formula (IV), Specific water-glycol-based agents have been found as one preferred aqueous formulation containing.

Such a preparation is a water-glycol mixed solvent comprising the compound of formula (II) and the compound of formula (IV):

General formula (Ⅶ): R ₁₀ -O (CH ₂ CH ₂ O) nH

A glycol-based organic solvent 1 composed of 50-100% by weight of a glycol compound represented by R ₁₀ is an alkyl group η having a carbon number of 4 represents 1 or 2 and 50-0% by weight of a water-soluble glycol compound of this benefit. It is prepared by dissolving in a water-glycol-based mixed solvent in which 0.8-4.5 parts by weight of water is blended with respect to parts by weight, and based on 1 part by weight of the total amount of the compound of formula (II) and the compound of formula (IV) It is an aqueous formulation in which the combined amount of the glycol-based compound of formula is 0.4 part by weight or more.

Since such aqueous preparations are water-based liquid preparations, they are not flammable and easy to handle, and are extremely stable preparations that can prevent the separation, separation and decomposition of compounds of general formula (II) or general formula (IV) over a long period of time. to be.

Thus, such aqueous preparations are particularly useful in practice.

Moreover, as a glycol type compound of the general formula in the said aqueous formulation, 2-butoxy ethanol (an alias, butyl vertical solvate) and 2- (2-butoxy ethoxy)-ethanol are suitable.

On the other hand, as another water-soluble glycol type compound which can be used in combination with the glyco type-compound of general formula (i), the following general formula (i):

R ₁₄ -CH ₂ CH ₂ OH (Ⅷ)

[Wherein, R ₁₄ is a carbon number of 1-3 or 5-6 alkoxy group, a phenoxy group, a benzyloxy group, a hydroxyl group, C ₁ ~ ₂ alkoxy, C ₁₄ alkyl or C ₁ - ₃ alkoxy, C ₁ - ₃ alkoxy Represents a group] is appropriate.

Specific examples thereof include 2-methoxy-ethanol: CH ₃ O- (CH ₂ CH ₂ O) H, 2-ethoxy-ethanol: C ₂ H ₅ O- (CH ₂ CH ₂ O) H, 2-methoxy Methoxy-ethanol: CH ₃ OCH ₂ O- (CH ₂ CH ₂ O) H, 2-isopropoxy-ethanol: (CH ₃ ) ₂ CHO- (CH ₂ CH ₂ O) H, 2-isopentyloxy- Ethanol: (CH ₃ ) ₂ CHCH ₂ CH ₂ O- (CH ₂ CH ₂ O) H, 2-phenoxy-ethanol: C ₆ H ₅ O- (CH ₂ CH ₂ O) H, 2-hexyloxy- Ethanol: C ₆ H ₁₃ O (CH ₂ CH ₂ O) H, 2-benzyloxy-ethanol: C ₆ H ₅ -CH ₂ O- (CH ₂ CH ₂ 0) H, Diethylene glycol: HO- (CH ₂ CH ₂ O) H, 2- (2-methoxyethoxy) -ethanol: CH ₃ O- (CH ₂ CH ₂ O) ₂ H, 2- (2-ethoxyethoxy) -ethanol: C ₂ H ₅ O (CH ₂ CH ₂ O) ₂ H, 3-methyl-3-methoxy-butanol: CH ₃ OC (CH ₃ ) ₂ CH ₂ CH ₂ OH, methoxy-butanol: CH ₃ CH (OCH ₃ )-( CH ₂ CH ₂ O) H, and the like.

In addition, the amount of confluence in the formulations of the compounds of the general formulas (II) and (IV) may be any amount that can be dissolved, but preferably 5-30% by weight, respectively, 5-25% by weight of the former and 10% of the latter. It is preferable to set it as -30 weight%.

In addition, it is preferable to set the liquidity of the formulation to pH9.0 or more, particularly pH 9.5-13.0, from the viewpoint of improving the stability of the formulation, and this liquid can be optionally added by adding a suitable alkali agent. Thus, even in such an aqueous preparation, a small amount of a suitable surfactant, in particular a nonionic surfactant or another water-soluble organic solvent, may be added.

On the other hand, the active ingredient of the present invention may be used in the form of a liquid composition for preventing adhesion of hydrolyzed elegance, such as a suitable membrane composition resin solvent.

As such a film-forming resin, various things can be applied including those widely known.

According to the invention of the present inventors, it is found that by combining a specific polymer having a free carboxyl group, it is possible to obtain a coating composition which can be maintained in the form of a salt of an amine component and effectively realize a long-term synergistic effect of the active ingredient. did.

Thus, according to the present invention general formula (V)

In the formula, Y represents a hydrogen atom or a methyl group, at least one 5-50% by weight of a monobasic polymerizable unsaturated carboxylic acid of general formula (VI)

Interpolymers with at least 95-50% by weight of a hydrophobic polymerizable unsaturated compound represented by [wherein Y represents a hydrogen atom or a methyl group, R ¹³ represents an alkyl group, benzyl group, or cyclohexyl group having 1 to 18 carbon atoms] And from 0.01 to 1 part by weight of the amine component having one or more of 0.3 equivalents of the general formula (I) or II per 1 equivalent of the carboxyl group in the carboxylic acid and 1 part by weight of the amine component (III) or (IV). Provided is a hydrolyzed elegance anti-adhesion agent [Invention (3)] comprising at least one of dialkyldithiocarbamic acid compounds.

In addition, a method of preventing hydrophilic elegance (Invention 4) by applying and adhering this antifouling agent to an object such as a fishing net or a marine structure is provided.

As monobasic polymerizable unsaturated carboxylic acid represented by General formula (V) used here, it is preferable to use 1 or more types of acrylic acid and methacrylic acid.

Next, as the hydrophobic polymerizable unsaturated compound represented by the general formula (VI), for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octymethacrylate, lauryl methacrylate and stearyl methacrylate. And acrylic acid derivatives such as acrylate, benzyl methacrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, oleyl acrylate, cyclohexyl acrylate and the like.

You may use 2 or more types of such hydrophobic polymerizable unsaturated compounds.

Among these, (meth) acrylic acid esters are C _1-3 alkyl esters or C ₉ or more alkyls in the same manner as C _4-8 alkyl esters of (meth) acrylic acid, in view of the strength and flexibility of the antifouling film formed. Preference is given to combining with esters.

Although the molecular weight of the hydrophilic interpolymer can be changed by the combination of monomer units, etc., the molecular weight is not particularly limited, but the molecular weight is about 10,000-100,000, particularly 30,000-6, in terms of strength or film composition of the coating film. Only about 10,000 are preferable.

Preparation of such interpolymers can be easily prepared by radical polymerization using radical generators such as benzoyl peroxide, t-buty peroxide, asobisisobutyronitrile and asobisisophthalonitrile as polymerization initiators. have.

At this time, suitable solvents include alcohols, aromatic solvents, naphtha, butyl acetate, longitudinal solver, and the like. The polymerization temperature is preferably about 70-90 ° C., and the polymerization time is about 2-12 hours. .

Here, the hybridization ratio between the polymerizable unsaturated carboxylic acid (A) and the hydrophobic polymerizable unsaturated compound (B) is 5-50% by weight of component (A) in the obtained copolymer (that is, component (B) is 95- 50 weight%] is suitable, and it is preferable to make (A) component 10-40 weight%.

Here, if the content of the component (A) is less than 5% by weight, the hydrophilicity of the interpolymer itself is poor in seawater, the release property of the antifouling active ingredient is lowered, and a long term antifouling effect cannot be obtained. When it exceeds weight%, it is not suitable because the hydrophilicity is so large that the antifouling film dissolves in seawater in a short time and cannot hold controllability of release of the active ingredient to seawater.

The anti-adhesion agent of the invention (3) is obtained by mixing and preparing a monobasic interpolymer and a higher aliphatic amine compound in a solvent, and then adding and preparing a dialkyldithiocarbamic acid compound.

Such a mixing aid is first prepared by adding a higher aliphatic amine compound to the solution in which the interpolymer is initially prepared, followed by mixing and stirring to sufficiently generate an amine salt of carboxylic acid in the interpolymer, followed by adding and stirring a dialkyldithiocarbamic acid compound. It can manufacture.

The solution temperature for mixing the monobasic interpolymer and the higher aliphatic amine compound is preferably about 20-60 ° C., and the stirring time is about 0.5-2 hours.

Next, the solution temperature at the time of adding a dialkyldithiocarbamic acid compound is suitably set to about 20-40 degreeC, and the stirring time is suitable about 0.5-2 hours.

At this time, the weight of the higher aliphatic amine compound added to the monobasic interpolymer is preferably 0.3 equivalent or more, particularly 0.8 equivalent or more, relative to 1 equivalent of the carboxylic acid group of the interpolymer.

If the amount is less than 0.3 equivalent, the elution amount of the higher aliphatic amine compound and the dialkyldithiocarbamic acid compound is too small, and the antifouling action is not effectively exerted.

In this case, even if the equivalent weight is exceeded, there is no particular problem, but if it is excessive, the density of the film-forming component in the antifouling film formed becomes low, so that the strength of the film is weak, the film melts easily in a short period of time, and is easily broken. Since anti-fouling effects cannot be expected, addition of more than 1.5 equivalents is not desirable in consideration of economical efficiency.

The weight of the dialkyldithiocarbamic acid compound to be blended into the higher aliphatic amine-containing interpolymer is determined based on the dialkyldithiocarbamic acid compound with respect to the amine component 1 (parts by weight) blended in the interpolymer as described above. It is preferable to mix | blend in the ratio of 0.01-1 (weight part).

If the dialkyldithiocarbamic acid compound to be blended is 0.01 or less, the effect of preventing adhesion to the hydrophilic elegance is insufficient, and when an amount of 1 (part by weight) or more is added, the adhesion of the coating agent to the culture network becomes poor, Can not stand for practical use, such as falling off by the power of.

Therefore, the compounding ratio of the invention (3) controls the formation of the forming coating film and the seawater elution which constitute the coating composition, and also the release and elution of the higher aliphatic amine compound and the dialkyldithiocarbamic acid compound. It is regulated to have a long-term stable pollution prevention effect.

The antifouling agent of such invention (3) is a liquid form normally.

At this time, the organic solvent used may include methanol, ethanol, xylene, toluene, cyclohexa, kerosene, methyl isobutyl ketone, butyl acetate, dimethylformamide, dimethyl sulfoxide, naphtha, methyl cellsolve, etc. Various solvents used in the field of can be used, and even if a little water is included, it does not interfere. Here, it is preferable that the liquid type antifouling agent dissolved or dispersed in the organic solvent solution is 25-60% by weight in terms of the film composition, film composition strength and the like.

On the other hand, this anti-sticking agent may be prepared as an antifouling paint in the form of an organic solvent solution or a dispersion liquid like other coating film forming aids. Here, as a coating film formation aid, a pigment or a coloring agent such as talc, titanium bag, sulfur lead, eavesdropping, red iron oxide, phthalocyanine blue, tributyl phosphate, trioctyl phosphate, tricre phosphate, dibutyl phthalate, dioctyl phthalate and dioctal Plasticizers and dispersants such as butyl maleate, polyoxyethylene alkyl ethers, polyoxyethylene, polyoxypropylene hybrid polymers, sorbitan alkyl esters, alkyltrimethylammonium salts and alkyl betaines that do not inhibit the release of the active ingredient Other natural resins, synthetic resins, and the like.

Such antifouling coating type anti-sticking agents include a compound containing a dialkyldithiocarbamic acid compound in the above-mentioned higher aliphatic amine-containing interpolymer, and a total amount of about 10-50% by weight and other coating film forming aids. It is suitable that it is prepared by weight%. This antifouling agent is useful as an antifouling paint for various seawater-based structures, and is most suitable to be applied by brush coating, spraying or the like.

In this way, the antifouling agent of the present invention applied to the antifouling object forms a antifouling film by drying, and exhibits a long-term antifouling effect.

[Examples and Comparative Examples]

Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited compared with this.

Example 1-6 and Comparative Example 1-6

Seawater is pumped from the seawater channel of the parent chemical plant with many obstacles caused by Hydroid's elegance, and the test equipment is placed in a vinyl chloride pipe with an inner diameter of 100 mm and a length of 2 m. Seawater was passed through for 40 days (water flow rate, 3 tons / hour), and each drug was injected with K-Cal pump, and hydrolyzed elegance and other adherent organisms attached to the test network at that time were examined.

Moreover, two chemical | medical agent injection sites were provided in the channel of Example 1-5 which investigates the synergism of chemical | medical agent, and each chemical | medical agent injection pump was inject | poured.

Preparation of the chemical liquid was performed by the following method.

The dialkyldithiocarbamic acid compound was dissolved in dimethylformamide, polyoxyethylene sorbitan monooleate (HLB, 15) was added as an emulsifier to form an emulsion, emulsified with water, and a predetermined amount was injected.

Next, the higher aliphatic amine compound was made into a solvent type and a water-soluble type. The solvent type was dissolved in alcohol, added polyoxyethylene sorbitan monooleate (HLB, 15) to form an oil material, emulsified with water, and a predetermined amount was injected.

The aqueous type was reacted with a higher aliphatic amine with hydrochloric acid or acetic acid, and then diluted with water to inject a predetermined amount. And in Example 6, one liquid formulation of the following chemical | medical agent was prepared and inject | poured into the said channel.

N-N-dimethyl stearylamine: 5 parts by weight

Tetraethylthiuram disulfide: 5 parts by weight

Polyoxy ethylene sorbitan monooleate (HLB, 15): 10 parts by weight

Isopropyl alcohol: 40 parts by weight

Xylene: 40 parts by weight

The channel test results for the Hydroid Elegance are shown in Table 1.

Consideration of waterway test

From the above test results, when dialkyldithiocarbamic acid is used in combination with a higher aliphatic amine compound, it can be seen that there is a synergistic effect on the prevention of adhesion of hydrolyzed elegance. (See Example 1-6)

In comparison with this, the higher aliphatic amine compound or the dialkyldithiocarbamic acid compound alone had no effect on the hydrolysis elegance. (See Comparative Example 1-4).

In addition, other compounds known as antifouling agents had no effect on hydroid elegance. (See Comparative Example 5).

Preparation Example 1-7

Into a 500 ml separable flask equipped with a cooler, a thermometer and a stirrer, 36 g of acrylic acid, 100 g of methyl methacrylate, 24 g of octyl acrylate, 2 g of benzoyl peroxide as an initiator, 80 g of isopropyl alcohol, and 160 g of xylene were replaced with nitrogen, The mixture was kept at 78-82 ° C. in water jade while stirring and polymerized for 10 hours.

Next, 4 g of dibutyl hydroxy toluene was added to terminate the polymerization.

The temperature of the contents was cooled to 20 ° C., and then taken out to obtain an average molecular weight. This was made into the polymer (A).

Hereinafter, the other component was superposed | polymerized in the compounding quantity similar to the above in the ratio shown to each component of 2nd table | surface in 2nd table | surface in the same way, and obtained polymer (B)-(G)-.

Next, 100 g of the polymer (A) was added to 500 ml of a detachable flask equipped with a cooler, a thermometer, and a stirrer, 29.7 g of dimethyl stearylamine was added, and the mixture was stirred at 40 ° C. for 2 hours to increase the temperature in the flask at 20 ° C. After cooling, tetraethylthiuram disulfide 1.5g was added, 100g of xylene was added while stirring, and it stirred for 1 hour, and the preparation example 1 was obtained.

Hereinafter, the formulation example 2-7 was obtained using the polymer (B)-(G) shown in the 2nd table using the same apparatus.

Formulation Examples 8-13, Formulation Comparative Example 1-7 Polymerization and Formulation The same apparatus and conditions as in Example 1, 32 g of acrylic acid, 20 g of methyl methacrylate, 80 g of octyl acrylate, 28 g of benzyl methacrylate, and N, N as an initiator -1 g of azobis isobutyronitrile, 80 g of isopropyl alcohol, and 160 g of xylene were added and polymerized.

After the end of the polymerization, 2 g of hydroquinone monomethyl ether was added to terminate the polymerization.

After cooling, the contents were taken out and the average molecular weight was measured.

This was made into the polymer (H).

Hereinafter, in the same manner, each component of the second table is polymerized in the analogy shown in the second table, and the other components are polymerized in the above-described compounding amounts to polymerize (I)-(M) and the polymer (N)-(Q) of the comparative example. Got.

Next, 100 g of the polymer (H) was added to a 500 ml detachable flask equipped with a cooler, a thermometer, and a stirrer, and 36.3 g of dimethyl stearylamine was added and stirred for 2 hours. Then, 10.9 g of tetrabutylthiuram disulfide was added, After stirring, 100 g of xylene was added, followed by stirring for 1 hour to obtain Formulation Example 8.

Next, the antifouling agent examples 9-13 and 1-7 were obtained by the apparatus and method similar to the formulation example 1.

[Test Example 1] (fish net pollution inhibitor, immersion test)

Formulation Examples 1-13, Formulation Comparative Example 1-8 and the dialkyl dithio carbamic acid compound were formulated in a proportion of the amounts shown in Table 2 by using the usual oil-soluble resins in the components shown in Table 2. The formulations of Examples 8-11 were obtained and the respective antifouling effects were compared.

Immersion Test Method

As a test network, it was performed using a culture network made of polyethylene (100 pieces, every 4, 50 cm x 60 cm).

The test network was immersed in each antifouling agent, and the antifouling agent was attached to the net. After drying for 3 days, the adhesion rate of the active ingredient was calculated, and then the adhesion to the net and the hardening were examined.

Thus, during the three months of May-July, the rafts in Koishura Bay, Mijushun, Japan, were tied down to the depths of 1.0m-1.5m below sea level, regularly monitoring the anti-pollution effect of Hydroids Elegance.

These results are shown in Table 3.

(Note) The meaning of each symbol in the table is as follows.

-: No attachment of Hydroid Elegance

±: No problem in practical use to the extent that hydrolyzed elegance is slightly attached

+: Hydrophilic elegance adheres and cannot withstand use already.

+ +: Hydrolyzed elegance is remarkably attached.

Consideration of Immersion Test

From the above test results, it was found that the antifouling agent of the present invention obtained by mixing dialkyl dithiocarbamic acid in a higher aliphatic amine-containing interpolymer was exhibited an antifouling effect over a period of 3 months or more with respect to hydrolyzed elegance. Can be. (See Preparation Example 1-13)

In comparison, the higher aliphatic amine-containing interpolymers alone did not have a long-term antifouling effect on the hydrophilic elegance (see Comparative Example 1-4). Also, with respect to the higher aliphatic amine compound 1 (part by weight) in the higher aliphatic amine-containing interpolymer, the compounding ratio of 0.008 (part by weight) of the dialkyldithiocarbamic acid compound had no effect on the hydrolysis elegance (Comparative Example 5 Reference).

On the other hand, when the dialkyl dithio carbamic acid compound is excessively 2 (parts by weight), the adhesion to the net becomes worse, and it falls off during immersion and has no effect (see Comparative Example 6).

In addition, there was no effect on hydroid elegance even when other antifouling agents were added to the polymer used in the present invention (see Comparative Example 7).

Next, it was found that the dialkyl dithiocarbamic acid compound represented by the general formula (VIII) did not exert an antifouling effect only by mixing with ordinary oil-soluble resins (see Comparative Example 8-11).

Polymer composition in the table

AA: acrylic acid

MA: Methacrylic Acid

MMA: Methyl Methacrylate

EHA: Octyl acrylate

BMA: benzyl methacrylate

DA: Dodecyl acrylate

BA: Butyl acrylate

OMA: octyl methacrylate

DMA: dodecyl methacrylate

Higher aliphatic amine compounds

DMSA: N, N-dimethyl-stearyl amine

DMA: dodecyl methylamine

DMβDHA: N, N-dimethyl-βhydroxydodecyl amine

CA: Cetyl Amine

SDEDA: Stearyl Diethylene Diamine

DEβHHDA N, N-diethyl-βhydroxy-hexadecylamine

SA: Stearyl Amine

βHHDA: βhydroxy-hexadecyl amine

TMDA: Uzaalkyl Trimethylene Diamine

Dialkyl Dithiocarbamic Acid Compounds

TETD: Detraethyl uriram disulfide

DBDTCZn: Dibutyl Dithio Carbamate

TiPTDS: Tetraisopropyl Thiuram Disulfide

TMTDS: Tetramethyl Thiuram Disulfide

TBTDS: Tetramethyl Thiuram Disulfide

DEDTCZn: Zinc Diethyl Dithiocarbamate

TMTMS: Tetramethyl Thiuram Mono Sulfide

DMDTCZn: Zinc Dimethyl Dithio Carbamic Acid

DiPDTCZn: Diisopropyl Dithiocarbamate Zinc Others

TCMTB: thiocyano methylthiobenzothiazole.

(Note) *: The coating film is peeled off.

Using Polymers (A), (B), (D), (G), (I) and (M) synthesized in Formulation Examples 14-19, Formulation Comparative Example 13-18 and Formulation Examples 1-13, Preparations The pollution prevention chart of Examples 14-19 was prepared. Moreover, the pollution prevention chart of the formulation comparative examples 13-17 was prepared using polymer (N), (O), (P).

As a preparation method, reaction of a polymer and a higher aliphatic amine compound was performed using the apparatus similar to what was used in the preparation example 1.

Namely, 100 g of the polymer (A) and 29.7 g of dimethyl stearylamine were added, the mixture was stirred at 40 ° C. for 2 hours, the temperature in the flask was cooled to 20 ° C., and 49.5 g of the content thereof (40 g of polymer (A), dimethyl). 9.5 g of stearylamine] was placed in a 300 ml bowl mill and the raw materials shown in the fourth table were added sequentially, followed by rotation for 24 hours to obtain Formulation Example 14.

Formulation Examples 15-19 and Comparative Example 13-17 were obtained at the blending ratios shown in Table 4 in the same manner as below.

In addition, Formulation Comparative Example 18 was obtained by putting a predetermined amount of raw materials in the same bowl mill and rotating the same time.

Test Example 2 (Anti-fouling paint, chart test)

Formulation Examples 14-19 and Formulation Comparative Examples 13-18 were used to compare the respective antifouling effects.

Dipping method of paint

Formulation Examples 14-19 and Formulation Comparative Examples 13-18 were plotted twice on individual 7 cm x 20 cm hard vinyl chloride plates so that the coating amount was 1.5-2.0 kg / cm < 2 >.

Thus, the anti-pollution effect on the Hydroid Elegance was regularly observed, tied to a depth of 1.5-2.0m below the sea level from the raft within the Japanese Miju-chan Koishura Bay for one year from May.

The results are shown in Table 5.

(Note) The number in a table | surface shows the adhesion area percent of hydrolysis elegance.

Consideration of Immersion Test

From the above test results, the antifouling agent of the present invention obtained by mixing a dialkylditido carbamic acid compound with a higher aliphatic amine-containing interpolymer exhibits an antifouling effect over a period of 9 months or more with respect to hydrolyzed elegance. It can be seen that (see 14-19 of the formulation example)

In contrast, only the higher aliphatic amine-containing interpolymers had no long-term antifouling effect on hydrolyzed elegance (see Formulation Comparative Example 13-15).

In addition, with respect to the higher aliphatic amine compound 1 (part by weight) in the higher aliphatic amine-containing interpolymer, as a blending ratio of 0.008 (part by weight) of the dialkyl dithiocarbamic acid compound, there was no effect on the hydrolysis elegance (preparation agent) See Comparative Example 16).

In addition, even if other antifouling agent components were blended into the polymer used in the present invention, there was no effect on hydrolyzed elegance (see Formulation Comparative Example 17).

Next, it was found that the antifouling agent which mixed only the dialkyl dithio carminic acid compound represented by the general formula with ordinary oil-soluble resins did not exhibit sufficient antifouling effect against Hydroid Elegance. (See Preparation Comparative Example 18.)

High aliphatic amine compound in table

DMSA: N, N-dimethylstearylamine

DMA: dodecylmethylamine

DEβHHDA: N, N-diethyl-hydroxy-hexadecylamine

βHHDA: be-hydroxy-hexadecylamine

SA: Stearylamine

βHDA: β-hydroxy-dodecylamine

Dialkyldithio Carbamic Acid Compounds

TETDS: Tetraethylthiuram disulfide

DBDTCZn: Dibutyl dithiocarbamate zinc

TMTMS: Tetramethylthiuram monosulfide

TBTDS: Tetramethylthiuram disulfide

DMDTCZn: Tetrabutylthiuram disulfide

DMDTCZn: Diketylenedithiocarbamate Zinc and others

TCMTB: Thiocyanomethyl

Thiobenzothiazole

[Test Example 2]

A compound of the general formula (IV) [active ingredient (a)] and a compound of the general formula (III). [Aqueous ingredient (b)], a glycol solvent of general formula and general formula is used, and optionally, surfactant is added or PH is adjusted. Prepared.

Therefore, in order to investigate the stability of each aqueous preparation, it was left to stand in a water bath at 20 ° C. and 40 ° C. for 24 hours to investigate whether liquid separation or the like occurred. It was examined whether or not precipitation occurred. And the storage stability at the time of leaving for 3 months indoors and the emulsion stability (24 hours) of 1 weight% water lime liquid were also evaluated.

This result is shown in Table 6 with a composition.

Thus, it can be seen that the aqueous formulation of Test Nos. 1 to 18 is extremely high in stability.

Example 7

Next, mainly experiments to investigate the effect of the modified agent of the present invention on fouling organisms were conducted by the following method. At first, in the summer (July-August) when there are many generations of foul organisms and hydroids elegance, and red tide occurs, we sprinkle seawater with an underwater pump from the seawater tap water of the parent chemical plant, and the inner diameter is 100mm, chloride of 2m in length Using a test equipment with a test pipe in a vinyl pipe, seawater was passed through a daily diet (3 tons / hour for each water flow rate) to an attachment such as Heidle's Elegance, and each chemical prepared in Test Example 2 was transferred to a chemical pump. It injected | poured and investigated the hydroid elegance and other fouling organisms which were attached at that time.

The results are shown in Table 7 together with the comparative examples.

These test results show that the liquid preparations of Experiment Nos. 1 to 18 exhibit excellent storage stability and sufficiently inhibit fouling organisms such as hydroid elegance.

As described above, according to the anti-adhesion agent and the anti-adhesion method of the present invention, the amine component and the dialkyldithio group are attached to various members, fishing nets, underwater structures, bottoms of ships, etc., which have been difficult to prevent. The synergistic effect with a garbamic acid compound can effectively prevent or suppress it.

Claims (4)

The following general formula [I] or [II]:

[Wherein R 'is a saturated or unsaturated straight-chain aliphatic hydrocarbon group having 12-18 carbon atoms, R ² is a hydrogen atom or a methyl group, R ³ is a hydrogen atom, a methyl group,-(CH ₂ ) ₂ -NH ₂ or-( CH ₂ ) is a group represented by ₃ -NH ₂ , provided that when R ² is a methyl group, R ³ means a methyl group.

[Wherein, R ⁴ denotes an alkyl group having 10-28 carbon atoms and, R ⁵ is an amino group, a C ₁ - ₂ alkyl group substituted by an amino group, (where these alkyl groups may be substituted with an amino group) or di-C ₁ - ₁₂ alkyl group-substituted amino group], 0.01-1 part by weight of the general formula (III) or (IV) based on the amine component comprising one or more of the higher aliphatic amine compound and salts thereof;

[Wherein, R ⁶ -R ⁹ each represent a lower alkyl group, and X represents -S-, -SS- or -S-Zn-S-.

[Wherein, R and R ¹² each represent a lower alkyl group Z is a monovalent alkali metal or ammonium. However, R and R ¹² may be bonded to each other to form a cyclic group.] An antiadhesive agent for hydrolyzed elegance comprising at least one of dialkyl dithiocarbamic acid compounds represented by . General formula (I) or (II)

[Wherein R 'is a saturated or unsaturated straight chain aliphatic hydrocarbon group of hydrocarbon 12-18, R ² is hydrogen atom or methyl group, R ³ is hydrogen atom, methyl group,-(CH ₂ ) ₂ -NH ₂ or-) CH ₂ ) is a group represented by ₃ -NH ₂ , provided that when R ² is a methyl group, R ³ means a methyl group.]

Represented by - [wherein R ⁴ stands for an alkyl group having 10-28 carbon atoms and, R ⁵ is an amino group (provided that these alkyl groups may be substituted with an amino group) or di-C _{1 2} alkyl group means a substituted amino group; An amine component comprising one or more of the higher aliphatic amine compounds and salts thereof, and 0.01-1 parts by weight of the general formula (III) or (IV) to

[Wherein, R ⁶ -R ⁹ each represent a lower alkyl group, and X represents -S-, -SS- or -S-Zn-S-. ]

[Wherein R ¹¹ and R ¹² each represents a lower alkyl group Z is a monovalent alkali metal or ammonium. Provided that at least one of the dialkyl dithiocarbamic acid compounds represented by R ¹¹ and R ¹² may be bonded to each other to form a cyclic group to the seawater channel, and the hydroid elegance in the channel. Method of preventing the attachment of hydrolyzed elegance, characterized in that the attachment and prevention or suppression of. General formula

In the formula, Y represents a hydrogen atom or a methyl group, 5-50% by weight of one or more kinds of the monobasic polymerizable unsaturated carboxylic acid, and general formula (IV):

[Wherein, Y represents a hydrogen atom or a methyl group and R ¹³ represents an alkyl group, benzyl group or cyclohexyl group having 1 to 18 carbon atoms. 0.3 or more equivalents of the general formula (I) or (II) per 1 equivalent of carboxyl groups in the said carboxylic acid, and the interpolymer with at least 90-50 weight% of hydrophobic polymerizable unsaturated compounds represented by]:

[Wherein R ¹ is a saturated or unsaturated straight chain aliphatic hydrocarbon group having 12-18 carbon atoms, R ² is a hydrogen atom or a methyl group, R ³ is a hydrogen atom, a methyl group-(CH ₂ ) ₂ -NH ₂ or-(CH ₂ ) a group represented by ₃ -NH ₂ , provided that when R ² is a methyl group, R ³ means a methyl group.

[Wherein, R ⁴ represents an alkyl group having 10 to 28 carbon atoms, R ⁵ represents an amino group, a C _1-2 alkyl substituted amino group (however, these alkyl groups may be substituted with an amino group) or di C _1-2. Means an amino group substituted amino group] 0.01-1 parts by weight of the general formula (III) or (IV) based on one or more amine components of the higher aliphatic amine compound represented by the above-mentioned amine component.

[Wherein R ⁶ -R ⁹ each represent a lower alkyl group, and X represents -S-, -SS- or -S-Zn-S-]

[Wherein, R ¹¹ and R ¹² each represent a lower alkyl group, and Z represents a monovalent alkali metal or ammonium. Provided that at least one of the dialkyl dithiocarbamic acid compounds represented by R ¹¹ and R ¹² may be bonded to each other to form a cyclic group]. . An anti-adhesion method of claim 3, wherein the anti-adhesion agent according to claim 3 is applied or adhered to an object to be treated in contact with seawater, thereby preventing or inhibiting adhesion of the hydrolyzed elegance to the object.