JPS6141944B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an underwater object surface treatment composition for protecting the surface of objects under water from corrosion and contamination by organisms living in the sea. The present invention relates to an underwater object surface treatment composition used in a ship antifouling paint containing a polymer.

The ionene polymer means a polymer containing a nitrogen atom of a quaternary ammonium group, as defined by the general formula described below.

(Prior Art) Conventionally, the surfaces of objects under water are usually treated by applying multiple layers of paint coatings, and in order to prevent the growth of marine organisms,
Antifouling paint is usually applied as a top coat. Antifouling paints contain toxic substances such as copper oxide. Copper oxide gradually reacts with seawater to form water-soluble salts, which are leached from the paint film. This leaching action cannot be uniformly controlled, and leaching occurs undesirably quickly after the vessel is put into use or re-use, resulting in initially unnecessarily high concentrations. Toxic substances will be present around the ship's hull, causing wastage of the toxins and contamination of the water, and the concentration will then decrease, thereby increasing the growth of organisms living in the sea. Furthermore, the paint becomes rough over time due to toxic substances leaching out.
Marine life becomes very easily attached to the paint surface. The growth of the organism is inhibited until enough poison has oozed out, but this is not the case for long and the growth of the organism is promoted.

When marine organisms grow under these conditions, they usually have to be placed in a dry dock, scraped off, and then repainted, which is an expensive and time-consuming process. Alternatively, some improvement can be achieved by hosing high-pressure water or mechanically scrubbing. However, due to the porous nature of the paint, biological roots cannot be removed, so this improvement is only temporary.

(Problem to be Solved by the Invention) In the above-mentioned situation, ship owners are faced with problems such as whether their ships are docked and cannot be used for a short period of time, or frequently but not frequently. We are faced with a long-term choice problem.

Thus, there is a strong need and need to develop improved antifouling compositions that maintain antifouling properties for long periods of time.

(Means for Solving the Problems) The present inventors have now discovered that a novel ionene polymer exhibits good antifouling properties.

According to the present invention, an underwater object surface treatment composition for use as a marine antifouling coating comprises substantially water as a polyionene or as a film-formable ionene copolymer dissolved or dispersed in a film-formable base. a dihalide containing an insoluble ionene polymer, wherein the polyionene or ionene copolymer has an alkyl group or an alkenyl group each having 1 to 30 carbon atoms;
and a diamine having an alkyl group having 5 carbon atoms.

Polyionene is a polymer having positively charged nitrogen atoms in its main chain. These are the general formula It can be produced by reacting a diamine represented by the formula with a dihalide represented by the general formula halogen-R ¹ -halogen. In the formula, R, R ¹ and R ² may be the same,
or may be different, but the number of carbon atoms is 1 to
100, preferably 1 to 30 saturated or unsaturated hydrocarbyl groups, such as alkyl, alkenyl,
It is a cycloalkyl, cycloalkenyl or aryl group. The halogen is Br, Cl, I or F, preferably Br or Cl.

The basic structural unit of polyionene is It is.

The above compound is described as a polyionene in the strict sense. Ionene copolymers can be further cross-linked, either directly or through other active molecules, as described below.

Ionene polymers made of such polyionene and ionene copolymers are included within the scope of the present invention.

Polyionene can be produced by reacting a diamine and a dihalide in a solvent for the reactant at a temperature of 0 to 150°C. Suitable reaction temperatures are from 20 to 100°C, and suitable solvents are water, methanol, xylene, dimethylformamide and dimethylformamide/water mixtures. The reaction time is from 2 hours to several days. When the reaction is complete, the polymer is precipitated by adding a large excess of a non-solvent, such as a ketone. The molecular weight of the produced polyionene varies depending on the reaction temperature and reaction time, and the water solubility of polyionene is proportional to the molecular weight, which is proportional to the viscosity. Therefore, viscosity control is convenient for controlling the reaction to obtain a predetermined solubility, and the solubility is 0.4M KBr.
The solubility in solution at 25°C is the standard.

Although polyionene is an antifouling agent, it does not itself have strong film-forming properties. However, in the case of ionene copolymers, it is convenient to use ionene copolymers since they are the major film-forming components of the composition.

A preferred method for producing film-forming ionene copolymers is to produce polyionenes using diamines or dihalides having reactive groups, such as double bonds, hydroxyalkyl groups, or epoxyalkyl groups, and or by cross-linking this, mixed with other reactive molecules, with known amine curing agents used in the epoxy resin art.

It has been found that diamines and/or dihalides containing epoxy groups can be polymerized without interference of the epoxy groups. The epoxy group-containing component may be used in an amount of 5 to 100 mol%, preferably 30 to 70 mol%, of the reactant.

Furthermore, it has been found that polyionenes containing epoxy groups can be cross-linked with amine curing agents used in the conventional epoxy resin art without interference from the quaternary ammonium groups of the polymer. The amount of amine curing agent used depends on the proportion of epoxy groups in the polymer and follows known practices. Polyionenes containing epoxy groups may be mixed with other epoxy compounds before cross-linking. As mentioned above, the proportion of the epoxy group-containing component is 5 to 100 mol% of the reactant, preferably 30 to 100 mol%.
It is 70 mol%. An amine curing agent is added and then cured, the reaction generally proceeding at room temperature, thus yielding a ternary polymer, ie, an ionene copolymer.

The ionene copolymer corresponds to a copolymer of an epoxy resin and a polyionene and can be applied at ambient temperature by known methods, for example by brushing or spraying as an alcoholic solution. It is convenient to carry out the reaction for producing the ionene copolymer in an alcohol solvent to obtain an alcohol solution of the ionene copolymer, and directly use the solution as a coating solution.

In the case of polyionenes, the polyionenes are dispersed in known film-forming components, such as commonly used antifouling paint bases. Typical polyionene carriers include one or more of polyester, polyurethane, epoxy resin, epoxy coal tar resin, chlorinated rubber, polyvinyl compounds (polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, etc.), polyethylene, and polytetrafluoroethylene. Consists of. Preferably, the carrier is such that it can be applied to the surface of the object by brushing or spraying at ambient temperature and that it contains a conventional solvent for the film-forming component, such as white spirit or similar petroleum derivatives, It may also include a ketone solvent such as methyl isobutyl ketone, or an aromatic solvent such as toluene. The paint may contain a pigment, such as an aluminum silicate, and a drying agent, such as a cobalt or manganese naphthenate.

The present invention is characterized in that the long-term retention of the polyionene's antifouling properties is achieved using the polyionene in a porous conventional antifouling paint base.

The amount of polyionene used may range from 5% to 75% by weight of the final dry film, preferably from 10% to 75% by weight of the final dry film.
Use 50% by weight.

The polyionene is preferably substantially water-insoluble in order to prevent it from being eluted into seawater.
0.007 at 25°C in 0.4M KBr solution as standard
Solubility of Kg/ ^m3 or less, preferably 0.005
It is set to have a solubility of Kg/m ³ or less. Since water insolubility is proportional to molecular weight, and molecular weight is proportional to viscosity, therefore,
In preparing the polyionene, the reaction time and other conditions are set so that the viscosity and solubility are predetermined.

In addition to having anti-fouling properties, it is desirable for the surface of objects under water to have a smooth surface with a low coefficient of friction. It is especially desirable to have one.

(Function) The effectiveness of polyionene as an antifouling agent is believed to be due to the presence of positively charged nitrogen atoms in the main chain of the polymer. The antifouling effect is related to the polyionene content in the film, and the results of Examples 7 and 8 and Comparative Example 1 show that the antifouling effect does not improve even if the solubility of polyionene is increased more than necessary. .

(Effects of the Invention) By using the underwater object surface treatment composition containing the polyionene polymer according to the present invention, it is possible to maintain the antifouling properties of the ship's hull against marine organisms for a long period of time.

(Examples) Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples.

Example 1 195.2 g of 1,6-dibromohexane was added to a solution of 92.8 g of N,N, ^N1 , ^N1 tetramethylethylenediamine in 400 ml of dimethylformamide/ _H2O (4:1) mixed solvent for 45 minutes. It was added dropwise over a period of time.
The reaction mixture was stirred at 20 °C for 24 h and then poured into a large excess of vigorously stirred acetone.
The precipitated polyionene was filtered and placed in a vacuum.
Dry at 60°C (yield 232g). Polymer is 0.4M
It had a solubility of 0.005 Kg/m ³ in KBr and was virtually insoluble in water.

Example 2 24.4 g (0.1 mol) of 1,6-dibromohexane in 25 ml of methanol
The solution was added dropwise to a solution of 11.6 g (0.1 mol) of N, N, N ¹ , N ¹ tetramethylethylenediamine with stirring. The reaction mixture was stirred at 20° C. for 150 hours and then poured into a large excess of vigorously stirred acetone. The precipitated polyionene was filtered and dried in vacuo at 60°C (yield 32
g). The polymer had a solubility of 0.003 Kg/m ³ in 0.4 M KBr and was essentially water insoluble.

Example 3 125g of 1,4-dichlorobutene-2 was added to 250ml
was added dropwise over a period of 45 minutes to a solution of 116 g of N,N,N ¹ ,N ¹ tetramethylethylenediamine in a dimethylformamide/H ₂ O (4:1) mixed solvent. After the reaction was allowed to run for 24 hours at 20°C, the reaction mixture was poured into a large excess of acetone. The precipitated polyionene was filtered and then dried (yield 200
g). The solubility of polyionene in 0.4M KBr was 0.007 Kg/m ³ and it was substantially water-insoluble.

Example 4 7.2 g of 1,4-dichloro-2,3-epoxybutane in 12.5 ml of xylene was added to 5.8 g of N,N,N ¹ ,N ¹ tetramethylethylenediamine in 12.5 ml of xylene over 15 minutes. It was added dropwise. 25℃
The mixture was reacted for 3 hours at 60 to 70°C, and further reacted for 3 hours at 60 to 70°C. The resulting polymer was separated by pouring into a large excess of vigorously stirred acetone.
The solubility of the polymer was 0.005 Kg/ ^m3 in 0.4M KBr.

Example 5 The polyionenes obtained in Examples 1 and 2 were powdered in a ball mill and 1 g of each was dispersed in 5 g of each Cellobond polyester supplied by BP Chemihals International. 0.1 ml of cobalt naphtate and 0.1 ml of hardener (50% MEKP) were then added, and this mixture was then brushed onto a primed metal test plate. The coating was cured to a smooth finish. The coating contains about 17% polyionene and its marine pollution effectiveness testing is shown in Example 7.

Example 6 3.6 g of 1,4-dichloro-2,3-epoxybutane and 3.1 g of dichlorobutene-2 in 12.5 ml of xylene, 5.8 g of N in 12.5 ml of xylene,
10 to N, N ¹ , N ¹ tetramethylethylenediamine
Added dropwise over a period of minutes. The reaction was carried out at 50°C for 6 hours. The product was isolated by pouring into a large excess of vigorously stirred acetone. The solubility of the obtained polyionene is 0.005 in 0.4M KBr
It was Kg/ ^m3 .

Next, 7.0 g of the obtained epoxy group-containing polyionene was mixed with 7.0 g of a commercially available polyamide curing agent (Velsamd 115) in a methanol/cellosolve mixed solvent, whereby the cross-linking reaction proceeded to form an ionene copolymer solution. I got it. This solution was brushed onto a mild steel plate to obtain a hard film that was stable in seawater. The antifouling effect of this test plate in seawater is shown in Example 8.

Example 7 Metallic test plates with the polyionenes of Examples 1 and 2 obtained in Example 5, and in various amounts with the polyionenes obtained in Example 3, sold under the trade name Epotane by Gutdrus, Wall and Company. Added to epoxy coal tar paint, this paint is added to a 4.5" x 1.5"(11.4"
A series of plates coated with epoxy coal tar resin films having various polyionene contents of Example 3 were coated on mild steel plates measuring 3.8 cm x 3.8 cm) and recovered after being immersed in seawater for 6 weeks in Singapore. , pollution degree is 1 (no pollution)
Rated visually on a scale of ~10 (severely contaminated).

The results obtained were as follows.

Plate Number Polyionene Content Pollution Degree Weight % Test plate obtained in Example 5 for the polyionene of Example 1 (solubility 0.005 Kg/m ³ in 0.4M KBr at 25°C) 1 17 2 Polyionene of Example 2 (25°C The test plate obtained in Example 5 for the solubility in 0.4 M KBr (0.003 Kg/m ³ ) 2 17 2 In addition, the polyionene of Example 3 (0.4 M at 25 °C
The results of the above test plate with a solubility in KBr of 0.007 Kg/m ³ were as follows.

Plate number Polyionene content Contamination level Weight % 3 9.0 5 4 26.0 2 The above results indicate a fair degree of antifouling effect, and the effect is mainly related to the polyionene content, and the influence of solubility is small within the specified range. It is shown that it is small.

Comparative Example 1 Polyionene produced in the same manner as in Examples 1 to 3 except that the reaction time was shortened and the solubility of the resulting polyionene was increased.
In Example 7, coating was carried out in the same manner as in Example 3 for making polyionene into a paint and preparing a test plate.
A sample and a test plate were prepared, and the anti-pollution effect in seawater was measured in the same manner as in Example 7.

The results obtained were as follows.

Plate number Polyionene content Contamination degree Weight % Solubility in 0.4M KBr at 25℃ 0.0105Kg/
m ³ of chlorine-containing polyionene 1 9.0 5 2 26.0 2 Solubility in 0.4M KBr at 25°C 0.0274Kg/
Comparing these results with ^Example 7, the antifouling effect of polyionene is mainly related to the polyionene content, and increasing the solubility of polyionene more than necessary does not improve the effect. First, it is undesirable because it shortens the active life of the marine antifouling paint, and it is shown that a specified solubility is preferable and economical.

Example 8 The test plate coated with the ionene copolymer obtained in Example 6 was recovered after being immersed in seawater for 6 weeks in Singapore in the same manner as in Example 7, and the degree of contamination was visually measured using the scale described in Example 7. The results of the evaluation were as follows.

Plate number Contamination degree 1 1 2 1 3 1 4 1 This result was in agreement with the result predicted from the high ionene copolymer content.

Claims (1)

[Scope of Claims] 1. A substantially water-insoluble ionene polymer as a polyionene or as a film-formable ionene copolymer dissolved or dispersed in a film-formable base; characterized in that the polymer is prepared from a dihalide having an alkyl or alkenyl group each having from 1 to 30 carbon atoms and a diamine having an alkyl group having from 1 to 30 carbon atoms. An underwater body surface treatment composition used as an antifouling paint for ships. 2. The underwater object surface treatment composition according to claim 1, wherein the halogen of the dihalide is bromine or chlorine. 3. The underwater object surface treatment composition according to claim 1, wherein polyionene is dissolved or dispersed in a film-formable base in an amount of 5 to 75% by weight based on the weight of the dry film. 4. The underwater object surface treatment composition according to claim 3, wherein polyionene is dissolved or dispersed in a film-formable base in an amount of 10 to 50% by weight based on the weight of the dry film. 5. The underwater object surface treatment composition according to claim 1, wherein the ionene copolymer is a cross-linked product of an epoxy group-containing polyionene and an amine curing agent. 6. The underwater object surface treatment composition according to claim 5, wherein the epoxy group-containing polyionene is used in an amount of 30 to 70 mol% of the amine curing agent. 7. The underwater object surface treatment composition according to claim 1, wherein the substantially water-insoluble ionene polymer has a solubility of 0.007 Kg/m ³ or less in 0.4 M KBr at 25°C. 8. The underwater object surface treatment composition according to claim 7, which has a solubility of 0.005 Kg/m ³ or less.