JPH0446969A - Antifouling paint composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which has a high antifouling effect against marine organisms and can maintain the antifouling performance stably over a long period of time by using as constituents an adhesive and a resin having chelate groups substituted by copper ions. CONSTITUTION:The title composition contains an adhesive (e.g. a polyester-base adhesive) and a resin having chelate groups partially or wholly substituted by copper ions (e.g. a 140-mesh or smaller powder obtained by allowing a phenol-formaldehyde chelate resin containing iminodiacetic acid groups to adsorb 10wt.% copper ions and grinding it). In some cases, a copper powder can be incorporated therein in addition. This composition has a high antifouling effect against marine organisms and can maintain the antifouling performance stably over a long period of time, so that it can prevent the adhesion of marine organisms to a fishing net, the bottom of a ship, a marine structure, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is an effective preventive device for preventing marine organisms from adhering to fishing nets, lobes, ship bottoms, underwater structures, etc. that are used for long periods in seawater. The present invention relates to a stain paint composition.

(Conventional technology) Fishing nets and robes used for long periods in seawater.

There is a problem in that marine organisms such as algae and shellfish adhere to and grow on the bottoms of ships and underwater structures. For example, when algae and shellfish adhere to and grow on the surface of fishing nets used for fish farming, the nets become blocked, impeding the passage of water, and fish diseases and parasites occur due to lack of oxygen and poor water quality, making it difficult to fish aquaculture. Problems such as fish death occur.

As a measure to prevent marine organisms from adhering to fishing nets, paints containing tributyltin compounds and triphenyltin compounds as antifouling ingredients have traditionally been used. but.

These tin compounds are harmful to the human body, and if they come into contact with human skin when coating or impregnating fishing nets, they may cause problems such as rashes and the possibility of antifouling agents leaching into seawater. , has been detected to be accumulating in the bodies of fish, causing problems of environmental pollution.

Therefore, as an antifouling agent to replace this tin compound.

Various inorganic or organic compounds are being studied.

For example, JP-A-63-205374 and JP-A-64
Publication No. 6071 proposes an antifouling paint using an organic compound with antifouling properties, and Japanese Patent Publication No. 63-55547 proposes an antifouling paint composition containing copper alloy powder as a color vehicle. ing.

(Problems to be Solved by the Invention) Even with the above-mentioned measures, although it shows an excellent anti-adhesion effect initially, when used in the ocean for a long period of time,
There was a problem in that these antifouling components dissolved into seawater and their performance deteriorated in a short period of time.

An object of the present invention is to provide an antifouling paint composition that has high antifouling properties against marine organisms and maintains the antifouling performance stably for a long period of time.

(Means for Solving the Problems) In order to solve these problems, the inventors of the present invention have made extensive studies and found that copper ions can be attached to chelate groups that have the ability to form chelates against metals, thereby providing a protective solution. The present invention was achieved by discovering that the elution of copper ions, which are dirt components, into seawater can be controlled and a coating composition having a stable antifouling effect for a long period of time can be obtained.

That is, the gist of the first invention is an antifouling paint composition comprising an adhesive and a resin having a chelate group in which some or all of the chelate groups are substituted with copper ions.

Moreover, the gist of the second invention is an antifouling paint composition comprising a resin having a chelate group, an adhesive, and copper powder.

The present invention will be explained in detail below.

In the present invention, the chelate group may be any functional group as long as it forms a chelate ring by forming two or more coordinate bonds with a metal ion. Acetic acid group, diethylenetriamine group, triethylenetetramine group, tetraethylenepentamine group.

Amidoxime group, glucamine group, aminophosphate group.

Examples include a dithiocarbamate group, a thiourea group, a bispicolyl amino group, and a monopicolyl amino group. Among them,
Iminodiacetic acid, dithiocarbamate, and aminophosphoric acid groups have strong stability with copper ions.

A bispicolyl amino group and the like are preferred.

Examples of the resin matrix of the resin having a chelate group in the present invention include phenol-formaldehyde resin and styrene-divinylbenzene resin.

Methacrylic acid - divinylbenzene resin, acrylic acid -
Examples include divinylbenzene resin, acrylonitrile-divinylbenzene resin, polyethyleneimine resin, and ethylene vinyl alcohol resin. As these resins, three-dimensionally crosslinked resins, linear high molecular weight materials, or solvent-soluble low molecular weight materials are used. Among these, a reaction product of polyethyleneimine and carbon disulfide, which is a resin having a chelate group, is highly effective as an antifouling paint composition. As for the blended amount of carbon disulfide.

The molar ratio to the ethyleneimine unit, which is a constituent unit of polyethyleneimine, is preferably 0.2 to 1.0, particularly preferably 0.4 to 0.8.

The reaction product of this polyethyleneimine and carbon disulfide is
It can be created using conventional methods. For example, it can be produced by adding carbon disulfide dropwise to an aqueous solution of polyethyleneimine using an alkali catalyst and causing one reaction.

The molecular weight of the polyethyleneimine used in the present invention is preferably in the range of 200 to 100,000.

This resin, which is a reaction product of polyethyleneimine and carbon disulfide, has excellent adhesive properties to the base material, so the amount of adhesive used can be reduced.
Moreover, since it has excellent retention of copper ions, it has an excellent property that the antifouling effect lasts for a long time.

In the present invention, part or all of the chelate groups of the resin having chelate groups can be substituted with copper ions in the following manner, for example.

In other words, if the resin is three-dimensionally crosslinked or has a high molecular weight, a predetermined amount of copper ions can be adsorbed to the resin prepared in fine powder form, or after a predetermined amount of copper ions have been adsorbed to the resin in advance. .

This can be done by crushing, pulverizing, and then dispersing it in an adhesive.

In addition, in the case of low molecular weight resins that are soluble in solvents, a resin that has adsorbed copper ions dissolved in a solvent together with an adhesive can be applied, or a mixture of the resin and adhesive dissolved in a solvent can be applied, and then .

It can also adsorb copper ions.

The copper ion content at this time is preferably 5 to 50% by weight based on the solid content of the antifouling paint composition. If the content is 5% by weight, the antifouling effect tends to be lost;
If it exceeds 0% by weight, the performance as a paint tends to deteriorate.

The adhesive used in the present invention may be any adhesive as long as it has adhesive properties to the substrate to which the resin having a chelate group or the coating composition is applied, such as polyester, urethane, and acrylic. Adhesives such as epoxy, vinyl, and epoxy can be preferably used.

The amount of the adhesive to be blended at this time is preferably 20 to 80% by weight based on the solid content of the antifouling coating composition. If the blending amount is 20% by weight, the adhesion to the substrate will be poor,
The paint tends to fall off easily, and if it exceeds 80% by weight, the durability of the antifouling performance tends to deteriorate.

Further, in the present invention, copper powder is blended into a composition consisting of a resin having a chelate group and an adhesive, and the amount of copper powder blended at this time is preferably 20 to 80% by weight based on the solid content.

In addition, as for the copper powder, considering the surface condition of the coating film, etc.
Particulate materials with an average particle diameter of 10 μm or less, preferably 5 μm or less are preferred.

The copper powder blended in this way gradually dissolves into seawater and provides an antifouling effect, but some of it is adsorbed by the chelate groups, and the antifouling effect is reduced due to the equilibrium relationship between the chelate groups and the seawater. The sustainability of the process is improved.

Note that the chelate group used here may not be substituted with copper ions at all, or may be partially or entirely substituted with copper ions.

(Function) In the present invention, the chelate group stably retains copper ions, which have an excellent antifouling effect, thereby serving to maintain the antifouling effect for a long time.

(Example) Next, the present invention will be specifically explained with reference to Examples.

Note that parts in the examples represent 1 part by weight.

Example 1 Phenol-formalin chelate resin containing iminodiacetic acid group as a chelate group (UNISELECT UR-3)
After 10% by weight of copper ions were adsorbed onto the powder (No. 0, manufactured by Unitika), it was pulverized to create a fine powder of 140 meshes or less.

Next, 40 parts of this chelate resin fine powder and an average particle size of about 4
An antifouling paint composition was obtained by dispersing and mixing 40 parts of copper powder with a size of less than μm in an adhesive prepared by dissolving 100 parts of a polyisocyanate-curable polyester adhesive (UE3400, manufactured by Unitika) in a mixed solvent of toluene and methyl ethyl ketone. Ta.

This antifouling paint composition was applied to a vinylon fishing net so that the solid content was 20% of the weight of the fishing net.

It was immersed in seawater for 4 months, and the presence or absence of seaweed adhesion was observed.

As a result, fishing nets coated with antifouling paint had less seaweed adhesion than fishing nets that were not coated.

Good antifouling performance was observed.

Example 2 30% aqueous solution of polyethyleneimine with a molecular weight of 1800 (
Evomin 5P-018, manufactured by Nippon Shokubai Chemical Co., Ltd.) 140
200 g of a 10% aqueous solution of caustic soda was mixed with 200 g of a 10% aqueous solution of caustic soda, and 38 g of carbon disulfide was added dropwise to this mixed solution, followed by a reaction for 2 hours to obtain a reaction product having a chelating functional group.

When copper ions were added to the reaction product (chelate solution) thus obtained, a fine powder was precipitated, and a resin composition containing 60% by weight of copper ions was obtained.

An antifouling paint composition was obtained by dispersing 80 parts of this resin composition in an adhesive prepared by dissolving 20 parts of a polyurethane adhesive (manufactured by Nippon Polyurethane Co., Ltd.) in a mixed solvent of toluene and methyl ethyl ketone.

This antifouling paint composition was applied to a vinylon fishing net so that the solid content was 20% of the weight of the fishing net.

It was immersed in seawater for 4 months, and the presence or absence of seaweed adhesion was observed.

As a result, fishing nets coated with antifouling paint had less seaweed adhesion than fishing nets that were not coated.

Good antifouling performance was observed.

Comparative Example 1 An antifouling paint composition was prepared in the same manner as in Example 2 without adsorbing copper ions to the chelate resin, applied to fishing nets, and tested for adhesion of seaweed. However, the effect of

As the test period became longer, the adhesion of the nets came to be almost the same as that of fishing nets that were not treated with antifouling paint, and the sustainability of the effect was not recognized.

Comparative Example 2 An antifouling paint composition was prepared in the same manner as in Example 1 except for the chelate resin that adsorbed copper ions, and it was applied to a fishing net, and a seaweed adhesion test was conducted.

At the initial stage of the test, antifouling effects were observed.

As the test period became longer, the adhesion of the nets came to be almost the same as that of fishing nets that were not treated with antifouling paint, and the sustainability of the effect was not recognized.

(Effects of the Invention) Since the antifouling paint composition of the present invention has the above structure, it has high antifouling properties against marine organisms.

Furthermore, the antifouling performance can be maintained stably for a long period of time.

Claims (2)

[Claims] (1) An antifouling paint composition comprising an adhesive and a resin having a chelate group in which some or all of the chelate groups are substituted with copper ions. (2) An antifouling paint composition comprising a resin having a chelate group, an adhesive, and copper powder.