WO1996004341A1

WO1996004341A1 - Antifouling paint

Info

Publication number: WO1996004341A1
Application number: PCT/JP1994/001287
Authority: WO
Inventors: Mitsuhiro Nakamura; Takashi Nakao; Toshiyuki Katayama; Kenzo Kimura; Shin-Ichiro Goto
Original assignee: Nichirin Co., Ltd.
Priority date: 1994-08-03
Filing date: 1994-08-03
Publication date: 1996-02-15
Also published as: AU7276094A

Abstract

An antifouling paint for preventing the deposition of marine organisms on the things where sea water is utilized, such as ships, marine structures, sea water cooler and sea water duct, without using any compound containing heavy metals causative of marine pollution, such as organotin compounds and copper oxides. The paint contains an organic compound having an electron-withdrawing group such as a thiocyano or isothiocyano group as the active ingredient.

Description

Description Antifouling paint Technical field

The present invention relates to a waterproof coating. More specifically, prevent the attachment of marine life to equipment that uses seawater, such as ships, marine structures, coolers that use seawater, and seawater conduits. Protective paints. Background art

Bottom of a ship, underwater structures, props and nets for aquaculture, seawater intake channels used as cooling water, seawater conduits, seawater contact surfaces such as seawater coolers, etc. Because marine organisms such as moss, cellulas and ascidians attach and grow, their functions are impaired and serious damage may occur. As a method for preventing such marine organisms from adhering, for example, a toxic compound such as an organic silver compound or copper oxide is added to a paint, and the toxic compound is prevented from adhering. It is known that a method for preventing the adhesion of the marine organisms by the killing action of the compound, which is applied to the marine organism and gradually eluted in the sea, is known.

However, there is a major transliteration in such methods that would cause marine pollution by the heavy metals contained in the compounds.

Therefore, in recent years, from such a viewpoint, the development of a marine organism adhesion inhibitor containing no heavy metal has been awaited.

The present invention is based on the above prior art, and is a compound containing a heavy metal such as an organic compound and a copper oxide. It is intended to provide an antifouling paint that prevents marine organisms from adhering without using a paint. Disclosure of the invention

The present invention provides an antifouling paint composition characterized by comprising an RY effect I of an antifouling organic compound having an electron-withdrawing group as an active ingredient, and an organic binder. Offer things.

In the present invention, the organic compound may further include, as an electron-withdrawing group, a thiocyano group, an isothiocyano group, a nitrogen group, a dinitro group, or a trinitro group. Provide at least one antifouling paint composition selected from the group consisting of mouth groups and carbonyl groups.

The present invention further relates to the present invention, wherein the organic compound has at least one of a thiocyano group and an isothiocyano group as an electron-withdrawing group.

Provided is an antifouling paint composition having one kind.

The present invention further relates to the present invention, wherein the organic compound has at least one of a thiocyano group and an isotioshiano group as electron-withdrawing groups.

One species, and at least one species from the group consisting of C, C, C, C, C, and C Disclosed is an antifouling paint composition.

The present invention further provides an antifouling method wherein the organic compound is at least one of the compounds represented by the general formula (I), the general formula (（), or the general formula (Π). Provide a coating composition.

R one Y 1

(I) Y-R 2 ^έ -Ύ (π)

Y 3 Υ (m)

6

Two

(Where YY Υ, γ ⁴ , γ ^tf and γ ⁶ are the same. — Or, differently, a thiocyano group, an isothiocyano group, a nitrogen group, a nitro group, a tri- or carbonyl group; In the formula, R ¹ is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, or a carbon atom number. Represents 7 to 20 monovalent saturated hydrocarbon groups substituted with an aromatic hydrocarbon group; R ² represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms; Or a divalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, and R ³ is a 318 saturated hydrocarbon group having 1 to 20 carbon atoms, or a carbon number of 318. Represents 2 to 20 3 镢 unsaturated hydrocarbon groups).

In the present invention, the organic compound may further include a methyl thiosocyanate, a methyl thiosocyanate, a benzyl thiosocyanate, Role methyl cyanate, methyl isocyanate, aryl isocyanate, benzyl isocyanate , Ethylene bath io cyanate, vinyl io io io cyanate, black mouth ethylene bus io cyanate and black Provided is at least one kind of an antifouling paint composition selected from a group consisting of romelen bisulfate.

The present invention further provides an antifouling coating composition comprising 100 to 100 parts by weight of the organic binder and 5 to 50 parts by weight of the organic compound.

The present invention further provides a protective coating composition in which the organic binder is a rubber binder or a synthetic resin binder.

In the present invention, the rubber-based binder may be a liquid polystyrene, a chlorosulfone diphenyl polyethylene, a tangified rubber. At least one antifouling paint composition selected from the group consisting of rubber, silicone rubber and urethane rubber o

In the present invention, the synthetic resin binder may be a vinyl resin, a urethane resin, a chlorinated polypropylene, an acryl resin, a silicone resin, Disclosed is an antifouling coating composition which is at least one selected from the group consisting of epoxy resin and polyester resin.

In the antifouling coating composition of the present invention, an organic compound having an electron-withdrawing group such as, for example, a thiocyano group or an isothiocyan group is used as an active ingredient. Yes.

An organic compound having an electron-withdrawing group has an antibacterial action to prevent slime adhesion observed at the initial stage of marine organism attachment. It has been found by the present inventors that they have such properties. In this way, by preventing the attachment of slime, the establishment, metamorphosis and germination of floating larvae and algae spores are suppressed.

Its antibacterial activity is improved by using methylene bisulfate or chloromethylthiosinate, which is a typical compound of the active ingredient in the present invention. This is explained using an example. Methylene bisthionate has a carbon atom to which two electron-withdrawing groups called thiosiano groups (one SCN) are bonded. Chromomethylthiothionate has a carbon atom to which an electron-withdrawing group such as a thiosano group and a chlorine group (1-C1) is bonded. . These low-electron-density carbon atoms participate in the reaction with an enzyme having a thiol group (one SH) in slime cells, and the activity of the enzyme depends on the activity. Has antibacterial activity o It is presumed that other organic compounds also have an antifouling effect due to a decrease in the electron density of the carbon atom to which the electron-withdrawing group is bonded.

The active ingredient used in the present invention has a thiosiano group (-SCN) or an isothiosano group (one NCS) as an electron-withdrawing group. Although an organic compound is required, it can be judged from the magnitude of the electron density by NMR and is equivalent or less than a thiocyan group or an isothiocyan group. Organic compounds having a group having a higher electron-withdrawing effect, for example, a halogen group, a nitrile group, a nitrile group, a carbonyl group, etc. Can be used. In this case, chlorine, bromine, fluorine, etc. are added as the nod gen group.

That is, those selected from the following group of organic compounds can be preferably used:

A. An organic compound having at least one of a thiocyano group and an isochocyano group as electron-withdrawing groups.

B. at least one electron-withdrawing group selected from the group consisting of a nitrogen group, a nitro group, a nitrile group and a luponyl group; An organic compound having

C. As electron-withdrawing groups, at least one of a thiosiano group and an isothiosano group, as well as a halogen group, a nitro group, and a An organic compound having at least one species that is transmitted from a group consisting of tri- and carbonyl groups.

Preferred among such organic compounds are compounds represented by the general formula (I), (（) or (Itt). RY (I)

Y ^L -R ^L- Y (π)

Y one R Y 5 (m)

Y

(In the formula, Y 1 Y 丫³ , 丫⁴ , ¥ ^{5 and}丫⁶ are the same or different, and are thio cyano group, isotio cyano group, halogenogen R ¹ is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ² is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. Represents up to 20 monovalent unsaturated hydrocarbon groups, or monovalent saturated hydrocarbon groups having 7 to 20 carbon atoms and substituted by an aromatic hydrocarbon group; R ² represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms or a divalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, and R ³ represents a carbon atom. (Shows a trivalent saturated hydrocarbon group having 1 to 20 carbon atoms or a trivalent unsaturated hydrocarbon group having 2 to 20 carbon atoms)

1 to 20 carbon atoms represented by R 1 (preferably

(8) monovalent saturated hydrocarbon groups (alkyl groups) include methyl, ethyl, propyl, butyral, isobutyl and t-butyl, etc. Is overwhelmed.

As a monovalent unsaturated hydrocarbon group having 2 to 20 (preferably 2 to 4) carbon atoms represented by R ¹ , vinyl 2 —pronyl ( ), 1-pronil, 1-butenyl, 2-butenil, 2—methylol 2—pronyl (21-methylaryl) ), Etc.

As a monovalent saturated hydrocarbon group substituted by an aromatic hydrocarbon group having 7 to 20 (preferably 7 to 8) carbon atoms represented by R ¹ , Is an arylalkyl group such as benzene The throat is broken.

As a divalent saturated hydrocarbon group having 1 to 20 (preferably 1 to 8) carbon atoms represented by R ² , methylene ethylene, Alkylen groups such as propylene, trimethylene, tetramethylene, etc. are exposed.

Examples of the divalent unsaturated hydrocarbon group having 2 to 20 (preferably 2 to 4) carbon atoms represented by R ² include vinylene and propylene. 2, 2-butenelen etc. are removed.

As a trivalent saturated hydrocarbon group having 1 to 20 (preferably 1 to 8) carbon atoms represented by R ³ , methyl lysine (methine ),

-CH-CH2-CHH-CH-CH2-

The throat is broken.

As an unsaturated hydrocarbon group of 3 plows having 2 to 20 (preferably 2 to 4 炭素) carbon atoms represented by R ³ ,

C = C H — and so on.

Specific compounds represented by the general formulas (1), (II) or (m) include, for example, those shown in Table 1.

[Margins below]

Compound name Chemical formula

Methylenebisthiocyanate NCS-CHo-SCN methylthiocyanate CHo-SCN

Benzyl thiocyanate Or CH ₂ ~ SCN

Chloromethyl thiosinate C £-CH ₂ ~ SCN Methyl isothiosinate CH ₃ -NCS Aryl isothiosinate CU _? = CH-CHo- NCS

Benzyl isothiocyanate <Q)-CH ₂ -NCS

Ethylene bisthiosinate NCS-CH ₂ ~ CH ₂ ~ SCN Vinylene bis thiosinate NCS-CH = CH-SCN

NCS-One CH-CH ₂ -SCN C £

Chloromethylenebisthiosinate

NCS-CH—SCN Examples of the organic binder that is a paint base in the present invention include, for example, liquid polybutadiene rubber and cross-linked polyolefin rubber. Rubber binders such as polyethylene, rubber chloride, silicone rubber and urethane rubber; vinyl resins such as vinyl chloride resin, urethane resin, Synthetic resin binders such as chlorinated polypropylene, acrylic resin, silicone resin, epoxy resin, polyester resin, etc. However, the present invention is not limited to only such examples. As the rubber binder, those which can be vulcanized at a low temperature as described above are preferable.

With the use of the organic binder, the formed coating is more flexible, less susceptible to cracks and cracks, and less abrasion resistant. Excellent properties are exhibited as compared with conventional modified oil-based paints. In particular, when liquid polybutadiene rubber is used as the organic binder, a solvent-free paint is obtained, and a thick coating film can be obtained in one application. It is particularly preferred in the present invention because it can be formed.

When the amount of the organic compound having an electron-withdrawing group is too small, marine organisms are liable to adhere to the compound, and when it is too large, the amount is too small. Although the antifouling property is improved, the coating strength is reduced and the coating becomes brittle, and when the coating is stored for a long period of time, the coating does not spread or the coating does not spread during coating. Therefore, the range of 5 to 50 parts by weight relative to 100 parts by weight of the organic binder is preferable, since it is difficult to paint uniformly.

The antifouling paint of the present invention is obtained, for example, by dissolving an organic binder in a solvent, adding an organic compound having an electron-withdrawing group thereto, and, if necessary, a vulcanizing agent ( (Cross-linking agent) It can be manufactured by blending additives such as rubium, pigments and silica. When using liquid polypropylene jengom as an organic binder, the liquid polybutane jengo can be electron-withdrawn without using a solvent. The compound can be produced by blending an organic compound having a functional group, a vulcanizing agent, and, if necessary, the above-mentioned additives. If a vulcanizing agent is used, it is preferable to use a two-component paint if the resulting paint has a short pot life.

The antifouling paint of the present invention thus obtained can be applied by a usual method such as a spray coating method.

Next, the antifouling paint of the present invention will be described in detail with reference to Examples, but the present invention is not limited to only such Examples. BEST MODE FOR CARRYING OUT THE INVENTION Examples 1 to 11 and Comparative Examples 1 to 2

The active ingredients and organic binders shown in Tables 2 and 3, as well as vulcanizing agents and solvents as needed, were blended, and the mixture was kneaded thoroughly with a kneader to prepare a paint. The antifouling coatings of Examples 7 to 9 were composed of a component consisting of PBD and methyl bisthiosinate, and a 4, 4'-diphenyl methacrylate. Prepared as a two-component paint consisting of components consisting of diisocyanate (vulcanizing agent) o

An iron plate is used as the object to be coated, the surface of the iron plate is removed with a sandblast, and a chlorinated rubber-based primer (Nichirin Co., Ltd., Adbon Co., Ltd.) is used. 100 000) so that the film thickness becomes l O d / zm, and after drying, apply the paint obtained above. The cloth and drying were repeated four times so that the film thickness became 0.8 to lmm, and then left at room temperature for 7 days to cure, and test specimens were obtained.

Using the obtained test pieces, the antifouling property of the coating film was examined according to the following method. Tables 2 and 3 show the results.

(Antifouling)

The obtained test specimen was suspended at a depth of 1.5 m from a raft installed in Sakagoshi Bay in Ako City, Hyogo Prefecture, Japan, for approximately one power month from May to June 1994. The IB was released, and the area of the ボ bobo adhering to the surface of the ε> ΐ piece was measured, and the adhesion rate (%) was determined (Table 2). In the same manner, the test piece was kept abandoned for about two years and two months from August 1990 to October 1994, and the area of the Fujibobo adhered to the surface of the test piece was measured. ) (Table 3).

Each abbreviation in Tables 2 and 3 means the following.

PBD Liquid polybutadiene rubber

C S P E o o Slephonized polystyrene

C P P Chlorinated Polypropylene

A F Commercially available antifouling paint for water conduits (China Paint Co., Ltd. antifouling paint for seawater introduction pipes, containing cuprous oxide as a heavy metal)

[Margins below]

Table 2 Coating composition (mass part)

Example number methylenebischloromethinole benzylthio

Organic binder xylene [Adhesion rate (%)]

Nan-na-to-na-na-to-na-to-a

1 CPP 100 5 100 0

2 CPP 100 20 100 0

3 CPP 100 5 100 5

4 CPP 100 20 100 0 t

5 CPP 100 5 100 10

6 CPP 100 20 100 5

Comparative example

1 AF 0

Table 3 Composition of paint (weight section)

Antifouling performance M number Methylene bis 4,4 dipheninoleme

Organic binder Xylene f Adhesion rate ί%) Ί Thiocyanate Tandiisocyanate

7 PBD 100 10 25 20

8 PBD 100 20 25 10

9 PBD 100 30 25 0

10 CSPE 100 30 100 10

11 CPP 100 30 100 0 Comparative example

2 AF 10

From the results shown in Tables 2 and 3, the antifouling paint of the present invention was excellent in antifouling property at least as much as the conventional paint (AF) containing the heavy metal. You can see that it is Ο

Since the antifouling paint of the present invention does not contain heavy metals, it does not have problems such as causing marine pollution, and has a good antifouling property. For example, it is applied to equipment that comes in contact with seawater, such as cooling water intake channels of thermal power plants, seawater conduits, inner surfaces of coolers, and outer panels on the bottom of ships, for example. This has the effect of preventing the attachment of marine organisms for a long period of time.

Claims

Range of request

1. An antifouling paint composition characterized by an effective antifouling amount of an organic compound having an electron-withdrawing group as an active ingredient and an organic binder.

2. The organic compound is selected from the group consisting of a thiosiano group, an isothiocyano group, a halogenogen group, a nitro group, a nitro group, and an electron withdrawing group. 2. The antifouling paint composition according to claim 1, wherein the antifouling paint composition has at least one kind that is at least one type that is sought from a group consisting of a carbonyl group.

3. The claim that the compound has at least one of a thiosiano group and an iso-succino group as electron-withdrawing groups. 2. The antifouling paint composition according to range 1.

4. The organic compound has at least one of a thiosiano group and an iso-sociosiano group as an electron-withdrawing group, and a halogen ¾k, The antifouling composition according to claim 1, wherein the antifouling substance has at least one kind passed from a group consisting of a π group, a tri-group and a carbon group. Paint composition.

5. The method according to claim 1, wherein the organic compound is at least one compound represented by the general formula (I), the general formula (II) or the general formula (m). Waterproof coating composition.

R-I Y (I)

Y one R one Y ³ (π)

Y one R one Y ⁵ (m)

Y

(Wherein, Y 1 Y 2 Y 3 ^a , Y ⁴ , Y ⁵ and Y ⁶ are the same or different and each represents a thiocyan group, an isothiocyan group, or a halogen group. , Nitro, nitrile or carbohydrate R ¹ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, or a carbon atom; Number of atoms? Represents up to 20 monovalent saturated hydrocarbon groups that have been replaced by aromatic hydrocarbon groups, and R ² represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. Or a divalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, and R ³ is a trivalent saturated hydrocarbon group having 1 to 20 carbon atoms, or Represents a trivalent unsaturated hydrocarbon group having 2 to 20 carbon atoms).

6. The organic compound is selected from the group consisting of methyl benzoate, methyl oleate, benzyl thiosinate, and chloromethyl Thiosocyanate, methyl isocyanate, arsenal of thiosocyanate, penzinoliso thiocyanate, ethizo Levi-bio-sci-net, vinylene-bio-sci-net, black mouth ethylene-bio-sci-net and chrome-metal 6. The antifouling paint composition according to claim 5, wherein the composition is at least one member selected from the group consisting of ambiostionates.

7. The antifouling coating composition according to claim 1, wherein 5 to 50 parts by weight of the organic compound is blended with respect to 100 parts by weight of the organic binder.

8. The antifouling coating composition according to claim 1, wherein the organic binder is a rubber-based binder or a synthetic resin-based binder.

9. The rubber binder is liquid polybutadiene rubber, chlorosulfonated polyethylene, rubber chloride, silicone rubber and rubber.汚 At least one member selected from the group consisting of returnable rubbers. object.

10. Synthetic resin binder is vinyl resin, urethane resin, chlorinated polypropylene, acrylic resin, silicone resin, epoxy resin. Claims which are at least one member from a group different from the resin and the polyester resin.

8. The antifouling paint composition according to 8.