JP3188948B2 - Resin for antifouling paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for an antifouling paint which has improved antifouling performance and coating film properties in an antifouling paint and in which the paint film gradually dissolves from the surface in seawater.

[0002]

2. Description of the Related Art An antifouling paint using an organotin-containing copolymer as a resin for an antifouling paint is based on the fact that a coating film formed by applying the antifouling paint gradually dissolves in seawater from the surface. They have been widely used because they exhibit an antifouling effect over a long period of time and can reduce fuel consumption during navigation of ships and the like. However, the use of antifouling paints using an organotin-containing copolymer as a resin for antifouling paints has been restricted in recent years due to the problem of marine pollution.

[0003]

In order to cope with such a situation, a resin for an antifouling paint in which an ester moiety which is soluble in seawater is introduced into a polymer side chain is being developed, but it is still suitable for use in seawater. Resins for antifouling paints which dissolve in water and exhibit antifouling properties for a long time have not been provided. In addition, as a resin for antifouling paint instead of a resin using an organotin-containing copolymer, rosin and other resins, for example, chlorinated rubber,
Vehicles using a combination of a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-isobutyl vinyl ether copolymer, and an acrylic resin have been used. However, antifouling paints using these resins show some improvement in the antifouling effect, but have drawbacks such as a significant decrease in the physical properties (performance) of the antifouling coating film. That is, in a vehicle in which rosin and a resin such as chlorinated rubber are used in combination, if the amount of rosin used is small, the solubility of the coating film in seawater is reduced, so that the antifouling effect is not maintained. In addition, the use of a large amount of rosin improves the dissolution of the coating film in seawater, and the antifouling effect is somewhat maintained.
The physical properties and adhesiveness of the coating film of the antifouling paint are reduced, and peeling and cracks are liable to occur, causing problems in aspects other than the antifouling performance. Therefore, development of a resin for an antifouling paint which is excellent in the properties of the antifouling paint film and which enables a long-term antifouling by dissolving the coating film appropriately in seawater is desired.

[0004]

Means for Solving the Problems Accordingly, the present inventors have
As a result of earnest study, as a vehicle, a copolymer of a (meth) acrylic monomer having an ether bond and a (meth) acrylic monomer having a hydroxy group or a (meth) acryl monomer having an ether bond By using a copolymer of a (meth) acrylic monomer having a monomer and a hydroxy group and an ethylenically unsaturated monomer, a coating film formed by applying an antifouling paint is appropriately dissolved in seawater. Furthermore, if the resin for antifouling paint composed of these copolymers and the slightly water-soluble resin are used in combination, the antifouling paint has no peeling, no cracks, has good coating properties such as adhesiveness, and is long. The present inventors have found that an antifouling paint composition that maintains the antifouling effect for a period can be obtained, and have reached the present invention.

The present invention relates to an antifouling paint comprising: (a) a compound represented by the general formula (1):

[0006]

Embedded image (Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, a phenylene group or a benzylene group, and X represents an alkoxy group or a phenoxy group having 1 to 12 carbon atoms). Having a represented ether bond (meth)
Acrylic unit 30 to 99.9% by weight, (b) general formula (2)

[0007]

Embedded image (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkylene group having 2 to 10 carbon atoms) 0.1 to 30% by weight of a (meth) acrylic unit having a hydroxy group represented by c) An antifouling paint resin comprising a copolymer formed from 0 to 50% by weight of an ethylenically unsaturated monomer unit, and a resin composition for an antifouling paint using this resin in combination with a slightly water-soluble resin.

In the present invention, the unsaturated monomer having an ether bond represented by the general formula (1) is, for example, 2
-Methoxyethyl acrylate, 1-methyl-2-methoxyethyl acrylate, 1-ethyl-2-methoxyethyl acrylate, 2-methoxypropyl acrylate
3-methoxypropyl acrylate, 3-methoxybutyl acrylate, 4-methoxybutyl acrylate
3-methyl-3-methoxybutyl acrylate, 2
-Methoxyphenyl acrylate, 3-methoxyphenyl acrylate, 4-methoxyphenyl acrylate,
4- (2-methoxyethyl) phenyl acrylate, 2
-Methoxy-4-methylphenyl acrylate, 4-methoxybenzyl acrylate, 2-ethoxyethyl acrylate, 1-methyl-2-ethoxyethyl acrylate
3-ethoxypropyl acrylate, 3-ethoxybutyl acrylate, 2-butoxyethyl acrylate
2-phenoxyethyl acrylate, 1-methyl-
Examples thereof include 2-phenoxyethyl acrylate, 3-phenoxybenzyl acrylate and methacrylate thereof. These (meth) acrylic monomers having an ether bond are used alone or in combination of two or more.

The unsaturated monomer having a hydroxy group represented by the general formula (2) includes, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxypropyl acrylate.
Hydroxybutyl acrylate and their methacrylates; These (meth) acrylic monomers having a hydroxy group are used alone or in combination of two or more.

Further, as the ethylenically unsaturated monomer to be copolymerized with the unsaturated monomer represented by the general formula (1) and the unsaturated monomer represented by the general formula (2), for example, Acrylic or methacrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methacrylate esters thereof, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, and vinyl acetate Vinyl compounds having a functional group such as vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, N-vinyl pyrrolidone, aromatic compounds such as styrene, vinyl toluene and α-methyl styrene, dimethyl maleate , Dibutyl maleate, dimethyl fumarate
And dialkyl ester compounds of unsaturated dibasic acids such as

The antifouling paint resin of the present invention has the general formula (1)
By copolymerizing an unsaturated monomer having an ether bond represented by the following formula with an unsaturated monomer having a hydroxy group represented by the general formula (2), or The unsaturated monomer represented by the formula (2), the unsaturated monomer represented by the general formula (2) and the ethylenically unsaturated monomer unit are copolymerized.

The general formula (1) for forming the copolymer of the present invention
The content of the unsaturated monomer having an ether bond represented by the formula is in the range of 30 to 99.9% by weight. If the content is less than 30% by weight, the solubility of the antifouling coating film in seawater decreases, and the desired antifouling effect cannot be exhibited.
Further, the content of the unsaturated monomer having a hydroxy group represented by the general formula (2) that forms the copolymer of the present invention is:
It is in the range of 0.1 to 30% by weight. If the content exceeds 30% by weight, the water resistance of the coating film is reduced, and swelling and peeling of the coating film may occur.

The weight average molecular weight of the copolymer of the present invention is 5
It is desirable that it is 000 to 300,000. If the molecular weight is less than 5000, the coating film of the antifouling paint becomes brittle,
This is because peeling and cracking are likely to occur, and if it exceeds 300,000, the viscosity of the copolymer solution increases, and handling becomes difficult.

Next, the unsaturated monomer having an ether bond represented by the general formula (1) of the present invention and the general formula (2)
In The slightly water-soluble resin used in combination with an antifouling coating resin composed of a copolymer formed from an unsaturated monomer having a hydroxy group represented by moths Murojin, wood rosin, tall oil rosin rosin, rosin zinc salt, rosin metal salt such as rosin copper salts, rosin ether, modified rosin, polymethyl vinyl ether of hydrogenated rosin, vinyl ether copolymer and poly ethyl vinyl ether, poly N- Binirupirorido emissions and the like.

When a slightly water-soluble resin is used in combination, the resin for antifouling paint comprising the copolymer of the present invention is preferably contained in the resin composition for antifouling paint in an amount of 20% by weight or more. If the content is less than 20% by weight, the coating film of the antifouling paint becomes fragile and may peel off. On the other hand, the slightly water-soluble resin is preferably contained in the resin composition for antifouling paint in an amount of less than 80% by weight. If the content is more than 80% by weight, the adhesion of the coating film of the antifouling paint is reduced, and the coating is easily peeled off.

An antifouling agent can be added to a resin for antifouling paint comprising the copolymer of the present invention or a resin composition for antifouling paint using the resin for antifouling paint and a slightly water-soluble resin for a long time. An antifouling paint that maintains the fouling effect is obtained. The antifouling agent is not limited as long as it has a killing or repelling effect on marine fouling organisms. For example, copper compounds such as cuprous oxide, rhodan copper, copper powder, zinc oxide, 2-mercaptopyridine- Zinc compounds such as N-oxide zinc and zinc dimethyldithiocarbamate; and organic compounds such as 2,4,5,6-tetrachloroisophthalonitrile, 3,4-dichlorophenyldimethylurea, and maleimide compounds. Can be The amount of the antifouling agent used in the present invention is not particularly limited, but is preferably 1 to 80% by weight in the antifouling paint.

Further, a dye, a pigment, a plasticizer, a thixotropic agent, an organic solvent and the like can be added to the antifouling paint resin of the present invention, if necessary, to obtain an antifouling paint. Examples of the pigment include red iron oxide, talc, titanium oxide, silica, calcium carbonate, barium sulfate, calcium oxide, and the like.
One or two or more can be added and used. Examples of the thixotropic agent include bentonite, polyethylene oxide, various amide compounds, and the like.

[0018]

Next, the present invention will be described with reference to examples.
The% in each Example is% by weight, the viscosity is a value measured at 25 ° C., and the molecular weight is a weight average molecular weight by GPC (in terms of polystyrene). However, the amount of each component in Table 1 represents weight (g).

Production example 1 of copolymer Production example 1 equipped with thermometer, reflux condenser, stirrer and dropping funnel
After charging 500 g of xylene into a 2,000 ml flask, the temperature was raised to 95 to 100 ° C. under a nitrogen atmosphere, and 400 g of 2-methoxyethyl methacrylate, 2-g
A mixture of 10 g of hydroxyethyl methacrylate, 90 g of methyl methacrylate and 3 g of benzoyl peroxide was added dropwise while maintaining the temperature at 95 to 100 ° C. After dripping,
Polymerization reaction is conducted at 95-100 ° C for 5 hours to obtain a copolymer solution P
-1 was obtained. The viscosity of P-1 is 1350 cps (25
° C), heating residue is 50.3%, weight average molecular weight is 5400
It was 0.

Production Examples 2 to 4 Polymerization was carried out in the same manner as in Production Example 1 using the organic solvents, monomers and polymerization initiators shown in Table 1 to obtain a copolymer solution P.
-2-P-4 was obtained. The viscosity of each obtained copolymer solution,
The heating residue and the weight average molecular weight were measured. The results are shown in Table 1.

Production Examples 5 to 6 Polymerization was carried out in the same manner as in Production Example 1 except that the polymerization temperature was 80 to 85 ° C. using the organic solvents, monomers and polymerization initiators shown in Table 1. Polymer solutions P-5 and P-6 were obtained. The viscosity, heating residue and weight average molecular weight of each of the obtained copolymer solutions were measured. The results are shown in Table 1.

Reference Example 1 A thermometer equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was used.
After charging 500 g of xylene into a 2,000 ml flask, the temperature was increased to 95 to 100 ° C. under a nitrogen atmosphere, and 100 g of 2-methoxyethyl methacrylate, 250 g of methyl methacrylate, and n-butyl acrylate 1 were stirred.
A mixed solution of 50 g and 3 g of benzoyl peroxide was added to 9
The solution was added dropwise while maintaining the temperature at 5 to 100 ° C. After dripping, 95-1
Polymerization reaction was carried out at 00 ° C for 5 hours, and comparative copolymer solution Q-1 was used.
I got The viscosity of Q-1 was 830 cps (25 ° C.), the heating residue was 50.6%, and the weight average molecular weight was 52,000.

Reference Example 2 1 equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel
A 300 ml flask was charged with 300 g of xylene and 200 g of butyl acetate, and then charged under a nitrogen atmosphere at 80 to 85 g.
Temperature, and stirred with methyl methacrylate 300
g, n-butyl acrylate 150 g, styrene 30
g, 20 g of 2-hydroxyethyl methacrylate and 2 g of azobisisobutyronitrile at 80 to 85 ° C.
The solution was dropped. After the dropwise addition, a polymerization reaction was carried out at 80 to 85 ° C for 5 hours to obtain a comparative copolymer solution Q-2. Q-2
Has a viscosity of 1800 cps (25 ° C.) and a heating residue of 50.
The weight average molecular weight was 70000 and 7%.

Preparation of rosin metal salt Rosin zinc salt 200 g of gum rosin, 200 g of ZnO and 230 g of xylene were added to a 1000 ml flask equipped with a thermometer, a reflux condenser and a stirrer, stirred at 70 to 80 ° C. for 3 hours, and cooled to room temperature. After filtration, a dark brown clear solution of rosin zinc salt was obtained. The heating residue of the obtained rosin zinc salt xylene solution was 50.5%.

Rosin copper salt 200 g of gum rosin, 200 g of Cu ₂ O and xylene 2
Using the same operation as in the case of the rosin zinc salt using 30 g,
A rosin copper salt xylene solution was obtained. The heating residue of the obtained rosin copper salt xylene solution was 50.1%.

[0026]

[Table 1]

Preparation of antifouling paints Examples 1 to 9 Using the copolymer solutions P-1 to P-6 obtained in Production Examples 1 to 6, the antifouling paints of the present invention were prepared according to the formulations shown in Table 2. Prepared.

[0028]

[Table 2]

Comparative Examples 1 to 5 Comparative copolymer solutions Q-1 and Q-2 obtained in Reference Examples 1 and 2.
And a commercially available resin to prepare an antifouling paint according to the formulation shown in Table 3.

[0030]

[Table 3]

Coating adhesion test Each of the antifouling paints obtained in Examples 1 to 9 and Comparative Examples 1 to 5 was applied as a dry coating on a hard PVC plate (75 × 150 × 1 mm) to about 100 μm. Then, after drying at 40 ° C. for one day, a Goban test was performed. The results are shown in Table 4.

[0032]

[Table 4]

A coating drum was provided with a rotating drum having a diameter of 318 mm and a height of 440 mm at the center thereof, which was rotatable by a motor. Next, a heating device and a cooling device were installed to keep the temperature of the seawater constant, and a pH automatic controller was installed to keep the pH of the seawater constant. Examples 1 to 9 and Comparative Example 1
Each of the antifouling paints obtained in Nos. 1 to 5 was applied to a hard PVC plate (75 × 150
× 1 mm), and dried at 40 ° C. for 1 day after coating so as to have a dry film thickness of about 100 μm. The test plate to which the antifouling paint was applied was fixed to the rotating drum of the rotating device of the above device so as to be in contact with seawater, and rotated in seawater at a speed of 37 km / hr for 3 months. During that time, the seawater temperature is 25 ℃
The pH was maintained at 8.0 to 8.2, and the seawater was replaced every week. The initial film thickness of each coated test plate and the remaining film thickness after three months were measured with a microscope, and the dissolved coating thickness was calculated from the difference. The results are shown in Table 5.

[0034]

[Table 5]

Antifouling test Each of the antifouling paints obtained in Examples 1 to 9 and Comparative Examples 1 to 5 was dried on both sides of a hard PVC plate (100 × 200 × 2 mm) so as to have a dry film thickness of about 200 μm. Applied. This test plate was immersed 1.5 m below the sea surface in Owase City, Mie Prefecture, and the test plate was stained with attached organisms for 18 months. This result is the sixth
It is shown in the table. The numbers in the table represent the percentage of the area of the soiled organisms that adhered.

[0036]

[Table 6]

[0037]

[Effects] As is clear from the results of various tests, the antifouling paint using the antifouling paint resin of the present invention has excellent properties of the antifouling coating film, good adhesion to an object to be coated, and a base treatment. And the like, and the coating film is gradually dissolved in the seawater from the surface, so that the antifouling effect is exhibited for a long period of time. Therefore, the frictional resistance of the ship is reduced, and it is possible to save fuel during navigation.

Continuing from the front page Examiner Hideji Sasaki (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 220/26 C09D 5/16 C09D 133/14

Claims (2)

(57) [Claims] 1. An antifouling paint comprising: (a) a compound represented by the general formula (1): (Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, a phenylene group or a benzylene group, and X represents an alkoxy group or a phenoxy group having 1 to 12 carbon atoms). Having a represented ether bond (meth)
Acrylic unit 30 to 99.9% by weight, (b) general formula (2) (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkylene group having 2 to 10 carbon atoms) 0.1 to 30% by weight of a (meth) acrylic unit having a hydroxy group represented by c) Resins for antifouling paints comprising a copolymer formed from 0 to 50% by weight of ethylenically unsaturated monomer units. 2. The resin for an antifouling paint according to claim 1,
5% by weight of rosin, rosin metal salt, modified rosin, vinyl
From an ether copolymer and poly N-vinylpyrrolidone
A resin composition for an antifouling paint, characterized by using 5 to 80% by weight of a selected resin in combination.