JP3455671B2 - Antifouling paint composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifouling coating composition capable of maintaining stable antifouling performance for a long period of time as well as excellent coating film physical properties and water resistance.

[0002]

2. Description of the Related Art An antifouling paint that uses an organic tin copolymer whose coating film gradually dissolves in seawater has excellent antifouling properties that prevent marine organisms from adhering to the surface of ships and the like. However, its use has been restricted in recent years due to the problem of marine pollution. In order to prevent this marine pollution, an antifouling paint using an organosilicon-containing polymer having a hydrolyzable organosilicon ester group introduced in its side chain is disclosed in US Pat. No. 4,593,055. There is. The coating film formed using this antifouling paint maintains its antifouling effect by the surface of the coating film being hydrolyzed and gradually dissolved in seawater to prevent the adhesion of marine organisms to the bottom of the ship and It reduces fuel consumption.

[0003]

However, when the above-mentioned organosilicon-containing polymer is used as an antifouling paint, water gradually penetrates into the coating film and the coating film swells or peels off. Therefore, there is a problem that the antifouling performance becomes insufficient.

In Japanese Patent Laid-Open No. 10-30071, there is an example in which trimethylsilanol is used in combination, but silanol having a small alkyl group such as trimethylsilanol has a low boiling point and is added to a paint to form a coating film. When it is set, the coating film is not improved at all because it volatilizes with the solvent.

In view of the above points, the present invention is directed to coating film physical properties,
An object is to provide an antifouling paint that has excellent water resistance and can maintain stable antifouling performance for a long period of time.

[0006]

Therefore, the present inventors have
In order to achieve the above object, as a result of extensive studies, by adding a specific organosilicon compound to the organosilicon-containing polymer, excellent coating film physical properties and water resistance can be obtained, and the antifouling performance can be maintained for a long time. They have found that they can do so and have completed the present invention.

That is, the present invention provides (1) A) in the molecule,
At least one of the following formulas:

[0008]

[Chemical 3]

[In the formula, R ^{1 to} R ³ each have 1 to 1 carbon atoms.
8 alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, which may be the same or different from each other, and at least 1 of R ^{1 to} R ³ In which an organosilicon-containing polymer having a triorganosilicon ester group represented by the formula:

[0010]

[Chemical 4]

[In the formula, R ^{4 to} R ⁸ each have 1 to 1 carbon atoms.
8 alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, which may be the same or different from each other, and have ^{4 to 6} carbon atoms. Is ⁹ or more, R ⁹ is a hydrogen atom, a chlorine atom, a hydroxyl group or a group selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group, and n is 0 or 1] is contained in the antifouling coating composition.

Furthermore, the present invention (2) comprises the organosilicon compound in an amount of 0.1 to 30% by weight based on the solid content of the coating composition, as described in the above item (1). Regarding things.

Further, in the present invention, (3) the organosilicon polymer is a (meth) acrylic acid ester copolymer having a triorganosilicon ester group, a maleic acid ester copolymer or a fumaric acid ester copolymer. The present invention relates to the antifouling coating composition according to item (1) or (2).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The organosilicon-containing polymer used in the present invention includes an organosilicon-containing monomer having a triorganosilicon ester group represented by the above formula (I) (hereinafter referred to as monomer A). 1), or 2 or more polymers thereof (hereinafter referred to as polymer A), and 1 or 2 or more of the monomers A,
And a copolymer (hereinafter, referred to as a copolymer AB) with one or two or more kinds of a vinyl-based monomer (hereinafter, referred to as a monomer B) capable of being copolymerized, and if necessary, Polymer A
And the copolymer AB may be used in combination.

In the formula (1), examples of the alkyl group having 1 to 18 carbon atoms represented by R ^{1 to} R ³ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and s. Examples thereof include linear or branched alkyl groups such as -butyl, t-butyl, n-amyl, i-amyl, hexyl, octyl, lauryl and stearyl. The cycloalkyl group includes cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclohexyl, methoxycyclohexyl, chlorocyclohexyl, etc., and one or more kinds of unsubstituted cycloalkyl groups or alkyl groups, alkoxy groups, halogen atoms and the like. Examples thereof include a cycloalkyl group substituted with a substituent. As the aryl group, phenyl, tolyl, xylyl, mesityl, ethylphenyl, isopropylphenyl, methoxyphenyl, phenoxyphenyl, chlorophenyl, naphthyl, etc., an unsubstituted aryl group or an alkyl group, an alkoxy group, a halogen atom, etc., or 2 An aryl group substituted with one or more substituents can be mentioned. Examples of the aralkyl group include benzyl, 2-phenylethyl, 1-phenylethyl, methylbenzyl, methoxybenzyl, phenoxybenzyl, chlorobenzyl, etc.
Examples thereof include an unsubstituted aralkyl group or an aralkyl group substituted with one or more substituents such as an alkyl group, an alkoxy group and a halogen atom.

At least one of R ^{1 to} R ³ has a carbon number of 3 or more, that is, an alkyl group or a cycloalkyl group having a carbon number of 3 or more, so that the consumption rate of the organosilicon-containing polymer is not too high. An aryl group and an aralkyl group are preferred.

Examples of the monomer A include (meth) acrylate having a triorganosilicon ester group represented by the formula (1), malate, itaconate and fumarate. Malate, itaconate and fumarate are of formula (I)
It may have one or two triorganosilicon ester groups represented by. In one case, the remaining carboxyl group is also preferably esterified, and in this case, the alcohol residue portion is R ^{1 to} R ³ described above.
Examples of the alkyl group having 1 to 18 carbon atoms, cycloalkyl group, aryl group, aralkyl group and the like.

Specific examples of the monomer A include, for example, tri-n-propylsilyl (meth) acrylate and tri-i.
-Propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-i-butylsilyl (meth) acrylate, tri-s-butylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tribenzylsilyl ( (Meth) acrylate, tri-2-phenylethylsilyl (meth) acrylate, dimethyllaurylsilyl (meth) acrylate,
Dimethylstearylsilyl (meth) acrylate, dimethylphenylsilyl (meth) acrylate, di-i-propyl-n-butylsilyl (meth) acrylate, cyclohexyldiphenylsilyl (meth) acrylate, n
-Butyldiphenylsilyl (meth) acrylate, t-
Butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl (meth) acrylate, tri-n-
Butylsilylmethylmalate, tri-n-butylsilyl-n-butylmalate, tri-n-butylsilyl-i-
Amyl malate, tri-n-butylsilyl stearyl malate, tri-n-butylsilyl cyclohexyl maleate, tri-n-butylsilyl phenyl maleate, tri-
n-Butylsilylbenzylmalate, tri-i-propylsilylmethylmalate, tri-i-propylsilyl-
n-butylmalate, tri-i-propylsilyl-i-
Amyl malate, tri-i-propylsilyllaurylmalate, tri-i-propylsilylstearylmalate, t-butyldiphenylsilyllaurylmalate, bis (tri-n-butylsilyl) malate, bis (tri-
i-Propylsilyl) malate, bis (triphenylsilyl) malate, bis (dimethyllaurylsilyl) malate, bis (dimethylstearylsilyl) malate, bis (dimethylphenylsilyl) malate, bis (n-butyldiphenylsilyl) malate, bis (T-Butyldiphenylsilyl) malate, bis (cyclohexyldiphenylsilyl) malate, tri-n-butylsilylmethyl itaconate, tri-n-butylsilyl-n-butyl itaconate, tri-n-butylsilyl lauryl itaconate, tri -I-propylsilylmethyl itaconate, tri-i-propylsilyl-n-butyl itaconate, tri-i-propylsilyl lauryl itaconate,
Bis (tri-n-butylsilyl) itaconate, bis (tri-i-propylsilyl) itaconate, bis (triphenylsilyl) itaconate, bis (dimethyllaurylsilyl) itaconate, bis (dimethylphenylsilyl) itaconate, bis (n-butyl) Diphenylsilyl) itaconate, bis (cyclohexyldiphenylsilyl) itaconate, tri-n-butylsilylmethyl fumarate, tri-n-butylsilyl-n-butyl fumarate, tri-n-butylsilyllauryl fumarate, tri-n-butyl Silyl stearyl fumarate, tri-i
-Propylsilylmethyl fumarate, tri-i-propylsilyl-n-butyl fumarate, bis (tri-n-butylsilyl) fumarate, bis (tri-i-propylsilyl) fumarate, bis (triphenylsilyl) fumarate, bis (Dimethyllaurylsilyl) fumarate, bis (dimethylphenylsilyl) fumarate, bis (n-
Butyldiphenylsilyl) fumarate, bis (t-butyldiphenylsilyl) fumarate, bis (cyclohexyldiphenylsilyl) fumarate and the like.

The monomer B which is a constitutional unit of the copolymer AB includes methyl (meth) acrylate and ethyl (meth).
Acrylate, n-butyl (meth) acrylate, i-
Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) such as 4-hydroxybutyl (meth) acrylate and dimethylaminoethyl (meth) acrylate
Acrylic esters; vinyl chloride, vinylidene chloride,
Functionality of (meth) acrylonitrile, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, Veova (trade name of Shell Co., vinyl ester monomer), i-butyl vinyl ether, lauryl vinyl ether, N-vinyl pyrrolidone, etc. Group-containing vinyl compounds; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; unsaturated dibasic acids such as dimethylmalate, di-n-butylmalate, dimethylfumarate and di-n-butylfumarate A dialkyl ester compound of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, monomethyl maleate, mono-n-butyl maleate,
Monolauryl malate, monostearyl malate, fumaric acid, monomethyl fumarate, mono-n-butyl fumarate, monolauryl fumarate, monostearyl fumarate, itaconic acid, monomethyl itaconate, mono-n
-Unsaturated carboxylic acid compounds such as butyl itaconate, monolauryl itaconate and monostearyl itaconate. These Monomer B together with Monomer A
One kind or two or more kinds can be used.

In the present invention, the copolymer AB is preferably used from the viewpoint of easily controlling the consumption rate of the coating film. The copolymerization ratio of the copolymer AB may be appropriately determined in consideration of coating film physical properties, consumption rate, etc., but the molar ratio of the monomer A and the monomer B is usually 10:90 to 90:10, especially The range of 20:80 to 60:40 is preferable. When the proportion of the monomer A is more than the above range, the consumption rate of the coating film tends to be fast, while when the proportion of the monomer A is less than the above range, the consumption rate of the coating film tends to be slow.

The weight average molecular weight of the polymer A or the copolymer AB is 5,000 to 500,000, especially 10,
The range of 000 to 200,000 is preferable. When the weight average molecular weight is less than the above range, the coating film tends to be brittle and weak, while when the weight average molecular weight exceeds the above range, the coating film tends to be strong, but it tends to be difficult to dissolve in seawater.

The synthesis method of the polymer A or the copolymer AB is as follows:
It is optional and can be synthesized by a known polymerization method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method or a bulk polymerization method using various radical polymerization catalysts such as organic peroxides and azo compounds. .

A vehicle comprising such a polymer A or / and a copolymer AB is usually contained in the total solid content of the coating material in an amount of 5%.
It is preferable to set the ratio to be about 80% by weight.

The organosilicon compound used in the present invention is a compound represented by the above formula (II).

In the formula (II), the alkyl group having 1 to 18 carbon atoms represented by R ^{4 to} R ⁸ and R ⁹ , the cycloalkyl group, the aryl group and the aralkyl group are the above-mentioned R ¹
To R ³ are exemplified.

When the organosilicon compound used in the present invention remains in the coating film for a long period of time, the water resistance of the coating film can be improved and the consumption rate can be controlled.

If the total number of carbon atoms of the groups represented by R ^{4 to} R ⁸ is too small, the boiling point of the organic silicon compound is low and the organic silicon compound also volatilizes along with the evaporation of the solvent in the coating film, and almost all remains in the coating film. Will not do. From this point, the total number of carbon atoms of the groups represented by R ^{4 to} R ⁶ is preferably 6 or more.

Specific examples of the organic silicon compound include, for example, tri-n-propylsilanol, tri-i-propylsilanol, tri-n-butylsilanol and tri-.
i-butyl silanol, tri-s-butyl silanol,
Silanol compounds such as triphenylsilanol, tribenzylsilanol, tri-2-ethylhexylsilanol, dimethyllaurylsilanol, dimethylstearylsilanol, dimethylphenylsilanol, n-butyldiphenylsilanol, t-butyldiphenylsilanol, lauryldiphenylsilanol, cyclohexyldiphenylsilanol. Hexa-n-propyldisiloxane, hexa-i-propyldisiloxane, hexa-
n-butyldisiloxane, hexa-i-butyldisiloxane, hexa-s-butyldisiloxane, hexaphenyldisiloxane, hexabenzyldisiloxane, hexa-2-ethylhexyldisiloxane, tetramethyldilauryldisiloxane, tetramethyldisiloxane Stearyldisiloxane, tetramethyldiphenyldisiloxane, di-n
-Siloxane compounds such as butyltetraphenyldisiloxane, di-t-butyltetraphenyldisiloxane, dilauryltetraphenyldisiloxane, dicyclohexyltetraphenyldisiloxane; tri-n-propylchlorosilane, tri-i-propylchlorosilane, tri- n-butylchlorosilane, tri-i-butylchlorosilane, tri-s-butylchlorosilane, triphenylchlorosilane, tribenzylchlorosilane, tri-2-ethylhexylchlorosilane, dimethyllaurylchlorosilane, dimethylstearylchlorosilane, dimethylphenylchlorosilane, n-butyldiphenyl Chlorosilane such as chlorosilane, t-butyldiphenylchlorosilane, lauryldiphenylchlorosilane and cyclohexyldiphenylchlorosilane. Run compound; tri-n-propylsilane, tri-i-propylsilane, tri-n-butylsilane, tri-i-butylsilane, tri-s-butylsilane, triphenylsilane, tribenzylsilane, tri-2-ethylhexylsilane, Examples thereof include silyl hydride compounds such as dimethyllaurylsilane, dimethylstearylsilane, dimethylphenylsilane, n-butyldiphenylsilane, t-butyldiphenylsilane, lauryldiphenylsilane and cyclohexyldiphenylsilane. These organosilicon compounds are used alone or in combination of two or more.

The organic silicon compound is preferably a liquid or solid compound having a boiling point of 150 ° C. or higher at normal pressure.
When the boiling point is less than 150 ° C., the coating film is likely to volatilize during drying, so that the amount remaining in the coating film is small and the expected effect cannot be exhibited.

In the present invention, the amount of the organic silicon compound used is 0.1 to 30% by weight, preferably 0.1 to 20% by weight, based on the solid content in the coating composition.
Even if the organosilicon compound exceeds 30% by weight, no further effect can be expected.

In the present invention, the method of mixing the organosilicon compound is not particularly limited, and a method of adding it at the time of synthesizing the polymer, a method of adding it at the time of preparing the coating material, or a method immediately after the preparation thereof can be used.

The coating composition of the present invention contains the above-mentioned organosilicon-containing polymer and an organosilicon compound as essential components, and if necessary, cuprous oxide, zinc oxide, rouge, titanium dioxide,
Pigments such as talc, dioctyl phthalate (DOP),
Trickle diphosphate (TCP), plasticizer such as chlorinated paraffin, acrylic resin, chlorinated rubber, resin such as rosin, tetrachloroisophthalonitrile, 3,4-dichlorophenyl-1,1-dimethylurea, 2-mercaptopyridine N -Organic agents such as zinc oxide, ethyl silicate, ethyl orthoformate, water binders such as zeolites, solvents such as xylene, toluene, butyl acetate, methyl isobutyl ketone, thixotropic agents, dyes and the like can be used.

The coating composition of the present invention is excellent in physical properties, adhesiveness and water resistance when formed into a coating film, and is used for cooling the bottom of ships, fish nets, power plants, etc., where it is necessary to prevent biofouling in the sea. It can be used for water conduits and undersea structures, and can maintain an excellent antifouling effect against biofouling stains on the surface of these objects for a long period of time.

[0034]

EXAMPLES Next, the present invention will be specifically described with reference to production examples, examples and comparative examples. Parts and% in the examples are by weight. The molecular weight indicates the weight average molecular weight (in terms of polystyrene) by GPC.

Production Examples 1 to 7 A flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with a reaction solvent in accordance with the blending ratio shown in Table 1, heated to a predetermined temperature and stirred. Monomer A,
Mix the mixed solution of the monomer B and the polymerization catalyst a into the flask.
After the dropping, the temperature was maintained for 1 hour at the same temperature. Then, after adding the polymerization catalyst b, stirring was continued for 1 hour at the same temperature, and then a diluent solvent was added and cooled to obtain each of the polymer solutions A to G.

[0036]

[Table 1]

Examples 1 to 8 and Comparative Examples 1 and 2 Polymer solutions, organosilicon compounds, pigments, other resins, organic antifouling agents, water binders and solvents were mixed and dispersed according to the blending ratios shown in Table 2. To prepare a coating composition.

[0038]

[Table 2]

The paints of Examples 1 to 8 and Comparative Examples 1 and 2 above were subjected to a water resistance test, a coating film consumption test and an antifouling performance test by the following methods.

<Water resistance test> Each of the paints prepared in Examples 1 to 8 and Comparative Examples 1 and 2 was 70 mm x 150 m.
Approximately 100 μm of dry coating on one side of a glass plate of mx 1 mm
To the temperature of 40 ° C and dried for 1 day in an oven at a temperature of 40 ° C. Then, each test piece is immersed in natural seawater kept at a temperature of 30 ° C and pulled out from the seawater every two weeks, and the temperature is raised to 40 ° C. After drying in an oven at ℃ for 1 day, the state of the coating film was observed. The test results are shown in Table 3.

[0041]

[Table 3]

<Coating Film Consumability Test> Each of the paints prepared in Examples 1 to 8 and Comparative Examples 1 and 2 was 70 mm × 150.
A 1 mm × 1 mm hard polyvinyl chloride plate was coated on one side with an applicator so that the dry coating film had a thickness of about 100 μm, and dried in an oven at a temperature of 40 ° C. for 1 day to give a test piece. After fixing each test piece to the outer surface of a cylindrical drum having a diameter of 50 cm, the test piece was immersed in natural seawater having a pH of 8.1 to 8.2 at 25 ° C. and rotated by a motor so that the peripheral speed of the drum was 20 knots. The state of the coating film of each test piece was observed every three months, and the amount of consumption of the coating film was measured to obtain the consumption rate (μm / month). The results are shown in Table 4.

[0043]

[Table 4]

<Anti-fouling performance test> Each of the paints prepared in Examples 1 to 8 and Comparative Examples 1 and 2 was 100 mm × 200.
Apply a dry coating film on both sides of a 2mm x 2mm rigid polyvinyl chloride plate with a brush to a temperature of 40 ° C.
Was dried in an oven for 1 day to prepare a test piece. This test piece was immersed in Owase Bay, Mie Prefecture, for 18 months at a depth of 1 m below the sea level, and the ratio of the area occupied by adherent organisms on the coating film of the test piece was observed and measured over time. The results are shown in Table 5.

[0045]

[Table 5]

[0046]

The antifouling coating composition of the present invention in which a specific organosilicon compound is added to an organosilicon-containing polymer has the following properties:
It has excellent water resistance, the wear rate of the coating film is constant for a long time, and stable antifouling performance can be maintained for a long time.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hisashi Taniguchi 5-23-35 Mukonosou, Amagasaki City, Hyogo Prefecture 5A-203 (72) Inventor Shigeru Masuoka 138-6 Setagayacho, Hodogaya-ku, Yokohama, Kanagawa Prefecture 102 (72) Inventor Masayasu Ito 447-1 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa (56) References JP-A-9-220525 (JP, A) JP-A-63-46269 (JP, A) Special Kaihei 11-206993 (JP, A) JP 11-148022 (JP, A) JP 10-168350 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 4 / 00-7/14 C09D 101/00-201/10

Claims (3)

(57) [Claims] 1. A) At least one of the following formulas in the molecule: embedded image [In the formula, R ^{1 to} R ³ are each a group selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group, and they may be the same or different. Group, and at least one of R ^{1 to} R ³ has a carbon number of 3 or more], in an antifouling coating composition using an organosilicon-containing polymer having a triorganosilicon ester group as a vehicle, B). The following formula: [In the formula, R ^{4 to} R ⁸ are each a group selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group, and they may be the same or different. It may be a group, and the total number of carbon atoms of R ^{4 to} R ⁶ is 6 or more, and R ⁹ is a hydrogen atom, a chlorine atom, a hydroxyl group or an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, And a group selected from the group consisting of aralkyl groups, and n is 0 or 1]. 2. The antifouling paint composition according to claim 1, wherein the organosilicon compound is contained in an amount of 0.1 to 30% by weight based on the solid content of the paint. 3. The organosilicon polymer is a (meth) acrylic acid ester copolymer having a triorganosilicon ester group, a maleic acid ester copolymer or a fumaric acid ester copolymer. Antifouling paint composition.