JPH0948949A - Antifouling coating composition, coating film formed from the antifouling coating composition, antifouling method using the antifouling coating composition, and hull or underwater structure coated with the coating film - Google Patents

Abstract

(57) Abstract: A film forming copolymer having a number average molecular weight of 1,000 to 50,000 and having a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight. An antifouling paint composition comprising a polymer, chlorinated paraffin, and zinc pyrithione as an antifouling agent, a coating film formed from the antifouling paint composition, and the antifouling film An antifouling method using a coating composition and a hull or underwater structure covered with the coating film. [Effect] Especially, it is possible to form an antifouling coating film with excellent slime resistance, crack resistance, peeling resistance, antifouling property, and self-polishing property (consumable property), and it also has excellent storage stability. An antifouling coating composition is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifouling coating composition, a coating film formed from this antifouling coating composition, an antifouling method using the antifouling coating composition, and a coating film with the coating film. Regarding the hull or underwater structure, more particularly, a self-polishing antifouling paint composition that is particularly excellent in slime resistance and the like, and can effectively prevent adhesion of aquatic organisms to the ship bottom, underwater structure, fishing net, etc., The present invention relates to a coating film formed from this antifouling coating composition, an antifouling method using the antifouling coating composition, and a hull or underwater structure covered with the coating film.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ship bottoms, underwater structures, fishing nets, etc.
By being exposed to water for a long period of time,
When animals such as barnacles, algae such as seaweed, or various aquatic organisms such as bacteria attach and reproduce,
The appearance may be impaired and its function may be impaired.

Particularly, when such aquatic organisms adhere to and propagate on the bottom of the ship, the surface roughness of the entire ship increases, which may lead to a decrease in ship speed and an increase in fuel consumption. Moreover, in order to remove such aquatic organisms from the bottom of the ship, a great deal of labor and work time are required at the dock. Also, when bacteria adhere to and propagate on underwater structures and the like and slime (sludge-like substances) adhere thereto, they may rot and their physical properties may deteriorate, resulting in damage such as a significant reduction in life.

Conventionally, in order to prevent such damage,
As an antifouling paint with excellent antifouling properties on the ship bottom, for example,
A material containing a copolymer of tributyltin methacrylate and methyl methacrylate and cuprous oxide (Cu ₂ O) was applied. The copolymer in this antifouling paint is
In seawater is hydrolyzed Bisutoribuchiru tin oxide (tributyltin _{ether, Bu 3 Sn-O-SnBu} 3: B
u is a butyl group) or tributyltin halide (B
u ₃ SnX: X is an organic tin compound such as a halogen atom) and exerts an antifouling effect, and the hydrolyzed copolymer itself becomes water soluble and dissolves in seawater. Since it is a "self-polishing paint,"
No resin residue remains and an active surface can always be maintained.

However, such an organic tin compound is highly toxic and may cause marine pollution, malformed fish, adverse effects on the ecosystem due to the food chain, etc. Development of paint is required.

Examples of such tin-free antifouling paints include, for example, JP-A-4-264170 and JP-A-4-264170.
The silyl ester antifouling paints described in JP-A No. 264169 and JP-A No. 4-264168 are mentioned. However, for these antifouling paints, Japanese Patent Laid-Open No. 15794/1994
As taught in Japanese Patent Application Laid-Open No. 1 and Japanese Patent Application Laid-Open No. 6-157940, there is a problem that the antifouling property is poor and cracks and peeling occur.

Further, in Japanese Patent Laid-Open No. 2-196869, trimethylsilyl methacrylate, ethyl methacrylate and methoxyethyl acrylate are copolymerized in the presence of an azo-based polymerization initiator to obtain a carboxylic acid group blocked by a trimethylsilyl group. Antifouling paints containing a blocked acid-functional copolymer (A) containing and a compound (B) of a polyvalent cation are taught, examples of which include the above-mentioned acid-functional copolymer (A). An antifouling paint containing a chlorinated paraffin plasticizer in addition to a compound of a polyvalent cation is disclosed. However, the coating film obtained from the antifouling paint disclosed in this Example,
There is a problem that crack resistance is not sufficiently satisfactory. That is, this Japanese Patent Application Laid-Open No. 2-196869 teaches what kind of chlorinated paraffin and in what amount the antifouling paint is excellent in crack resistance, storage stability, especially crack resistance. It has not been.

In JP-A-60-500452 and JP-A-63-215780, a vinyl-based monomer having an organosilyl group such as a trialkylsilyl ester of (meth) acrylic acid is used as another vinyl-based monomer. A resin for antifouling paints, which is copolymerized with a monomer and has a number average molecular weight of 3,000 to 40,000, is described, and further, an organic water binder such as trimethyl orthoformate, an antifouling agent such as cuprous oxide, red iron oxide Although it is described that pigments and the like can be blended, as described in JP-A-6-157940,
This resin for antifouling paint is apt to gel during storage, and a coating film formed from this antifouling paint is inferior in crack resistance and peeling resistance.

Further, in Japanese Examined Patent Publication No. 52324/1993, which corresponds to the above-mentioned Japanese Patent Publication No. 60-500452, the poison (a) and the formula [(-CH ₂ -CXCOOR)-(B)-: X are H or is CH _3, R is SiR _'3 or Si (oR') ₃ in R 'represents an an alkyl group, B has a repeating unit represented by showing the ethylenically unsaturated monomer residue] , An antifouling coating composition comprising a polymer binder (b) having a specific hydrolysis rate and the like, further comprising a solvent, a water-sensitive pigment component,
Although it is described that an inert pigment, a filler, and a retarder may be contained, a coating film obtained from the antifouling paint described in this publication,
There is a problem that it is inferior in crack resistance.

In Japanese Patent Application Laid-Open No. 7-18216, A) has the formula: --COO--SiR ¹ R ² R ³ (R ^{1 to} R ³ represent an alkyl group having 1 to 18 carbon atoms) in the molecule. In a coating composition mainly composed of an organosilicon-containing polymer having a triorganosilicon ester group represented by the above and B) copper or a copper compound, as an essential component other than the above A and B components, C) formula:

[0011]

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(R ^{4 to} R ⁶ represent a hydrogen atom, an alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group, etc., and R ⁷
Represents an alkyl group having 1 to 18 carbon atoms, and n is 1 to 3
The coating composition containing an alkoxy group-containing silicon compound represented by the formula (1) is disclosed. Further, in the column of composition and action of the invention of the publication, the coating composition contains chlorinated paraffin, etc. It is described that a plasticizer, a resin such as an acrylic resin, and the like may be contained if necessary. However, the coating film obtained from the coating composition described in this publication has a problem that it is inferior in crack resistance.

In Japanese Patent Laid-Open No. 7-102193, the formula:

[0014]

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(In the formula, R ^{1 to} R ³ are all selected from an alkyl group and an aryl group, and may be the same group or different groups. X is a group. . acryloyloxy group, methacryloyloxy group, a maleoyl group or fumaroyloxy group) and a monomer a represented by the _{formula: Y- (CH 2 CH 2 O} ) n -R 4 ( where R ⁴ is an alkyl A group or an aryl group, Y is an acryloyloxy group or a methacryloyloxy group,
n is an integer of 1 to 25. The coating composition which contains the copolymer of the monomer mixture containing the monomer B represented by this) and an antifouling agent as an essential component is disclosed.

[0016]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is particularly excellent in slime resistance, crack resistance, peel resistance, antifouling property, and self-polishing. It is an object of the present invention to provide an antifouling coating composition capable of forming an antifouling coating film having excellent properties (consumability) and having excellent storage stability.

The present invention also provides a coating film formed from such an antifouling coating composition, an antifouling method using the antifouling coating composition, and a hull or underwater structure coated with the coating film. It is intended to be provided.

[0018]

The antifouling coating composition according to the present invention has a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight and a number average molecular weight of 1000 to. It is characterized by containing 50,000 film-forming copolymers, chlorinated paraffin, and zinc pyrithione as an antifouling agent.

In the present invention, the chlorinated paraffin is contained in an amount of 10 to 100 parts by weight of the film-forming copolymer.
65 parts by weight, preferably 18 to 55 parts by weight, more preferably 20 to 50 parts by weight, particularly preferably 20 to 40 parts by weight, and zinc pyrithione in an amount of 0.5 to 60 parts by weight.
It is preferably contained in an amount of 0 parts by weight, preferably 1 to 500 parts by weight.

In the present invention, it is preferable that the antifouling agent further contains copper or a copper compound (eg, cuprous oxide) in addition to the zinc pyrithione, and contains zinc white. In the present invention, the chlorinated paraffin preferably has an average carbon number of 8 to 30 and a chlorine content of 35 to 75%.

In a preferred embodiment of the present invention, the trialkylsilyl ester is a trialkylsilyl ester in which at least one of the three alkyl groups bonded to the silicon atom of the ester has 3 or more carbon atoms. Esters are desirable, and those in which the number of carbon atoms of these three alkyl groups are all 4 or more are preferable, and tributylsilyl (meth) acrylate is particularly preferable.

The antifouling coating film according to the present invention is formed from the above antifouling coating composition. The antifouling method for a hull or underwater structure according to the present invention is characterized by using the above antifouling coating composition.

The antifouling coating-coated hull or underwater structure according to the present invention is characterized in that the surface of the hull or underwater structure is coated with a coating film comprising the above antifouling coating composition.

According to such a one-pack type antifouling coating composition of the present invention, it is particularly excellent in slime resistance, crack resistance, and peeling resistance to a substrate such as a ship bottom or a primer layer. It has excellent physical properties such as antifouling property, and can form antifouling coating film with excellent wear resistance (self-polishing property). In addition, this antifouling coating composition also has excellent storage stability. There is.

[0025]

DETAILED DESCRIPTION OF THE INVENTION The antifouling coating composition according to the present invention will be specifically described below. [ Film Forming Copolymer ] The antifouling coating composition according to the present invention contains the following film forming copolymer, chlorinated paraffin, and zinc pyrithione as an antifouling agent. The film-forming copolymer has a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight and has a number average molecular weight of 10%.
It is from 00 to 50,000.

This trialkylsilyl ester has, for example, the following formula [I]:

[0027]

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It is represented by In this formula [I], R¹Is hydrogen
Represents an atom or an alkyl group such as a methyl group, R², R^ThreeOh
And R^FourIs a methyl group, ethyl group, propyl group, butyl
Represents an alkyl group having 1 to 18 carbon atoms, such as a group, R
², R^ThreeAnd R^FourMay be different from each other and are the same
You may. With such a trialkylsilyl ester
Specifically, for example, trimethacrylate (meth) acrylate
Methylsilyl ester, triethyl (meth) acrylate
Silyl ester, tripropylsilyl (meth) acrylate
Ester, (meth) acrylate tributylsilyl ester
R such as tell ², R^ThreeAnd R^FourSame triki
Rusilyl ester, dimethyl propy (meth) acrylate
Rusilyl ester, (meth) acrylic acid monomethyl dip
Ropylsilyl ester, methyl (meth) acrylate
R such as rupropylsilyl ester², R^ThreeAnd R
^FourSome or all of them are different from each other
Lusilyl ester and the like. In the present invention
Is one such trialkylsilyl ester
May be used, or two or more kinds may be used in combination.
Yes. Among such trialkylsilyl esters,
R², R^ThreeAnd R^FourAt least one alkyl of
It is preferable that the group has 3 or more carbon atoms.
The number of carbon atoms of all three alkyl groups of is 4 or more
Preferred, and R², R^ThreeAnd R^FourThe total carbon number of
It is preferably about 5 to 21. Such a triarch
Among the silyl esters, especially trialkylsilyl
Ease of ester synthesis, or
Film formation of antifouling coating composition using rusilyl ester
, Storage stability, controllability of scouring ability, etc. are considered.
Then, (meth) acrylic acid tributylsilyl ester
Most preferably used.

As the monomer (comonomer) copolymerized with such a trialkylsilyl ester, any polymerizable unsaturated compound (ethylenically unsaturated monomer) can be used. Specific examples of the saturated compound include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, and (meth)
Acrylic acid 2-ethylhexyl ester, (meth) acrylic acid cyclohexyl ester, and other (meth) acrylic acid alkyl esters, styrene, α-methylstyrene, and other styrenes, vinyl acetate, vinyl propionate, and other vinyl esters. And methacrylic acid methyl ester (MMA) is preferably used.
Such MMA is usually contained in a comonomer (ethylenically unsaturated monomer) in an amount of 30% by weight or more, preferably 50% by weight or more.
It is preferably contained in an amount of not less than wt%, and a copolymer containing MMA in such an amount has a high glass transition temperature (Tg) of, for example, 30 to 60 ° C., which will be described later. The strength of the coating film made of the antifouling coating composition containing chlorinated paraffin is not lowered.

The component unit derived from a polymerizable unsaturated compound such as (meth) acrylic acid alkyl ester and the component unit derived from a trialkylsilyl ester are used as raw materials in the copolymer. The ethylene bond of each of the obtained monomers is cleaved to normally bond randomly.

When a carboxylic acid residue is present in such a copolymer, the storage stability of the resulting antifouling coating composition is significantly reduced, so that the carboxylic acid residue in the copolymer is The absence of acid residues is desirable. At the time of synthesizing the copolymer, it is preferable to use a high-purity monomer having no carboxylic acid residue.

In such a film-forming copolymer, as described above, one or more component units derived from trialkylsilyl ester of polymerizable unsaturated carboxylic acid as described above (tri Alkyl silyl ester component units) may be contained, but such a trialkyl silyl ester component unit has a total amount of 20 to 6
When contained in the copolymer in an amount of 5% by weight, preferably 30 to 55% by weight, an antifouling coating film excellent in long-term antifouling property can be obtained from the antifouling coating composition. Therefore, it is preferable.

The number average molecular weight (Mn) of this copolymer measured by GPC is 1,000 to 50,000, preferably 2,000 to 20,000, more preferably 2,500.
˜15,000, particularly preferably 3,000 to 12,000, and the weight average molecular weight (Mw) is usually 1,000 to
150000 (150,000), preferably 2000-600
00 (60,000), more preferably 3000 to 30000
(30,000), and the molecular weight distribution (Mw / Mn) of this copolymer is usually 1.0 to 4.0, preferably 1.0 to 3.0, and particularly preferably 1.0. ~ 2.5
The glass transition temperature (Tg ° C) of this copolymer is usually 15 to 80 ° C, preferably 25.
To 80 ° C, more preferably 30 to 70 ° C, particularly preferably 35 to 60 ° C, and the viscosity of this copolymer in, for example, 50% xylene solution (25
C, CPS) is usually 30 to 1000, preferably 40.
It is desirable that it is ˜600.

When the number average molecular weight of this copolymer is within the above range (1000 to 50,000), long-term antifouling properties of the coating film, damage resistance (impact resistance) of the formed coating film and the obtained film can be obtained. The coating composition will have excellent storage stability and crack resistance of the coating film.

Specific examples of such a film-forming copolymer (silyl ester copolymer) include the followings, preferably the numbering, more preferably the numbering shown in the numbering. A sex copolymer is used. It is a copolymer of tributylsilyl methacrylate (a) and methyl methacrylate (MMA), and the copolymerization ratio ((a) / (MMA): weight ratio) is 35-65 / 65-3.
5 (total component 100 parts by weight) and number average molecular weight (Mn) of 1,000 to 50,000, preferably 3,000 to 12
000 and the weight average molecular weight (Mw) is 1000 to 1
50,000, preferably 3000 to 30000 (30,000), molecular weight distribution (Mw / Mn) is 1.0 to 4.0, preferably 1.0 to 2.5, and glass transition temperature (Tg
C) is 30 to 70 ° C, preferably 35 to 60 ° C,
For example, the viscosity in a 50% xylene solution (25 ° C,
CPS) is 30 to 1000, preferably 40 to 600
Of: a copolymer of tripropylsilyl methacrylate (II), methyl methacrylate (MMA) and 2-ethylhexyl acrylate (III), the copolymerization ratio of which is ((II) / (M
(MA) / (C): weight ratio) is 25 to 55/74 to 35/1 to 1
0 (total component 100 parts by weight) and number average molecular weight (Mn) of 1,000 to 50,000, preferably 3,000 to 12
000 and the weight average molecular weight (Mw) is 1000 to 1
50,000, preferably 3000 to 30000 (30,000), molecular weight distribution (Mw / Mn) is 1.0 to 4.0, preferably 1.0 to 2.5, and glass transition temperature (Tg
C) is 30 to 70 ° C, preferably 35 to 60 ° C,
For example, its viscosity in a 50% xylene solution (25 ° C,
CPS) is 30 to 1500, preferably 40 to 100
No. 0: a copolymer of tributylsilyl methacrylate (a), tripropylsilyl methacrylate (b) and methyl methacrylate (MMA) having a copolymerization ratio ((a)
/ (B) / (MMA): weight ratio) is 30-60 / 1-20 / 69
To 20 (total 100 parts by weight of all components) and number average molecular weight (Mn) of 1,000 to 50,000, preferably 3,000 to 1
2000, and the weight average molecular weight (Mw) is 1000 to
150,000, preferably 3000 to 30000 (30,000), molecular weight distribution (Mw / Mn) of 1.0 to 4.0, preferably 1.0 to 2.5, glass transition temperature (Tg
C) is 30 to 60 ° C, preferably 35 to 55 ° C,
For example, its viscosity in a 50% xylene solution (25 ° C,
CPS) is 30 to 1000, preferably 40 to 400
Of: Tributylsilyl methacrylate (a), tripropylsilyl methacrylate (b), methyl methacrylate (MMA), and 2-ethylhexyl acrylate (c)
And a copolymerization ratio ((a) / (b) / (MM
(A) / (C): weight ratio) is 30 to 60/1 to 20/68 to 1
9/1 to 10 (total 100 parts by weight of all components) and number average molecular weight (Mn) of 1,000 to 50,000, preferably 300.
0 to 12,000 and a weight average molecular weight (Mw) of 10
00 to 150,000, preferably 3000 to 30000 (3
10,000) and the molecular weight distribution (Mw / Mn) is 1.0 to
It is 4.0, preferably 1.0 to 2.5, and has a glass transition temperature (Tg ° C) of 30 to 60 ° C, preferably 35 to 55.
C., for example, its viscosity in a 50% xylene solution (25 ° C., CPS) is 30 to 1000, preferably 4
0 to 400: A copolymer of tributylsilyl methacrylate (a), methyl methacrylate (MMA), and 2-ethylhexyl acrylate (c), the copolymerization ratio ((a) /
(MMA) / (C): weight ratio) is 35-65 / 64.9-34.
9 / 0.1-10 (total 100 parts by weight of all components),
Number average molecular weight (Mn) is 1000 to 50,000, preferably 3
000 to 12,000 and a weight average molecular weight (Mw) of 1,000 to 150,000, preferably 3,000 to 30,000.
(30,000) and the molecular weight distribution (Mw / Mn) is 1.0
To 4.0, preferably 1.0 to 2.5, and a glass transition temperature (Tg ° C) of 30 to 70 ° C, preferably 35 to 6
0 ° C., for example, having a viscosity (25 ° C., CPS) in a 50% xylene solution of 30 to 1000, preferably 40 to 600: triisopropylsilyl acrylate (d), methyl methacrylate (MMA) and ethyl acrylate A copolymer with (e), which has a copolymerization ratio ((d) / (MMA) / (e):
(Weight ratio) is 40 to 65/59 to 20/1 to 20 (total weight of all components is 100 parts by weight), and the number average molecular weight (Mn) is 1.
000 to 50,000, preferably 3000 to 30,000 (3
10,000) and the weight average molecular weight (Mw) is 1000 to 15
10,000, preferably 3000 to 30,000, and the molecular weight distribution (M
w / Mn) is 1.0 to 4.0, preferably 1.0 to 3.
0, the glass transition temperature (Tg ° C) is 20 to 80 ° C,
The temperature is preferably 25 to 75 ° C., for example, the viscosity (25 ° C., CPS) in a 50% xylene solution is 30 to 15
00, preferably 40 to 1300, a copolymer of triisobutylsilyl methacrylate (f), methyl methacrylate (MMA) and 2-ethylhexyl acrylate (c) at a copolymerization ratio ((f)
/ (MMA) / (C): weight ratio) is 35-65 / 64.9-3
4.9 / 0.1-10 (total 100 parts by weight of all components), number average molecular weight (Mn) of 1,000 to 50,000, preferably 3,000 to 12,000, and weight average molecular weight (M
w) is 1000 to 150,000, preferably 3000 to 300
00 (30,000), and the molecular weight distribution (Mw / Mn) is 1.
0-4.0, preferably 1.0-2.5, glass transition temperature (Tg ° C) 25-80 ° C, preferably 30-
70 ° C., for example, one having a viscosity (25 ° C., CPS) in a 50% xylene solution of 30 to 2000, preferably 40 to 1500.

To prepare such a film-forming copolymer, for example, usually under an inert atmosphere such as a nitrogen stream,
In an organic solvent such as xylene, trialkylsilyl ester such as tributylsilyl methacrylate and methyl methacrylate in a comonomer are 50% by weight or more (for example, 8%).
0% by weight) and a polymerizable unsaturated compound contained in an amount of
In the presence of a polymerization initiator such as an azo type or a peroxide type such as 2,2′-azobisisobutyronitrile, and a polymerization regulator such as n-octyl mercaptan if necessary,
The reaction may be performed by a method such as radical polymerization at a temperature of about 50 to 120 ° C. for about 2 to 12 hours.

The film-forming copolymer thus obtained contains each component unit in an amount corresponding to the amount of each monomer used. The polymerization method is not limited to the simple radical solution polymerization method described above, and various conventionally known methods can be adopted. In addition to the above-mentioned aromatics (eg, xylene), the solvent can be arbitrarily selected from various solvents commonly used for paints such as aliphatic, ketone, ester and ether. As the solvent,
In particular, a solvent having a low water content is preferable, and use of such a low water content solvent is preferable because it is possible to avoid the hydrolysis reaction during and after the above reaction. Since the alcoholic solvent has a high initial water content and has reactivity with silanol, it is not appropriate to use it in the above reaction from this viewpoint.

[ Chlorinated Paraffin ] Chlorinated paraffin (chlorinated paraffin; salt para) is a crack resistance of a coating film (also referred to as "antifouling coating film" in the present specification) composed of the obtained antifouling coating composition. Such a chlorinated paraffin may be linear or branched, and may be liquid or solid (powder) at room temperature.
The average carbon number is usually 8 to 30, preferably 10 to 2.
No. 6 is preferably used, the number average molecular weight is usually 200 to 1200, preferably 300 to 1100, and the viscosity is usually 1 or more (poise / 25 ° C.), preferably 1.2 or more (poise / 25 ° C.). ), And its specific gravity is 1.05 to 1.80 / 25 ° C., preferably 1.10 to
Those of 1.70 / 25 ° C. are preferably used. When a chlorinated paraffin having such a carbon number is used, a coating film with less cracking and peeling can be formed using the resulting antifouling coating composition. The carbon number of the chlorinated paraffin is preferably in the range of 8 to 30 in view of the effect of suppressing cracks, the consumability (renewability) of the resulting coating film surface, and the antifouling property. The chlorination ratio (chlorine content: weight%) of this chlorinated paraffin is usually 35 to 75%, preferably 35 to 65%. When the chlorinated paraffin having such a chlorination rate is used, the resulting antifouling coating composition can be used to form a coating film with less cracking and peeling. The chlorination ratio of chlorinated paraffin depends on the miscibility (compatibility) with the film-forming copolymer (silyl ester copolymer), the effect of suppressing cracks, the surface of the resulting coating film, and the antifouling property. From the above point, it is preferably in the range of 35 to 75%. Examples of such chlorinated paraffins include Toyo Parax 150 and Toyo Parax A-70 manufactured by Tosoh Corporation. In the present invention, two or more kinds of chlorinated paraffins having different chlorine contents, carbon numbers, etc. can be appropriately combined and used. When two or more kinds of chlorinated paraffins are used in combination as described above, the carbon number and the chlorination rate of the chlorinated paraffin are the same as those of the chlorinated paraffin contained in the antifouling coating composition or chlorine. The average value of the conversion rate is shown.

In the antifouling coating composition of the present invention, such chlorinated paraffin is 10 to 65 parts by weight, preferably 18 to 55 parts by weight, based on 100 parts by weight of the above film-forming copolymer. Parts, more preferably 20 to 50 parts by weight, particularly preferably 20 to 40 parts by weight. The amount of chlorinated paraffin is 10
When the amount is in the range of from 65 to 65 parts by weight, the effect of suppressing cracks generated in the coating film formed from the antifouling coating composition is excellent, and the coating film strength and damage (impact) resistance are excellent.

[Antifouling agent (zinc pyrithione) ] As the antifouling agent, zinc pyrithione represented by the following formula [II]:
[Bis (1-hydroxy-2 (1H) -pyridinethionate-O, S) -zinc] is used.

[0041]

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In the present invention, in addition to such zinc pyrithione (2-pyridinethiol-1-oxide zinc salt), "another antifouling agent" may be contained. As the above, various conventionally known organic or inorganic antifouling agents can be used. Specifically, for example, cuprous oxide (Cu ₂ O), copper powder, and thiocyanated first
In addition to copper or copper compounds such as copper (Rhodan copper), the following formula [II
And a derivative thereof [wherein R ^{1 to} R ⁴ each independently represent hydrogen, an alkyl group, an alkoxy group, or a halogenated alkyl group, and M is Cu,
Metals such as Na, Mg, Ca, Ba, Pb, Fe and Al are shown, and n is a valence]:

[0043]

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Tetramethylthiuram disulphide,
Carbamate poisons (eg zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate), 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 4,5-
Examples thereof include dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,6-trichlorophenylmaleimide and pyridinetriphenylborane / rodane copper, and cuprous oxide is preferably used. In the present invention, such an antifouling agent is treated with zinc pyrithione (the above formula [I
I], that is, in the above formula [III], R ^{1 to} R ⁴ = H,
(Corresponding to M = Zn and n = 2), and one kind or a combination of two or more kinds can be used.

In the antifouling coating composition according to the present invention, the zinc pyrithione is usually 0.5 to 600 parts by weight, preferably 1.0 to 500 parts by weight, based on 100 parts by weight of the above film-forming copolymer. It is desirable that it is contained in the amount of parts. When the content of zinc pyrithione is in the range of 0.5 to 600 parts by weight, the slime resistance and the crack resistance are excellent.

The zinc pyrithione is usually contained in the antifouling coating composition in an amount of 0.1 to 30% by weight, and preferably 0.5 to 30% by weight.
It is preferably contained in an amount of 20% by weight. The slime resistance of the antifouling coating composition containing zinc pyrithione greatly depends on the content of the zinc pyrithione in the antifouling coating composition, and the content is 0.1 to 30% by weight. The slime resistance is excellent and the crack resistance of the antifouling coating film when the coating film (antifouling coating film) formed of the antifouling coating composition applied on the ship bottom is submerged is excellent.

Further, the antifouling coating composition according to the present invention comprises
The zinc pyrithione and "other antifouling agents" are the types of antifouling agents, film-forming copolymers, etc. used in the preparation of antifouling coating compositions, or vessels on which such antifouling coating compositions are applied and formed. Etc. (for ships, for ocean-coast, for various seawater areas, for wooden-steel vessels, etc.), etc., it is not generally determined, but with respect to 100 parts by weight of the film-forming copolymer, The total amount of the soiling agent is usually 50 to 1500 parts by weight, preferably 80 to 1200 parts by weight.

When the total amount of the antifouling agent is 50 to 1500 parts by weight, the antifouling property and the crack resistance are excellent.

For example, when zinc pyrithione and cuprous oxide (Cu ₂ O) are used in combination as an antifouling agent, zinc pyrithione is used in the amount as described above, and cuprous oxide is used in the above-mentioned film-forming copolymer. It may be contained in the antifouling coating composition in an amount of usually about 30 to 1200 parts by weight based on 100 parts by weight of the combined product. Thus, even if it contains zinc pyrithione and cuprous oxide, the antifouling coating composition of the present invention is excellent in storage stability unlike the antifouling coating composition according to the conventional example as described above, and thickens during storage.・ Does not gel.

In the conventional antifouling paint, when zinc pyrithione is added, thickening and gelation occur, and, for example,
As described in JP-A-6-25560,
In a copolymer of tributyltin methacrylate, methyl methacrylate and butyl acrylate, a hydrolyzable self-polishing antifouling paint containing zinc pyrithione and cuprous oxide is stored as described in the publication. It was inferior in stability and gradually thickened and gelled after long-term storage.
However, the antifouling coating composition of the present invention contains zinc pyrithione, or has excellent storage stability as described above despite containing zinc pyrithione and cuprous oxide as another antifouling agent. Does not thicken or gel inside.

In the antifouling coating composition, a divalent copper compound, such as copper naphthenate or copper octylate, or a divalent copper compound of the metal-containing resin composition described in JP-A-62-57464 is used. If the composition containing a copper compound is contained, the antifouling paint containing zinc pyrithione even in the conventional antifouling paint, zinc pyrithione in the antifouling paint is converted into copper-pyrithione by chelate exchange. It may change and the slime resistance of the antifouling paint may decrease, but it becomes difficult to thicken and gel during storage.

Such an antifouling coating composition according to the present invention contains a film-forming copolymer, chlorinated paraffin and zinc pyrithione. In addition to this, zinc white, a dehydrating agent, an anti-sagging agent, It may contain an anti-settling agent, a pigment, a solvent as described above, and the like.

In the antifouling coating composition containing zinc white,
Although the strength of the obtained coating film is improved and the scavenging property of the coating film can be effectively controlled, such zinc white is contained in an amount of 5 to 400 parts by weight based on 100 parts by weight of the film forming copolymer (polymer). It is preferable to blend in the amount of parts.

In the antifouling coating composition of the present invention, even if zinc pyrithione and zinc white are thus contained,
The antifouling paint composition is suppressed in viscosity and gelation tendency due to hydrolysis in the presence of water during storage of the antifouling paint composition, and has excellent storage stability.

The antifouling coating composition containing a dehydrating agent can further improve the storage stability. As such a dehydrating agent, for example, anhydrous gypsum (C
aSO ₄ ), synthetic zeolite adsorbent (trade name: molecular sieve, etc.), orthoesters such as methyl orthoformate, methyl orthoacetate, orthoborates, silicates and isocyanates (trade name: Additive T
I) and the like, and anhydrous gypsum and molecular sieves are preferable, and molecular sieves are particularly preferably used. Such dehydrating agents can be used alone or in combination of two or more. The molecular sieve is more preferably used than the anhydrous gypsum for the following reason. That is, when an antifouling coating composition containing anhydrous gypsum is applied, water-soluble hydrated gypsum precipitates on the surface of the coating film during sweating or rainfall after application, which causes whitening of the coating film. In some cases, and when the surface of the antifouling coating film is further overcoated, the effect on the overcoating property tends to occur. Therefore, in order to avoid these, it is particularly preferable to use a molecular sieve.

Further, in relation to such a dehydrating agent, the present invention will be described in more detail in comparison with the coating composition described in JP-A-7-18216. The antifouling coating composition of the present invention is as follows. Since the film-forming copolymer contains a relatively low molecular weight one, the thickening gelation during storage is suppressed to some extent even in an antifouling coating composition not containing the dehydrating agent. . Further, even if it is observed that the antifouling coating composition thickens to some extent during the long-term storage and tends to gel, the antifouling coating composition is diluted with an appropriately selected solvent to obtain a ship bottom, etc. If it can be applied to, the formed coating film has a consumable property (self-polishing property), and good antifouling property is recognized. Even in a coating film formed by applying and forming an antifouling coating composition that is thus thickened and gelled, it has a consumable property mainly in the amount as described above. This is probably because a low molecular weight film-forming copolymer and a (meth) acrylic acid ester-based polymer are used in combination.

On the other hand, the above-mentioned Japanese Unexamined Patent Publication No. 7-18216
In the coating composition described in Japanese Patent Laid-Open Publication No. 2003-242242, when a dehydrating agent is not added, a remarkable tendency of thickening gelation is observed during storage of the coating composition, and the coating composition thus thickened gel is applied to the ship bottom. In a coating film formed by coating on, etc., almost no consumable property is observed and the antifouling property is poor.

The anti-sagging / precipitation agent may be blended in any amount other than those which impair the storage stability of the antifouling coating composition such as organic clay. Examples of the anti-sagging / precipitation preventing agent include salts of Al, Ca and Zn such as stearate salts, lecithin salts and alkyl sulfonates, polyethylene wax, amide wax, hydrogenated castor oil wax type, polyamide wax type and Examples thereof include a mixture of the two, synthetic fine powder silica, and oxidized polyethylene wax, and hydrogenated castor oil wax, polyamide wax, synthetic fine silica, and oxidized polyethylene wax are preferably used. As such an anti-sagging / precipitation agent, "Disparlon 30" manufactured by Kusumoto Kasei Co., Ltd.
Examples include those marketed under product names such as "5" and "Disparon 4200-20".

As the pigment, in addition to scale-like pigments (example: mica powder) described below, various conventionally known organic and inorganic pigments (example: titanium white, red iron oxide) can be used. Note that various colorants such as dyes may be included.

As the solvent, for example, various solvents such as an aliphatic type, an aromatic type (eg, xylene, toluene, etc.), a ketone type, an ester type, an ether type and the like which are usually blended in an antifouling paint are used. .

[ Production of Antifouling Paint Composition ] Such an antifouling paint composition can be produced by appropriately utilizing a conventionally known method. For example, the above film-forming copolymer and Chlorinated paraffin in an amount of 18 to 65 parts by weight based on 100 parts by weight of the film-forming copolymer, and 0.5 to
Zinc pyrithione in an amount of 600 parts by weight, for example 30 to
Cuprous oxide in an amount of 1200, preferably 50 to 1200 parts by weight (provided that the total amount of antifouling agent is 50 to 1500, preferably 8
0-1200 parts by weight), zinc flower optionally used in an amount of 5-400 parts by weight, and an optional amount of dehydrating agent (eg, anhydrous gypsum, molecular sieve), anti-sagging / precipitation preventing agent,
The pigment, the solvent and the like may be added at once or in any order and stirred, mixed and dispersed.

This antifouling coating composition is a one-liquid type and has excellent storage stability, and, for example, a coating film (antifouling coating film) formed by coating this antifouling coating composition on the bottom of a ship is submerged. However, cracks in the antifouling coating film are suppressed. Further, when the antifouling coating composition is applied to the primer surface, peeling of the antifouling coating film from the applied primer surface is suppressed.
In addition, the antifouling coating composition of the present invention is coated with the various antifouling coating materials such as the bottom of a ship a plurality of times, or the antifouling coating composition of the present invention is used to form the antifouling coating film of the present invention. In the case of performing repair coating on the surface of the ship bottom, etc., the peeling of the surface antifouling coating film of the present invention from the previously applied antifouling coating film surface is suppressed. Moreover, in the antifouling coating film of the present invention formed by coating on the surface of the primer or the surface of the ship bottom to be repaired in this manner, its consumption can be controlled, and the required degree of consumption and protection can be adjusted according to the environment in which it is used. It is possible to provide dirty power. Therefore, this antifouling coating composition is economically excellent because the film thickness of the antifouling coating film to be formed can be maximally reduced depending on the application.

The antifouling coating composition according to the present invention contains, in addition to the antifouling agent, the film-forming copolymer, the chlorinated paraffin and the antifouling agent zinc pyrithione, the film-forming copolymer. Number average molecular weight compatible with 1000 to 10
0000 (100,000) (meth) acrylic acid ester-based polymer [homopolymer or copolymer of (meth) acrylic acid-based ester other than (meth) acrylic acid silyl ester] may be contained.

In the antifouling coating composition of the present invention, in addition to the antifouling agent, the film-forming copolymer, the chlorinated paraffin and zinc pyrithione, they are compatible with the film-forming copolymer. When the (meth) acrylic acid ester-based polymer is blended, the crack resistance of the resulting coating film can be further improved, and the seawater consumption rate of the coating film and the durability of the antifouling performance can be improved. When the antifouling coating composition of the present invention is overcoated on an existing antifouling coating film, the effect of further improving the adhesiveness of the resulting coating film can be exhibited. There is also an advantage that the crack resistance of the obtained coating film can be improved even if the compounding amount of the chlorinated paraffin is reduced.

As the (meth) acrylic acid ester-based polymer compatible with such a film-forming copolymer, other than the (meth) acrylic acid silyl ester used for preparing the above-mentioned film-forming copolymer. Examples thereof include homopolymers or copolymers of (meth) acrylic acid ester, and homopolymers of (meth) acrylic acid ester, copolymers of at least two or more (meth) acrylic acid esters, and (meth) acrylic. Examples thereof include acid ester / styrene copolymers. Such (meth) acrylic acid ester-based polymers can be used alone or in combination of two or more.

These (meth) acrylic acid ester-based polymers may be, for example, linear or branched, and have a crosslinked structure as long as they are compatible with the film-forming copolymer. You may have.

Here, the (meth) acrylic acid ester-based polymer "compatible with" the film-forming copolymer is also referred to as a film-forming copolymer (trialkylsilyl (meth) acrylate copolymer). ) Whether a xylene solution having a concentration of 30% by weight and a xylene solution having a concentration of a (meth) acrylic acid ester polymer of 30% by weight are mixed at a volume ratio of 1: 1 at 25 ° C. to form a transparent homogeneous solution. Or a (meth) acrylic acid ester-based polymer that forms a milky white uniform solution without forming a two-liquid separation layer.

When the number average molecular weight of the (meth) acrylic acid ester-based polymer is within the above range, cracks can be suppressed and the degree of wear can be effectively controlled, and the static There is a tendency that an antifouling coating film having excellent antifouling property can be formed. Further, when the number average molecular weight of the (meth) acrylic acid ester-based polymer exceeds the above range, the resulting antifouling coating film has a large effect of suppressing cracks and a large effect of reducing the degree of wear. Sex tends to decrease,
When the molecular weight of the (meth) acrylic acid ester-based polymer is smaller than the above range, the antifouling effect tends to be reduced even if the antifouling coating film obtained can be kept highly antifouling.

Examples of such a (meth) acrylic acid ester-based polymer include, for example, methyl (meth) acrylate,
Homopolymers of (meth) acrylic acid esters such as butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenyl (meth) acrylate, or these Copolymers of various monomers such as styrene (ST), aromatic vinyl compounds such as styrene (ST), vinyl acetate, vinyl chloride, ethylene, propylene, butadiene, vinyl ether compounds, and (meth) acrylic acid ester-based monomers. Can be mentioned.

Specific examples of such a (meth) acrylic acid ester-based polymer include: a copolymer of methyl methacrylate (MMA) and butyl methacrylate (BMA), Copolymerization ratio (indicated by weight ratio of each component; the same applies hereinafter) (MMA / BMA) is 30 to 70
/ 70 to 30 (total 100 parts by weight) and number average molecular weight of 1000 to 100,000, preferably 1000 to 5
A copolymer of isobutyl methacrylate (i-BMA), t-butyl methacrylate (t-BMA), styrene (ST) and stearyl methacrylate (SLMA), Polymerization ratio (i-BMA / t-BMA / ST / SLMA) is 10-40 / 10-40
/ 20 to 60/5 to 20 (total 100 parts by weight), and the number average molecular weight is 1000 to 100,000, preferably 1
Methyl methacrylate (MMA) homopolymer having a number average molecular weight of 1,000 to 100,000, preferably 10 to 80,000.
About 100 to 20,000: a homopolymer of ethyl methacrylate (EMA) having a number average molecular weight of 1,000 to 100,000, preferably 10
About 00 to 20,000: A copolymer of methyl methacrylate (MMA) and butyl acrylate (BA) having a copolymerization ratio (MMA / BA)
Is from 99 to 50/1 to 50 (total 100 parts by weight), and the number average molecular weight is from 1000 to 100,000, preferably 1
000 to 50,000 or so: A copolymer of ethyl methacrylate (EMA) and butyl acrylate (BA) having a copolymerization ratio (EMA / BA)
Is 100-70 / 0-30 (total 100 parts by weight of all components)
And those having a number average molecular weight of 1,000 to 100,000, preferably about 1,000 to 30,000.

Among such (meth) acrylic acid ester-based polymers, the hydrophobic acrylic polymer [(meth) acrylic acid ester content is preferably more than 50% by weight and styrene content is less than 50% by weight is preferable. Or a styrene-based polymer [having a styrene content of 50% by weight or more] is used, and the (meth) acrylic acid ester-based polymer with the numbering is particularly preferably used.

The glass transition temperature (Tg) of such a (meth) acrylic acid ester polymer is preferably 0 ° C. or higher, and particularly preferably 20 to 105 ° C. A (meth) acrylic acid ester polymer having a low glass transition temperature (Tg) (eg, butyl acrylate (BA) homopolymer) may have a low effect of suppressing cracks in the resulting antifouling coating film. .

Such a (meth) acrylic acid ester-based polymer is added to 100 parts by weight of the film-forming copolymer in the film-forming copolymer-containing antifouling coating composition containing no chlorinated paraffin. On the other hand, it is usually used in an amount of 10 to 200 parts by weight, but it can be further reduced in the antifouling coating composition containing this chlorinated paraffin, and it is 5 to 100 parts by weight of the film-forming copolymer. It can be used in an amount of 200 parts by weight.

That is, in such an antifouling coating composition, the antifouling agent is usually 50 to 1500 parts by weight, preferably 80 to 100 parts by weight with respect to 100 parts by weight of the film-forming copolymer.
It is contained in an amount of 1200 parts by weight, the (meth) acrylic acid ester-based polymer is contained in an amount of 5 to 200 parts by weight, preferably 10 to 200 parts by weight, and particularly preferably 15 to 160 parts by weight. Chlorinated paraffin is usually 5 to 1
It is contained in an amount of 50 parts by weight, preferably 8 to 100 parts by weight, and zinc pyrithione is usually contained in the antifouling agent in an amount of 0.5 to 0.5 parts by weight.
It is desirable that the amount is 600 parts by weight, preferably 1 to 500 parts by weight, and particularly preferably 2 to 400 parts by weight. When the chlorinated paraffin content is in the range of 5 to 150 parts by weight, the resulting antifouling coating film has an excellent effect of suppressing cracks and the resulting antifouling coating film has excellent mechanical strength.

Incidentally, in such a (meth) acrylic acid ester-based polymer, when a carboxylic acid residue is present, as in the case of the above film-forming copolymer, the obtained antifouling coating composition is obtained. In order to significantly reduce the storage stability of the product, it is desirable that the carboxylic acid residue does not exist in the (meth) acrylic acid ester-based polymer, and the acid value (AV value) of the polymer is usually 15 or less, It is preferable to use a monomer having no carboxylic acid residue so that the amount is preferably 10 or less, and particularly preferably 5 or less. Especially,
In the antifouling coating composition containing zinc white, as the acid value of the (meth) acrylic acid ester-based polymer exceeds zero and increases, the resulting antifouling coating composition becomes poor in storage stability and increases in storage stability. Stickiness and gelation tend to occur. This tendency is particularly remarkable in the antifouling coating composition of the present invention containing zinc pyrithione (ZPT).

In the antifouling coating composition containing the (meth) acrylic acid ester-based polymer as described above, for example,
Even if the coating film (anti-fouling coating film) formed of this anti-fouling coating composition applied on the ship's bottom is submerged, cracks in the anti-fouling coating film are suppressed, and consumption control is possible. Accordingly, it is possible to provide the required degree of wear and antifouling performance. Therefore, in the antifouling coating composition containing the (meth) acrylic acid ester-based polymer as described above, the film thickness of the antifouling coating film can be reduced to the maximum depending on the application. Is also excellent.

The antifouling coating composition according to the present invention contains the following antifouling agent, the above film-forming copolymer, the above chlorinated paraffin and zinc pyrithione, and the following scale-like pigment. It may be contained.

Examples of the scaly pigment include mica powder, scaly aluminum powder, copper powder, zinc dust and pearl pigment, and mica powder is preferably used. As such a mica powder ore, more specifically, white sprouts, beni-unmo, sawdown moth, sericite, vanadin-mom, illite, etc.
In addition to the kurounmo series such as Tetsuunmo and Chinwaldo moum, Kairyoku stone, Celadon stone and the like can be mentioned, but in general, crushed syllables are used.

The average particle size and aspect ratio of the flaky pigment are not particularly limited, but preferably the average particle size is 0.1 to 200 μm and the aspect ratio is (long side / short side of particle). The ratio of sides) is preferably 10 or more.

In such an antifouling coating composition, the antifouling agent is usually contained in an amount of 50 to 1500 parts by weight, preferably 80 to 1200 parts by weight, based on 100 parts by weight of the film-forming copolymer. The chlorinated paraffin is usually 5 to
It is contained in an amount of 65 parts by weight, preferably 8 to 55 parts by weight, the scaly pigment is usually contained in an amount of 1 to 100 parts by weight, preferably 5 to 90 parts by weight, and zinc pyrithione is usually 0.5 to 600 parts by weight. It is preferably contained in an amount of 1 part by weight, preferably 1 to 500 parts by weight. When the scaly pigment is in the range of 1 to 100 parts by weight, the addition effect and the antifouling effect are excellent.

The antifouling coating composition containing such a scale-like pigment can form an antifouling coating film which is particularly excellent in crack resistance in addition to the above effects. In general, it is considered that the addition of a flaky pigment to an antifouling coating composition is effective in improving the crack resistance of the resulting coating film. However, in the conventional antifouling paint, when a scale-like pigment having no physiological activity is blended, the elution of the antifouling agent from the resulting antifouling coating film is prevented, and the antifouling effect is significantly reduced. There was a problem with doing it. However, the antifouling coating film formed from the silyl ester antifouling coating composition (AF) having excellent self-polishing property (consumable property) as in the present invention has excellent surface renewal property in seawater,
Even if there are scale-like pigments on the surface of the coating film, it has sufficient renewal property of the coating film, and since it also has an extremely high level of antifouling activity, it controls excessive elution of the antifouling agent to an appropriate range. While maintaining (controlling), the generation of cracks after submersion can be suppressed more efficiently.

The film-forming copolymer is an antifouling agent which is a copolymer of (meth) acrylic acid tributylsilyl ester [TBS (M) A] and methyl (meth) acrylate [M (M) A]. the antifouling coating film made of the coating composition as an example, further specifically described in the seawater, hydroxide ions (OH ^-)
Under the influence of, for example, the tributylsiloxy group (Bu ₃ SiO-) in the film-forming copolymer is cut off from the carbonyl group (-CO-) bonded to the main chain of the copolymer to give tributylsilanol. It becomes (Bu ₃ SiOH) and dissolves in seawater. Meanwhile, polymers constituted the main chains of the carboxylic acid salt structure (-COO ^-), the contact surface between the seawater antifouling coating film for going to fall off, dissolved in seawater (antifouling coating film surface) Are expected to be updated one after another. Therefore, the antifouling agent contained in the antifouling coating film is promptly released from the surface of the antifouling coating film. However, when the scale-like pigment is contained in the coating material as described above, the contact between seawater and the antifouling agent and the film-forming copolymer is suppressed, and therefore, in the present invention, the effects as described above are obtained. Will be obtained.

The antifouling coating composition according to the present invention contains, in addition to the above antifouling agent, the above film-forming copolymer, the chlorinated paraffin and zinc pyrithione, the above (meth) acrylic acid ester-based polymer. And a scaly pigment may be contained.

In such an antifouling coating composition, the antifouling agent containing zinc pyrithione is the film-forming copolymer 10 described above.
The amount of the chlorinated paraffin is usually 3 to 200 parts by weight, preferably 5 to 1500 parts by weight, preferably 80 to 1200 parts by weight, based on 0 parts by weight.
It is contained in an amount of 100 parts by weight, more preferably 10 to 100 parts by weight, and the (meth) acrylic acid ester-based polymer is usually 1 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 100 parts by weight. It is contained in an amount of 100 parts by weight, and the scale-like pigment is usually 0.5 to 400 parts by weight, preferably 1 to 200 parts by weight, more preferably 5 to 15 parts by weight.
The amount of zinc pyrithione contained in the antifouling agent is usually 0.5 to 600 parts by weight, preferably 1 to 500 parts by weight, and more preferably 2 to 400 parts by weight. desirable.

The antifouling coating composition as described above is applied to the surface of an underwater structure (eg, a water supply / drainage port of a nuclear power plant) on a bay road,
Always on the surface of sludge diffusion prevention film for construction of various marine civil engineering equipment such as undersea tunnels, harbor equipment, canals and waterways, or on the surface of various molded products such as ships and fishing gear (eg rope, fishing net). By applying once or a plurality of times according to the method, an antifouling coating film-coated hull or an underwater structure having excellent crack resistance and antifouling property can be obtained. The antifouling paint composition according to the present invention may be applied directly to the surface of the above-mentioned hull or underwater structure, or a hull or underwater structure to which a base material such as a rust preventive or a primer has been applied in advance. It may be applied to the surface of an object or the like. Furthermore, the surface of a hull, underwater structure, or the like, which has already been coated with a conventional antifouling paint or has been coated with the antifouling paint composition of the present invention, is used as a repair for the antifouling of the present invention. The coating composition may be overcoated. The thickness of the antifouling coating film thus formed on the surface of the hull, underwater structure, etc. is not particularly limited, but is, for example, 30 to 1
It is about 50 μm / time.

[0086]

EFFECTS OF THE INVENTION The antifouling coating composition according to the present invention is particularly excellent in slime resistance, crack resistance, peel resistance, antifouling property, and self-polishing property (consumable property). It can form a coating film and is excellent in storage stability.

[0087]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, “parts” means “parts by weight”. In addition, the amount of each component in the table, for example, the amount of copolymer component, the amount of chlorinated paraffin (salt para), the amount of color pigment, cuprous oxide, zinc white, etc.,
Alternatively, the amounts of solvents (eg, xylene) and the like are shown in “parts by weight” unless otherwise specified. [ Production Example of Polymer] ( Production of Copolymer S-1) 100 parts of xylene was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a heating / cooling jacket, and a temperature condition of 90 ° C. under a nitrogen stream. The mixture was heated and stirred.

While maintaining the same temperature, from the dropping apparatus, 40 parts of tributylsilyl methacrylate, 60 parts of methyl methacrylate and 2,2'- of the polymerization initiator were charged into the reactor.
A mixture of 1.2 parts of azobisisobutyronitrile was added dropwise over 4 hours.

Then, stirring was continued at the same temperature for 4 hours to obtain a colorless and transparent copolymer solution S-1. After heating the obtained copolymer solution S-1 at 105 ° C. for 3 hours, the heating residue was 4%.
It was 9.9% by weight, and 95% by weight or more of each monomer was incorporated into the copolymer based on the quantitative determination result of the residual monomer by GPC, and the change in the conversion rate during the reaction was almost the same for each monomer. It is considered that the derived component units are randomly arranged in the ratio of the amounts of the monomers used.

The glass transition temperature (Tg) of the copolymer (residual residue) S-1 in this copolymer solution S-1 was 51 ° C.
And the viscosity at 25 ° C. of the copolymer solution S-1 was 2
95 cps, and the number average molecular weight (M
n) is 11,200 and the weight average molecular weight (Mw) is 2
1200. (Production of Copolymer S-2 to Copolymer S-6) In the same manner as described above, except that the blending components were changed as shown in Table 1 during the production of the above copolymer S-1. Copolymer S-2, copolymer S-3, copolymer S-4, copolymer S-5 and copolymer S-6 were obtained, and these copolymers (solution) were obtained in the same manner as above. Was measured.

The results are also shown in Table 1.

[0092]

[Table 1]

Type and physical properties of compatible (meth) acrylic acid ester-based polymer component (solution) used when forming an antifouling coating composition [heating residue (% by weight / polymer solution)
And the viscosity of the compatible (meth) acrylic acid ester-based polymer contained in the polymer component (Gardner / 25
° C), molecular weight (Mn: measured by GPC), acid value (A
V) and glass transition temperature (Tg ° C.)] were measured.

Table 2 shows the results.

[0095]

[Table 2]

[0096]

[Examples 1 to 23, Comparative Examples 1 to 5] [Production Example of Antifouling Paint Composition] Each antifouling paint composition having the composition shown in Tables 3 to 8 was produced (the amount of each component is expressed in parts by weight). ).

In producing the antifouling paint compositions having the compositions shown in Tables 3 to 8, the ingredients were shaken together in a paint shaker containing glass beads for 2 hours, and then at room temperature. Aged for 12 hours. Then 1
A desired antifouling coating composition was obtained by filtering with a 00 mesh filter.

Tables 8 and 10 show the viscosities immediately after production (Ku value / 25 ° C.) of the antifouling coating composition as measured by a Stormer viscometer and the viscosities after storage at room temperature for 1 month. [Evaluation of Antifouling Property, Exhaustion Degree, and Physical Properties] A 70 × 200 × 3 mm sandblast plate was prepared that was bent so that it could be attached to the side surface of a rotary drum installed in seawater in Hiroshima Bay. Epoxy zinc-rich primer (zinc dust content in the dry coating film is 80% by weight), tar-epoxy anticorrosive paint, and vinyl binder coat are applied to the sandblast plate to obtain dry film thicknesses of 20 μm and 150 μm, respectively.
After successively coating so as to have a thickness of 50 μm, the test antifouling coating composition was coated so that the film thickness after drying was 200 μm to obtain a test plate.

After attaching this test plate to a rotating drum and simulating the operation of a ship for 12 months under a peripheral speed of 15 knots and an operation condition of 50% (alternate operation of 12 hours at night and 12 hours at daytime stop), antifouling was performed. Property (dynamic antifouling property, area of adhesion of various aquatic organisms on test plate), consumption degree μ (film thickness reduction),
Physical properties were evaluated.

The results are shown in Tables 9 and 10. [Standing antifouling test] Epoxy zinc-rich primer (zinc dust content 80% by weight in paint), tar epoxy anticorrosive paint, vinyl binder coat on 100 × 300 × 2 mm sandblasted steel sheet After coating every day to a thickness of 20 μm, 150 μm, and 75 μm, the test antifouling paint has a dry film thickness of 100 μm.
m to obtain a test plate.

A test test plate was hung at a water depth of 1 m from a test raft installed off Miyajima, and the degree of adhesion of slime to the test plate was evaluated at 2 months, 4 months, 6 months and 12 months.

The evaluation results are shown in Tables 9 and 10. Evaluation Criteria (Points) The evaluation criteria (points) for the degree of slime adhesion are as follows. 10: No adhesion of slime is visually observed.

9: Partially thin slime is visually observed. 8: An extremely thin slime is recognized. 7: A transparent thin slime layer that can be easily removed is recognized.

6: A semi-transparent slime layer which can be easily removed is observed. 5: Covered with a brownish-translucent slime layer, it is difficult to remove slime. 4: Covered with a dark brown slime layer, it is difficult to remove slime.

3: Covered with a blackish brown slime layer and slid
Difficult to remove. 2: Covered with a thick black-brown slime layer, removing slime
Is difficult. 1: Covered with a thick black-brown slime layer to remove slime
Is extremely difficult. Content such as ingredient name The component names in the table are as follows. "TOYO PARAX 150" Tosoh Co., Ltd. chlorinated para
Fin, average carbon number: 14.5, chlorine content (amount) 5
0%, viscosity: 12 poise / 25 ° C, specific gravity: 1.25 / 2
5 ° C. "TOYO PARAX A-40" Tosoh Co., Ltd. chlorinated para
Fin, average carbon number: 24.5, chlorine content (amount) 4
0.5%, viscosity: 18.5 poise / 25 ° C, specific gravity: 1.
16/25 ° C. "Toyo Parax 270" Tosoh Co., Ltd. chlorinated para
Fin, average carbon number: 12, chlorine content (amount) 70%,
Viscosity: 4 poise / 80 ° C, specific gravity: 1.50 / 80 ° C. "TOYO PARAX A-70" chlorinated para produced by Tosoh Corporation
Fin, average carbon number: 24.5, chlorine content (amount) 7
0%, white powder, specific gravity: 1.65 / 25 ° C. "Molecular sieve 4A" dehydrating agent, Union Showa
Co., Ltd., synthetic zeolite powder. "Disparon 305" Castor hydrogenated by Kusumoto Kasei Co., Ltd.
Oil-based anti-sagging agent. "Disparon 4200-20" Oxide porosity manufactured by Kusumoto Kasei Co., Ltd.
Polyethylene anti-settling agent, 20% xylene paste. "Mica Shiratama": Scaly face made by (Wakimoto Mica)
Material, average particle diameter: 15 μm, aspect ratio: 40. [Content of chlorinated paraffin, etc. in film-forming copolymer
(Wt%) Calculation method] In the table, "chlorinated paraffin (weight
%) (To copolymer) ”,“ Cu₂O (% by weight)
"Coalescence)", "ZnO (wt%) (to copolymer)", etc.
The delivery method is as follows.

For example, in the "antifouling coating composition P-1",
"Salt para (chlorinated paraffin) content (% by weight) (copolymer, ie, film-forming copolymer, hereinafter the same)" =
30.8 is obtained as follows.

That is, in the "antifouling coating composition P-1", chlorinated paraffin was added in an amount of 4 parts by weight, and "copolymer component (solution) S-1" was added in an amount of 26 parts by weight. This "copolymer component (solution) S-1" is blended in an amount of 2
In 6 parts by weight, the heating residue (copolymer S-1) was 49.
It is contained in an amount of 9% by weight. Therefore, in the "antifouling coating composition P-1", "chlorinated paraffin (% by weight) (relative to copolymer)" = [4 / {26 × 49.9 / 100}] ×
It becomes 100% = 30.8 (weight%).

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

[Table 7]

[0113]

[Table 8]

[0114]

[Table 9]

[0115]

[Table 10]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Makoto Tsuboi 7 Chugoku Paint Co., Ltd., 1 Shinjikai Meiji, Otake City, Hiroshima Prefecture

Claims (10)

[Claims] 1. A film-forming copolymer having a component number derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight and having a number average molecular weight of 1,000 to 50,000, and chlorine. An antifouling coating composition comprising a modified paraffin and zinc pyrithione as an antifouling agent. 2. The chlorinated paraffin is contained in an amount of 10 to 65 parts by weight, and zinc pyrithione is contained in an amount of 0.5 to 600 parts by weight, based on 100 parts by weight of the film-forming copolymer. The antifouling coating composition according to claim 1, wherein the antifouling coating composition is provided. 3. The antifouling paint according to claim 1, wherein the chlorinated paraffin is contained in an amount of 20 to 40 parts by weight with respect to 100 parts by weight of the film-forming copolymer. Composition. 4. The trialkylsilyl ester according to claim 1, wherein at least one of the three alkyl groups bonded to the silicon atom has 3 or more carbon atoms. The antifouling coating composition as described above. 5. The antifouling coating composition according to any one of claims 1 to 3, wherein the trialkylsilyl ester is tributylsilyl (meth) acrylate. 6. The average carbon number of the chlorinated paraffin is 8 to
The antifouling coating composition according to any one of claims 1 to 5, which has a chlorine content of 35 to 75%. 7. The antifouling coating composition according to claim 1, further comprising copper or a copper compound as an antifouling agent and containing zinc white. 8. A coating film formed from the antifouling coating composition according to any one of claims 1 to 7. 9. An antifouling method for a hull or an underwater structure, which comprises using the antifouling coating composition according to any one of claims 1 to 7. 10. A hull or underwater structure, wherein the surface of the hull or underwater structure is coated with a coating film comprising the antifouling coating composition according to any one of claims 1 to 7.