JP2002256176A - Composite antifouling coating, ship coated with the coating, underwater structure, fishing gear or fishing net, and antifouling method - Google Patents

Abstract

(57) Abstract: (A) On the surface of at least one antifouling coating film formed from an antifouling coating material containing a copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit, (B) A composite antifouling coating formed by laminating at least one antifouling coating formed from an antifouling coating containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit. The composite antifouling coating film of the present invention is a coating composition comprising an antifouling coating material containing a copolymer containing a polymerizable unsaturated metal carboxylate component unit provided on a substrate to be coated such as an old coating film. On the film, because it is a composite coating film formed of a coating film made of an antifouling paint containing a polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer, excellent adhesion with an old coating film,
It can be applied directly on the old paint film to be repaired or repainted, which is excellent in economy and work efficiency.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite antifouling coating, a ship coated with the coating, an underwater structure, a fishing gear or a fishing net, and an antifouling method using the coating. More specifically, the present invention is a composite antifouling coating excellent in adhesion with the old coating and economical even when applied on an old antifouling coating as a repair coating or a repainting coating, The present invention relates to a ship, an underwater structure, a fishing gear or a fishing net coated with the coating, and an antifouling method using the coating.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ship bottoms, underwater structures, fishing nets, etc.
Because they are exposed to water for a long period of time, various types of aquatic organisms such as oysters, mussels, barnacles, etc., plants such as laver (seaweed), and bacteria, often attach to and propagate on the surface. The appearance is impaired, and the functions of the ship bottom, underwater structures and the like are often impaired.

[0003] In particular, when such aquatic organisms adhere to or proliferate on the bottom of the ship, the surface roughness of the whole ship increases, which may cause a decrease in ship speed, an increase in fuel efficiency, and the like. Also, if bacteria, slime (sludge-like substance), or large attached organisms adhere to underwater structures, they will rot or damage coatings for corrosion prevention. There is a possibility that damages such as reduction of the service life may be caused. Therefore, it is necessary to remove such aquatic organisms from the bottom of the ship. However, such work requires a great deal of labor and work time.

[0004] To prevent such damage, various antifouling paints are applied to ship bottoms, underwater structures and the like. Among them, a coating film formed of an antifouling paint containing a polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer,
It is useful because it has excellent antifouling performance for a long time, and is frequently used. However, if the antifouling paint is used for a long period of time, it gradually wears out, is damaged, and the paint becomes old and peels off. Need to be repaired or repainted.

[0005] By the way, prior to such repair painting or repainting, if the work of removing the old paint film on the surface of the base material in advance is required, extra work and cost are required. From the surface, on the old coating,
It is desired to repair and apply new paint directly. When a new paint is applied over such an old paint film surface, adhesion between the paint to be used newly and the old paint film becomes a problem. In particular, when the old coating to be repaired is an antifouling coating containing a polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer, the old coating has a sponge-like skeleton layer. In many cases, when an antifouling paint containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit is to be newly applied on this coating film, a polymerizable unsaturated carboxylic acid silyl ester component is to be applied. A coating film made of an antifouling paint containing a unit-containing copolymer has a problem that the surface energy is small and sufficient adhesion performance cannot be exhibited.

Accordingly, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit is formed on the surface of a substrate to be repair-painted. An antifouling coating film (layer) made of an antifouling paint containing is provided, and a coating film made of an antifouling paint containing a polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer is provided on the surface of the coating film. The composite coating film formed by laminating is excellent in adhesion to the anti-fouling coating film containing the old polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer, and the old coating film The present invention has been found to be excellent in terms of economy and work efficiency because it can be applied directly on the surface of the substrate, and has completed the present invention.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems, and has an excellent adhesion to an old coating film, and can be applied directly on an old coating film. It is intended to provide an antifouling coating film having excellent coating work efficiency, and in particular, an antifouling coating film having excellent adhesion with a coating made of an old antifouling paint having poor adhesion. An object of the present invention is to provide a ship, an underwater structure, and an antifouling method using the coating film.

[0008]

SUMMARY OF THE INVENTION The composite antifouling coating of the present invention comprises (A) at least one antifouling coating formed from an antifouling coating containing a copolymer containing a polymerizable unsaturated metal salt of a carboxylic acid component unit. (B) at least one antifouling coating film formed from an antifouling coating material containing a copolymer containing (B) a polymerizable unsaturated carboxylic acid silyl ester component unit. Features.

The above-mentioned copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit is also preferably a copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit containing no hydroxy group bonded to a metal atom. The polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer has a general formula [I]: R ¹ —COO-ML _n ... [I] wherein R ¹ is _{, CH 2 = C (CH 3} ) -, CH 2 =
CH-, HOOC-CH = CH-, HOOC-CH = C
(CH ₃ ) — represents an organic group containing an unsaturated bond represented by any of formulas, and —COOH may form a metal salt or an ester. M represents a metal atom, L represents an organic acid residue: —OCOR ² , R ² has a carbon number of 1 to 25, and has a chain alkyl group, an alicyclic alkyl group, an aromatic hydrocarbon group, N represents an aralkyl group, and n represents the number of the valence number of the metal M minus one. It is also preferable that the copolymer has a component unit derived from the metal salt of a polymerizable unsaturated carboxylic acid represented by the formula:

It is also preferred that the copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit is a copolymer containing a polymerizable unsaturated carboxylic acid hydroxy metal salt component unit. The polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer has a general formula [II]: R ¹ -COO-M-OH... [II] [In the formula [II], R ¹ is _{CH 2 = C (CH 3)} -, CH 2 =
CH-, HOOC-CH = CH-, HOOC-CH = C
(CH ₃ ) — represents an organic group containing an unsaturated bond represented by any of formulas, and —COOH may form a metal salt or an ester. M represents a metal atom. It is preferable that the copolymer has a component unit derived from the polymerizable unsaturated hydroxycarboxylic acid metal salt in the molecule.

The polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer is represented by the following general formula [III]: R ¹ —COO—Si (L ¹ L ² L ³ ) [III] In [III], R ¹ is CH ₂ ＣC (CH ₃ ) —, CH ₂
= CH-, HOOC-CH = CH-, HOOC-CH =
C (CH ₃ ) — represents an organic group containing an unsaturated bond represented by any of formulas, and —COOH may form a metal salt or an ester. L ¹ , L ² , and L ³ may be the same or different from each other, each have from 1 to 20 carbon atoms, and are a chain alkyl group, an alicyclic alkyl group, an aromatic hydrocarbon group, an aralkyl group. And any of their substitutes. And a copolymer comprising an unsaturated monomer copolymerizable with the polymerizable silyl unsaturated carboxylate monomer.

The antifouling paint forming the antifouling coating film (A) or (B) may further contain copper, a copper compound, zinc oxide, a dehydrating agent, an organic antifouling agent and the like. The composite antifouling coating film of the present invention is suitably used for ships, underwater structures, fishing gear or fishing nets. The antifouling method for a ship, underwater structure, fishing gear or fishing net of the present invention is characterized in that the surface of a ship, underwater structure, fishing gear or fishing net is coated with any of the above-described composite antifouling coatings.

[0013]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the composite antifouling coating film of the present invention, ships, underwater structures, fishing gear or fishing nets and antifouling methods coated with the antifouling coating film will be described in detail. [Composite antifouling coating film] The composite antifouling coating film of the present invention comprises at least one antifouling film formed from an antifouling paint containing a copolymer (a) containing a polymerizable unsaturated metal carboxylate component unit. An antifouling paint (hereinafter also referred to as an overcoat layer) containing a copolymer (b) containing a polymerizable unsaturated carboxylic acid silyl ester component unit on the surface of a coating film (A) (hereinafter also referred to as an undercoat layer). ) Is formed by laminating at least one antifouling coating film (B). Such a composite coating film has an antifouling coating film (A) side directly adhered to the surface of a substrate to be coated such as a ship, an underwater structure, a fishing gear or a fishing net, or another layer (eg, a base layer, a primer). ) Is applied so as to face each other.

Antifouling coating film (A) The antifouling coating film (A) contains a copolymer (a) containing a polymerizable unsaturated carboxylic acid metal salt component unit (hereinafter also referred to as a copolymer (a)). At least one antifouling coating film formed from the antifouling paint. Hereinafter, the antifouling paint forming the antifouling coating film (A) (hereinafter, referred to as the antifouling paint (A)) will be described.

The copolymer (a) containing a polymerizable unsaturated carboxylic acid metal salt component unit contained in the antifouling paint (A) is disclosed in Japanese Patent Application Laid-Open No. H11-32320, previously proposed by the present applicant.
(Meta) described in columns [0036] to [0049] of JP-A-9
Metal acrylate copolymer or JP-A-11-3
Resins and the like described in columns [0015] to [0044] of JP-A-02572 can be used.

That is, the polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer (a) used in the present invention includes a polymerizable unsaturated carboxylic acid metal salt monomer (monomer (a)) and A polymerizable unsaturated carboxylic acid metal salt component unit copolymer obtained by copolymerizing the “other monomer” (b) copolymerizable with the metal salt monomer (a) is exemplified. Examples of the monomer (a) include a metal (meth) acrylate monomer.

Such a copolymer (a) usually contains a component unit derived from a polymerizable unsaturated metal carboxylate monomer (a) such as a metal (meth) acrylate monomer. 2 to 60% by weight, preferably 15 to 50% by weight
And the component unit derived from the other monomer (b) copolymerizable with this monomer (a) is the remaining amount, that is, 9
8 to 40% by weight, preferably 85 to 50% by weight (however,
(The sum of the component units (a) and (b) is 100% by weight).

Since the copolymer (a) containing a polymerizable unsaturated carboxylic acid metal salt component unit is excellent in wettability, a coating film composed of a coating material containing the copolymer (a) cannot be used for a long time. Stained paint film, for example, an old paint film (layer) made of an antifouling paint containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit, or a paint film (B) made of an overcoated antifouling paint (B)
The copolymer (a) has a hydrolytic property as a vehicle component and has a function of imparting long-term antifouling properties to a coating film.

Examples of the copolymer (a) containing a polymerizable unsaturated carboxylic acid metal salt component unit include (i) a polymerizable unsaturated carboxylic acid metal salt component unit containing no hydroxy group bonded to a metal atom. A polymer or (ii) a copolymer containing a polymerizable unsaturated carboxylic acid hydroxy metal salt component unit can be used. Examples of the metal atoms constituting the polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer (a) include Ib, IIa, IIb, IIIa and Ia of the periodic table.
IIIb, IVa, IVb, Va, Vb, VIb, VI
Group Ib and Group VIII metal atoms.
u, Zn, Ni, Co, Pb, Al, Sn, Mg, etc.
Metal atoms having a valence of valence or more are mentioned, and among them, Cu and Zn are particularly preferred.

Specific examples of the unsaturated carboxylic acid constituting the copolymer containing the polymerizable unsaturated carboxylic acid metal salt component unit include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. Among them, acrylic acid and methacrylic acid are particularly preferable, and in the present specification, these are collectively referred to as (meth) acrylic acid.

(I) No hydroxy group bonded to a metal atom
-Containing copolymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer
Examples of the copolymer (i) containing a polymerizable unsaturated carboxylic acid metal salt component unit containing no hydroxy group bonded to a body metal atom include:
General formula [I]: R ¹ —COO-ML _n ... [I] [In the formula [I], R ¹ is CH ₂ ＣC (CH ₃ ) —, CH ₂ =
CH-, HOOC-CH = CH-, HOOC-CH = C
An organic group containing an unsaturated bond such as (CH ₃ ) —
-COOH may react with a metal, an alcohol or the like to form a metal salt or ester. M represents a metal atom, L represents an organic acid residue: —OCOR ² , R ² has a carbon number of 1 to 25, and has a chain alkyl group, an alicyclic alkyl group, an aromatic hydrocarbon group, N represents an aralkyl group, and n represents the number of the valence number of the metal M minus one. It is preferable that the copolymer contains a component unit derived from a metal salt of a polymerizable unsaturated carboxylic acid represented by the following formula:

In the above formula [I], L is a carboxylic acid residue (—O
In the case of COR ² ), the carboxylic acid (HOCOR ² ) capable of deriving such a group may be in the form of a chain, or may have an alicyclic ring, an aromatic ring or the like. Specifically, propionic acid, valeric acid, oleic acid, linoleic acid, linolenic acid, stearic acid, versatic acid, abietic acid (acid contained in rosin), naphthenic acid, which are mainly monovalent carboxylic acids, (Meth) acrylic acid, benzoic acid and the like.

The polymerizable unsaturated compound represented by the above general formula [I]
Examples of the metal carboxylate monomer include (meth) amine
Acrylate metal salt monomers and the like, more specifically
Is zinc methacrylate: [(CH_Two= C (CH_Three) -CO
O-)_TwoZn], zinc acrylate: [(CH_Two= CH-C
OO-)_TwoZn], magnesium methacrylate: [(C
H_Two= C (CH_Three) -COO-)_TwoMg], acrylic acid
Gnesium: [(CH_Two= CH-COO-)_TwoMg]
Copper acrylate: [(CH_Two= C (CH_Three) -COO-)_Two
Cu], copper acrylate: [(CH_Two= CH-COO-)_Two
Cu], zinc versatate methacrylate: [(CH
_Two= C (CH_Three) -COO-) ((C_ThreeH₇) _ThreeC-COO
-) Zn], zinc versatate acrylate: [(C
H_TwoＣＨCH-COO-) ((C_ThreeH₇)_ThreeC-COO-) Z
n], zinc naphthenate methacrylate: [(CH_Two= C
(CH_Three) -COO-) (naphthenic acid residue) Zn],
Zinc phenate acrylate: [(CH_Two= CH-COO
−) (Naphthenic acid residue) Zn], zinc benzoate methacrylate
Rate: [(CH_Two= C (CH_Three) -COO-) ((C₆
H_Five) COO-) Zn], zinc benzoate acrylate:
[(CH_TwoＣＨCH-COO-) ((C₆H_Five) COO-)
Zn], magnesium benzoate methacrylate: [(C
H_Two= C (CH_Three) -COO-) (C₆H_FiveCOO-) M
g], magnesium versatate acrylate:
[(CH_TwoＣＨCH-COO-) ((C_ThreeH₇)_ThreeC-COO
-) Mg], copper versatate methacrylate: [(C
H_Two= C (CH_Three) -COO-) ((C_ThreeH₇)_ThreeC-CO
O-) Cu], copper benzoate methacrylate: [(CH_Two
= C (CH_Three) -COO-) ((C₆H_Five) COO-) C
u], copper naphthenate methacrylate: [(CH_Two= C
(CH_Three) -COO-) (naphthenic acid residue) Cu], na
Copper phenate acrylate: [(CH_Two= CH-COO
−) (Naphthenic acid residue) Cu], ethyl-stearic acid
Zinc maleate, isopropyl copper oleate maleate
Hexyl-copper versatate maleate, isopro
Pill-Zinc laurate fumarate, butyl abietic acid
Copper fumarate can be exemplified.

Other monomers (b) copolymerizable with the polymerizable unsaturated carboxylic acid metal salt-containing monomer represented by the above general formula [I] include aliphatic, alicyclic and aromatic monomers. Any compound such as an aromatic group may be used. Specific examples of (meth) acrylate monomers include methyl (meth)
Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 2-propoxyethyl (meth)
Aliphatic monomers such as acrylate, 2-butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and ethoxyethylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl ( Alicyclic monomers such as meth) acrylates; and aromatic monomers such as phenyl (meth) acrylate and benzyl (meth) acrylate.

Examples of the unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxyethyl (meth) acrylate.
Unsaturated monomers having one hydroxyl group such as hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; 2-3 such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate And monomers having a plurality of hydroxyl groups such as glycerol (meth) acrylate.

The unsaturated monomer having an amino group may be an unsaturated monomer in which part or all of the hydrogen of the amino group is substituted with a substituent such as a hydrocarbon group. Specifically, (meth) acrylamide, butylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
Acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate,
Monomers having primary to tertiary amino groups or amide groups, such as dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide, are exemplified.

Other monomers (b) other than the above include, for example, diethyl maleate, diisopropyl maleate, diisopropyl fumarate, dibutyl itaconate, ethyl maleate zinc stearate, and isopropyl oleate. Copper maleate, hexyl-copper maleate versatate, isopropyl-zinc laurate fumarate, butyl abietic acid copper fumarate, styrene, vinyl toluene, α-methyl styrene,
(Meth) acrylonitrile, vinyl acetate, vinyl propionate and the like.

Such other monomers (b) each have 1
They can be used alone or in combination of two or more. The above-mentioned copolymer (i) containing a hydroxyl group-free metal-bonded metallizable unsaturated carboxylic acid metal salt component unit is a monomer-free polymerizable unsaturated carboxylic acid metal salt-free metal salt bonded to a metal atom. When the monomer (a) and the polymerizable unsaturated carboxylic acid metal salt monomer (a) are copolymerized with another monomer (b) copolymerizable with the monomer (b), the polymerizable unsaturated carboxylic acid The component unit derived from the metal salt (a) is usually 2 to 60% by weight, preferably 15 to 50% by weight, and the remaining component unit derived from another monomer (b) copolymerizable with the monomer (a) is a balance. Quantity, ie 98-4
0% by weight, preferably 85 to 50% by weight (component unit (a)
+ (B) in an amount of 100% by weight).

A copolymer (i) containing a polymerizable unsaturated carboxylic acid metal salt component unit obtained by copolymerizing the unsaturated monomers (a) and (b), for example, containing a (meth) acrylic acid metal salt component unit The number average molecular weight of the copolymer is usually from 5,000 to
100,000, and the glass transition temperature Tg is usually −
20 ° C to + 50 ° C. As a method for producing such a copolymer (i) containing a polymerizable unsaturated metal carboxylate component unit, for example, a copolymer containing a metal (meth) acrylate component unit, the following (1) to (3) ) Can be adopted. These copolymers are
JP-B-7-64985, JP-A-4-80205, JP-A-4-80269, JP-A-4-802
No. 70, JP-A-63-128008, JP-A-63-128084, JP-A-1-16809, JP-A-5-171066, and
It can be easily produced by following or referring to the method disclosed in JP-A-15847.
Specifically, the following method can be used.

(1) As a first method, a polymerizable unsaturated carboxylic acid metal salt monomer, for example, a (meth) acrylic acid metal salt monomer (a), and a copolymer thereof with the monomer (a) Another polymerizable monomer (b) is mixed with an organic solvent, and the mixture is heated at a temperature of 60 to 120 ° C and a temperature of 5 to 1 in the presence of a radical polymerization initiator such as tert-butyl peroxyoctoate (t-BPO).
A method of producing by solution polymerization for 4 hours can be mentioned.

(2) As a second method, a polymerizable unsaturated carboxylic acid monomer such as (meth) acrylic acid (a),
Another monomer (b) copolymerizable with this monomer (a), and a `` saturated metal salt of a saturated aliphatic carboxylic acid, a metal salt of a saturated alicyclic carboxylic acid, or a metal salt of an aromatic carboxylic acid '' (C ) Is mixed with an organic solvent, and subjected to solution polymerization at a temperature of 60 to 120 ° C. for 5 to 14 hours in the presence of a radical polymerization initiator such as tertiary-butyl peroxyoctoate (t-BPO). There is a method.

(3) As a third method, a polymerizable unsaturated carboxylic acid monomer such as (meth) acrylic acid (a) and another monomer copolymerizable with this monomer (a) (B) is mixed with an organic solvent, and solution-polymerized at a temperature of 60 to 120 ° C for 5 to 14 hours in the presence of a radical polymerization initiator such as tertiary-butylperoxyoctoate (t-BPO), thereby performing polymerization. A copolymer comprising a unsaturated unsaturated carboxylic acid monomer, specifically (meth) acrylic acid (a) and another monomer (b) copolymerizable with this monomer (a) is produced. ,
Subsequently, the copolymer is reacted with a `` saturated aliphatic carboxylic acid metal salt, saturated alicyclic carboxylic acid metal salt, or aromatic carboxylic acid metal salt '' (c), or "Saturated aliphatic carboxylic acid, saturated alicyclic carboxylic acid or aromatic carboxylic acid" (C-1) and "Metal salt compound containing the same metal species as described above, other similar metal compounds" (2) A method of producing by reacting can be given.

(Ii) hydroxy polymerizable unsaturated carboxylic acid
Metal salt component unit-containing copolymer The polymerizable unsaturated carboxylic acid hydroxy metal salt component unit-containing copolymer (ii) is described in JP-A-8-209005.
[II]: R ¹ -COO-M-OH... [II] [wherein R ¹ is represented by the formula [II], as described in JP-A-9-286933. _{, CH 2 = C (CH 3} ) -, CH 2 =
CH-, HOOC-CH = CH-, HOOC-CH = C
An organic group containing an unsaturated bond such as (CH ₃ ) —
-COOH may form a metal salt or ester. M represents a metal atom, preferably a zinc atom or a copper atom. It is preferable that the copolymer has a component unit derived from the polymerizable unsaturated hydroxycarboxylic acid metal salt in the molecule.

The copolymer (ii) containing the polymerizable unsaturated carboxylic acid hydroxymetal salt monomer [II] component unit in the molecule represented by the formula [II] is specifically (meth) ) Copolymers containing hydroxy metal acrylate component units, and especially copolymers containing hydroxy zinc (meth) acrylate component units or copolymers containing (co) hydroxy copper (meth) acrylate component units (resins) Is preferred.

The polymerizable unsaturated carboxylic acid hydroxy metal salt monomer component unit-containing copolymer (ii), for example,
The copolymer containing hydroxy zinc (meth) acrylate component units or the copolymer containing hydroxy copper (meth) acrylate component units (resin) is a copolymer having a carboxyl group in the molecule and a divalent metal. Oxides or hydroxides of
For example, it can be obtained by reacting zinc (or copper) oxide or hydroxide in the presence of a small amount of water.

In this reaction, the above-mentioned metal oxide or metal hydroxide, for example, an oxide or hydroxide of zinc (or copper) is added to 1 mol of carboxyl group in the above-mentioned copolymer (resin). And water is used in an amount of 0.1 to 1 mole per mole of carboxyl group. As a more specific method for synthesizing the copolymer (ii), as described in JP-A-9-286933, a copolymer having a carboxyl group in the molecule is added to a copolymer having a carboxyl group. 0.5 to 5% by weight of water and a metal oxide or hydroxide, which is a divalent metal to be added, for example zinc (or copper) oxide or hydroxide, and if necessary A very small amount of a polar solvent for preventing turbidity is also added.
There is a method of reacting for a time.

The copolymer having a carboxyl group in the molecule is preferably a polymerizable unsaturated carboxylic acid monomer such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and the like. It can be formed by copolymerizing a polymerizable unsaturated carboxylic acid monomer with another copolymerizable monomer. The copolymer having a carboxyl group in the molecule is not limited to the above examples, as long as it contains a carboxyl group, other various vinyl polymers, polyester, polyurethane,
Natural resins and the like can also be used.

Examples of the monomer containing the polymerizable unsaturated carboxylic acid hydroxy metal salt or other monomer copolymerizable with the polymerizable unsaturated carboxylic acid monomer include the above-mentioned polymerizable unsaturated carboxylic acid metal salt-containing monomer. As the “other monomer” copolymerizable with the monomer, the same unsaturated monomer as described in (i) can be used. Examples of the oxide or hydroxide of zinc (or copper), which is a divalent metal, include zinc oxide, zinc hydroxide [Zn (OH) ₂ ], copper oxide, and copper hydroxide [Cu
(OH) ₂ ].

The polar solvent used in the polymerization reaction includes
Alcohols such as butanol, ketones, esters,
Ether type is used. The polymerizable unsaturated carboxylic acid hydroxy metal salt component unit-containing copolymer (ii),
For example, the copolymer containing a hydroxy metal (meth) acrylate component unit includes a polymerizable unsaturated carboxylic acid hydroxy metal salt-containing monomer (a) and the polymerizable unsaturated carboxylic acid hydroxy metal salt-containing monomer. The copolymerizable “other monomer” (b) is obtained by copolymerization, and the component unit derived from the polymerizable unsaturated carboxylic acid hydroxy metal salt monomer (a) is usually 2 to 60% by weight. , Preferably 15 to 50
% Of the component unit derived from the other monomer (b) copolymerizable with the unsaturated monomer (a), that is, 40 to 98% by weight, preferably 50 to 85% by weight (the component unit ( B) +
(B) of 100% by weight).

The copolymer (ii) containing the unsaturated carboxylic acid hydroxy metal salt component unit thus obtained, for example, the copolymer containing the (meth) acrylic acid hydroxy metal salt component unit has a number average molecular weight of usually 1 5,000 to 50,000
00, preferably 3,000 to 20,000, a glass transition temperature Tg of -10 ° C to + 60 ° C, preferably +10 to + 40 ° C, and an acid value of 60 to 200.

Production of antifouling paint for antifouling coating film (A) The antifouling paint for the antifouling coating film (A) can be produced by appropriately utilizing a conventionally known method. The copolymer containing the polymerizable unsaturated carboxylic acid metal compound component unit may be added, if necessary, to the following coloring pigments (especially zinc oxide), dehydrating agents (stabilizers), antifouling agents (especially copper or inorganic copper compounds, organic compounds). Antifouling agent), plasticizer, anti-sagging / anti-settling agent, other film-forming components, solvent (eg, xylene), dispersion medium, etc. are added at a predetermined ratio at once or in any order, and stirred and mixed. It can be produced by dissolving or dispersing in a solvent or the like.

<Optional Components> In addition to the polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer (a), the antifouling paint (A) for forming the antifouling coating film (A) further comprises: Color pigments (especially zinc oxide), dehydrating agents (stabilizers), antifouling agents (especially copper or copper compounds, organic antifouling agents), plasticizers, anti-sagging / anti-settling agents, (meth) acrylic acid Various components such as a film-forming component other than the metal compound-based copolymer and a solvent, which are usually blended in an antifouling paint, may be contained within a range that does not impair the object of the present invention.

<Pigment> As the pigment, conventionally known various organic and inorganic pigments can be used. Examples of the organic pigment include carbon black, phthalocyanine blue, and navy blue. Examples of inorganic pigments include, for example, neutral and non-reactive pigments such as titanium white, red iron oxide, barite powder, chalk, iron oxide powder; zinc white (ZnO, zinc oxide), lead white, lead tin, zinc Powders that are basic and reactive with acidic substances in paint, such as lead oxide powder (active pigment)
And the like. Note that various colorants such as dyes may be included.

In particular, when zinc oxide is blended, the zinc oxide is desirably contained in the antifouling coating composition in an amount of 0.1 to 20% by weight. <Dehydrating agent (stabilizer)> The dehydrating agent (stabilizer) can further improve the storage stability of the antifouling coating composition. Examples of such a dehydrating agent include anhydrous gypsum (CaSO ₄ ), a synthetic zeolite-based adsorbent (trade name: molecular sieve, etc.), orthoesters such as methyl orthoformate and methyl orthoacetate, orthoborates, silicates and isocyanates (Trade name: Additive TI), and inorganic dehydrating agents such as anhydrous gypsum and molecular sieve are preferred. Such dehydrating agents can be used alone or in combination of two or more.

<Antifouling Agent> Examples of the antifouling agent include copper or inorganic copper compounds, and organic antifouling agents. Copper and / or Inorganic Copper Compound Examples of the copper and / or inorganic copper compound include copper, cuprous oxide, copper thiocyanate (cuprous thiocyanate, copper rhodan), and basic copper sulfate, preferably thiocyanate. Copper oxide (rodan copper) is used. Such a copper compound is particularly preferably used for colored antifouling paints other than white antifouling paints. Such an inorganic copper compound can be used alone or in combination of two or more.

Organic antifouling agent Examples of the organic antifouling agent include boron compounds such as triphenylboron / amine complex, sodium tetraphenylboron / ammonium salt, metal pyrithiones, and carbamate poisons. Specific examples are shown below. Examples of the pyrithiones include metal pyrithiones of various metals such as sodium, magnesium, calcium, barium, aluminum, copper, zinc, iron, and lead. Among the above metal pyrithions, copper pyrithione and zinc pyrithione are preferable, and copper pyrithione is more preferable.

Organic antifouling agents other than boron compounds and metal pyrithione include tetramethylthiuram disulfide, carbamate-based poisons (eg, zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate), 2,4,5 , 6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 4,
5-dichloro-2-n-octyl-4-isothiazoline-3
-One, 2,4,6-trichlorophenylmaleimide,
2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, basic copper acetate and the like.

Among the above organic antifouling agents, zinc pyrithione, copper pyrithione, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide,
2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-2-
n-octyl-4-isothiazolin-3-one, 2,4
5,6-Tetrachloroisophthalonitrile is preferred.

The organic antifouling agent is generally added in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight.
Further, the organic antifouling agent is usually used as a solid content of 0.1 part by weight based on 100 parts by weight of the resin solid content contained in the coating composition.
To 150 parts by weight, preferably 0.1 to 100 parts by weight. When the organic antifouling agent is incorporated into the coating composition in such an amount, there is a tendency that more excellent antifouling performance can be exhibited for a long period of time.

<Plasticizer (chlorinated paraffin)> Examples of the plasticizer include TCP (tricresyl phosphate), chloride paraffin, and polyvinyl ethyl ether.
These plasticizers can be used alone or in combination of two or more. These plasticizers contribute to the improvement of the crack resistance of the antifouling coating film.
Chlorinated paraffin (chlorinated paraffin) is preferably used.

<Anti-Sagging / Anti-settling Agent (Thixotropic Agent)> As the anti-sagging / anti-settling agent, organic viscous Al, Ca, Z
n, stearate salts, lecithin salts, salts such as alkyl sulfonates, polyethylene waxes, amide waxes, hydrogenated castor oil waxes, polyamide waxes and mixtures thereof, synthetic finely divided silica, polyethylene oxide waxes and the like. Preferably, a polyamide wax, a synthetic finely divided silica, a polyethylene oxide wax, and an organic viscosity wax are used. As such an anti-sagging / anti-settling agent, "Dispalon" manufactured by Kusumoto Kasei Co., Ltd.
305 "," DISPARON 4200-20 "and the like, as well as those marketed under the trade names such as" DISPARON A630-20X ".

<Other film-forming components> As the film-forming components, resins other than the above-mentioned copolymer containing the polymerizable unsaturated carboxylic acid metal compound component unit are contained within a range not inconsistent with the object of the present invention. Such “other coating film forming components” include, for example, acrylic resin, acrylic silicone resin, unsaturated polyester resin, fluororesin, polybutene resin, silicone rubber, urethane resin (rubber), polyamide resin, vinyl chloride -Based copolymer resin, chlorinated rubber (resin), chlorinated olefin resin, styrene / butadiene copolymer resin, ethylene-vinyl acetate copolymer resin,
Difficult or non-water-soluble resins such as vinyl chloride resin, alkyd resin, coumarone resin, trialkylsilyl acrylate (co) polymer (silyl resin), petroleum resin (hereinafter also referred to as poorly water-soluble or water-insoluble resin) can give.

In the present invention, the above-mentioned poorly water-soluble or water-insoluble and the following water-soluble resins can be used in combination. Examples of the water-soluble resin include rosin (eg, trade name “Rosin WW”), monocarboxylic acids and salts thereof. Examples of the monocarboxylic acid include a fatty acid having about 9 to 19 carbon atoms and naphthenic acid. Examples of the monocarboxylic acid salt include a Cu salt, a Zn salt, and a Ca salt. Rosin includes gum rosin, wood rosin,
There are tall oil rosin and the like, and any of them can be used in the present invention. These water-soluble resins can be used alone or in combination of two or more.

<Solvent> In the antifouling paint (A) for the antifouling coating film (A), the various components described above are dissolved or dispersed in a solvent. As the solvent used herein, for example, various solvents such as an aliphatic type, an aromatic type, a ketone type, an ester type, an ether type, and an alcohol type which are usually blended in an antifouling paint are used. Examples of the aromatic solvent include xylene and toluene, and examples of the ketone solvent include MIBK and the like. Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (PMAC). Examples of alcohols include isopropanol, n-butanol, sec-butanol and tert-butanol.

Antifouling coating film (B) The antifouling coating film (layer) (B) is a copolymer (b) containing a polymerizable unsaturated carboxylic acid silyl ester component unit (hereinafter also referred to as a copolymer (b)). ) Is at least one antifouling coating film formed from the antifouling coating material containing Polymerizable unsaturated carboxylic acid silyl ester-containing copolymer
(B) In this antifouling coating film (B), the polymerizable unsaturated carboxylic acid silyl ester-containing copolymer (b) has the general formula [II]
I]: R ¹ —COO—Si (L ¹ L ² L ³ ) [III] [In the formula [III], R ¹ is CH ₂ ＣC (CH ₃ ) —, CH ₂
= CH-, HOOC-CH = CH-, HOOC-CH =
An unsaturated bond-containing organic group such as C (CH ₃ ) —;
OOH may form a metal salt or ester.
L ¹ , L ² and L ³ may be the same or different from each other;
Each has 1 to 20 carbon atoms, and represents any of a chain alkyl group, an alicyclic alkyl group, an aromatic hydrocarbon group, an aralkyl group, and a substituted product thereof. And a copolymer comprising a polymerizable unsaturated carboxylic acid silyl ester monomer represented by the formula [I] and an unsaturated monomer copolymerizable therewith.

L ¹ , L ² and L ³ bonded to the silicon atom of the polymerizable unsaturated carboxylic acid silyl ester-containing monomer may be the same or different, and each has 1 carbon atom.
And represents a linear or branched alkyl group, an alicyclic alkyl group, or an aromatic hydrocarbon group, and L ¹ , L ² , L
^It is preferable that at least one, preferably two, and particularly preferably three of the three are any of a branched alkyl group, an alicyclic alkyl group, and an aromatic hydrocarbon group, particularly a branched alkyl group or an alicyclic group. It is preferably an alkyl group. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-amyl, isoamyl, hexyl, octyl , Decyl group, alkyl groups such as dodecyl group, cyclohexyl group,
Examples thereof include a cycloalkyl group such as a cyclooctyl group, an aromatic hydrocarbon group such as a phenyl group, a tolyl group, and a xylyl group.

Specific examples of such a polymerizable unsaturated carboxylic acid silyl ester-containing monomer include the following silyl (meth) acrylates. Trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, trisec-butylsilyl (meth) acrylate,
Tritert-butylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, methyl-diisopropylsilyl (meth) acrylate, ethyl-diisopropylsilyl (meth) acrylate, n-butyl-diisopropylsilyl ( (Meth) acrylate, isobutyl-diisopropylsilyl (meth) acrylate, sec-butyl-diisopropylsilyl (meth) acrylate, phenyl-diisopropylsilyl (meth) acrylate, phenyl-disec-butylsilyl (meth) acrylate, cyclohexylphenyl-diisopropylsilyl ( (Meth) acrylate, phenyl-ditert-butylsilyl (meth) acrylate, phenyl-diisobutylsilyl (meth) acryl , Diethyl-isopropylsilyl (meth) acrylate, diethyl-isopropylsilyl (meth) acrylate, di-n-butyl-isopropylsilyl (meth) acrylate, diisobutyl-isopropylsilyl (meth) acrylate, disec-butyl-isopropylsilyl ( (Meth) acrylate, dicyclohexylphenyl-isopropylsilyl (meth) acrylate, diphenyl-sec-butylsilyl acrylate, diphenyl-tert-butylsilyl acrylate, diphenylisobutylsilyl acrylate, bis (triisopropylsilyl) maleate, bis (triisopropylsilyl) fumarate , Ethyl-triisopropylsilyl maleate, isopropyl-triisopropylsilyl fumarate, triisopropyl Le - copper stearate maleate, triisopropylsilyl - zinc maleate oleate, triisopropylsilyl - abietic acid zinc maleate, triisopropylsilyl - versatate copper fumarate, triisopropylsilyl - naphthenic acid acid zinc fumarate, triisopropylsilyl -
Specific examples thereof include zinc abietic acid fumarate and the like.

The "other monomer" copolymerizable with the polymerizable unsaturated carboxylic acid silyl ester includes an aliphatic monomer,
Any of alicyclic and aromatic unsaturated monomers may be used. For example, the polymerizable unsaturated carboxylic acid constituting the polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer (i) may be used. Unsaturated monomers exemplified as other monomers copolymerizable with the acid can be similarly used. Such unsaturated monomers can be used alone or in combination of two or more.

The copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit, for example, a copolymer containing a silyl (meth) acrylate component unit, has a long-term slightly water-soluble property as a vehicle component and has a long-term antifouling property on a coating film. Has the function of imparting Such a polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer includes a polymerizable unsaturated carboxylic acid silyl ester monomer and a polymerizable unsaturated carboxylic acid silyl ester monomer. Component units derived from a polymerizable unsaturated carboxylic acid silyl ester monomer.
0% by weight, preferably 15 to 50% by weight, and the remaining amount of a component unit derived from another monomer copolymerizable with the monomer, that is, 4%
It is contained in an amount of 0 to 98% by weight, preferably 50 to 85% by weight (the total of both component units is 100% by weight).

A polymerizable unsaturated carboxylic acid silyl ester component unit copolymer obtained by copolymerizing a polymerizable unsaturated carboxylic acid silyl ester monomer and "another monomer" copolymerizable with the monomer. The number average molecular weight of the coalesced, specifically, the copolymer containing the silyl (meth) acrylate component unit is usually 5,000 to 100,000, and the glass transition temperature Tg is usually -20C to + 50C. .

As a method for producing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit, a polymerizable unsaturated carboxylic acid silyl ester monomer (specifically, a silyl (meth) acrylate monomer) and Another monomer copolymerizable with this monomer is mixed with an organic solvent, and 2,2′-
In the presence of a radical polymerization initiator such as azobisisobutylnitrile (AIBN) at a temperature of 60 to 120 ° C and a temperature of 5 to 1
For example, there is a method in which solution polymerization is performed for 4 hours.

Production of antifouling paint for antifouling coating (B) The antifouling paint (B) for forming the antifouling coating (B) can be produced by appropriately utilizing a conventionally known method. For example, the polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer (b) may be used, if necessary, as described in the section "Production of antifouling paint for antifouling coating film (A)". Similar coloring pigments (especially zinc oxide), dehydrating agents (stabilizers), antifouling agents (especially copper or copper compounds, organic antifouling agents), plasticizers, anti-sagging / anti-sedimentation agents, and other film-forming components , A solvent (eg, xylene) or the like at a predetermined ratio at once or in an arbitrary order, followed by stirring and mixing, and dispersed or dissolved in a solvent.

Composite antifouling coating film and method of forming the same The composite antifouling coating film of the present invention comprises at least one layer of an antifouling paint formed from a copolymer containing a polymerizable unsaturated metal carboxylate component unit. On the surface of the antifouling coating film (A), at least one antifouling coating film (B) formed from an antifouling coating material containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit is laminated. It is formed.

The composite antifouling coating has a surface to be repaired or repainted on the surface of the substrate to be coated.
The antifouling paint (A) containing the polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer (a) produced as described above is applied and cured one to several times by a conventional method to form at least one layer. After the antifouling coating film (A) is formed, the antifouling coating material (B) containing a polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer (b) is formed on the surface of these antifouling coating films (A). B) can be formed by applying and curing B) one to several times by a conventional method, and laminating at least one antifouling coating film (B).

In order to dry and cure the coating film as described above,
After application of the paint (A), the solvent or dispersion medium may be volatilized and removed at room temperature or under heating. Next, the top coat (B) is applied on the coating (A) and cured in the same manner as in the case of the coating (A). At this time, even if the coating (A) is completely cured, It may be in a semi-cured state. In such an antifouling coating formed from the coating (A), especially the antifouling coating (A) containing the copolymerizable polymerizable unsaturated carboxylic acid hydroxy metal salt component unit (ii), the hydroxyl group contained It is considered that dehydration condensation and the like also occur partially between each other and they are cured.

In the antifouling coating film (A) comprising a plurality of layers, the components contained in each layer and their contents may be the same or different. The same applies to the case of the antifouling coating film (B) composed of a plurality of layers. In such a case, for example, the components may be changed continuously from the coating film (A) to (B) or may be changed stepwise.
In addition, on the surface of the substrate to be coated on which the composite antifouling coating is provided,
A sealer, a base coat, a base treatment, or the like may be performed in advance.

As described above, the composite antifouling coating film of the present invention is an antifouling coating material containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit, particularly a substrate to be repaired or repainted. On the surface of a substrate to be coated provided with an antifouling coating formed by applying a stain coating, a copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit having good adhesion to the substrate is contained. Antifouling paint is applied and cured first, and then the antifouling coating (A)
Is formed by applying an antifouling paint containing a polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer to form an antifouling coating film (B).
Excellent anti-fouling coating with excellent adhesion to old coating film (substrate) and containing copolymerizable unsaturated carboxylic acid silyl ester component unit without removing old coating film on substrate surface Can be laminated, so that the work efficiency and the like are excellent. Further, since the antifouling paint (A) for the antifouling coating film (A) is relatively inexpensive, the composite coating film of the present invention is also excellent in economic efficiency.

The antifouling method of the present invention can be applied to the composite antifouling coating film by using, for example, ships, fishing materials (eg, ropes, fishing nets, fishing gear,
Floats, buoys), underwater structures such as water supply / drainage ports for thermal and nuclear power plants, Gulf roads, submarine tunnels, port facilities, canals,
It covers the surface of various molded bodies (substrates to be coated) such as sludge diffusion prevention films for various marine civil works such as waterways. Such an antifouling method is suitable for repair coating or repainting of an old coating film covering the surface of various substrates to be coated.

The antifouling method of the present invention can be used for repairing and repainting the surface coating of fishing gear or fishing nets.
Thus, the thickness of the composite antifouling coating film formed on the surface of the ship, the underwater structure, etc. is not particularly limited, for example,
The antifouling paint (A) for the antifouling coating film (A) has a dry film thickness of 50
It is preferable that the antifouling paint (B) for the antifouling coating film (B) be applied in an amount of about 50 to 150 μm thickness / time.

When applied to a fishing net, use a fishing net 100
The antifouling coating (A) for the antifouling coating (A) is about 30 to 70 parts by weight / time, and the antifouling coating (B) for the antifouling coating (B) is 30 to 70 parts by weight. It is preferable to apply in an amount of about parts by weight / time. In the composite antifouling coating film of the present invention, each layer is formed from the antifouling coating composition as described above, respectively, has a low risk of environmental pollution, is excellent in interlayer adhesiveness of a substrate and the like, and the uppermost layer is Anti-fouling coating made of anti-fouling paint containing polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer, preventing long-term adhesion of organisms such as Aosa, Barnacle, Aonori, Serpula, Oyster, Fusakomushi, etc. Excellent long-term antifouling properties.

[0071]

The composite antifouling coating film of the present invention comprises a copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit provided on a substrate to be coated such as an old coating film. On the coating film made of antifouling paint containing, since a coating film made of antifouling paint containing a polymerizable unsaturated carboxylic acid silyl ester component unit containing copolymer is formed, the old paint film and It has excellent adhesion and can be applied directly on an old paint film to be repaired or repainted, which is excellent in terms of economy and work efficiency.

Further, according to the composite coating film of the present invention, an antifouling paint containing a copolymer containing a polymerizable unsaturated metal salt of a carboxylic acid component is used in advance in order to fill gaps in aged paint. Therefore, the antifouling paint containing the expensive polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer is not required to be consumed in a large amount, so that the present invention is excellent in economical efficiency. Further, the composite antifouling coating film of the present invention is useful because even when an old coating film has poor adhesion, it shows sufficient adhesion.

[0073]

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, "parts"
Indicates "parts by weight". 1. Production Example of Solution Containing Copolymers (a) and (b) (also referred to as Polymer Solution for Vehicle or Varnish) 1-1. Copolymer containing polymerizable unsaturated metal carboxylate component unit (a) PGM (propylene glycol methyl ether) in a reaction vessel equipped with a cooler, a thermometer, a dropping funnel and a stirrer
Charge 20 parts and 40 parts of xylene, and stir 1
The temperature was raised to 00 ° C. Then, PGM10 was dropped from the dropping funnel.
Parts and 10 parts of xylene, the monomers shown in Table 1, and t
A mixture consisting of 2 parts of -butyl peroctoate (polymerization initiator) was dropped at a constant speed in 4 hours. After completion of the dropwise addition, 1 part of t-butyl peroctoate and 10 parts of xylene were added dropwise for 1 hour, and after stirring for 2 hours, 10 parts of xylene was added, and a polymer solution for vehicle having the characteristic values shown in Table 1 was added. a1 to a4 were obtained.

[0074]

[Table 1]

1-2. Polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer (b) 100 parts of xylene was charged into a reaction vessel equipped with a cooler, a thermometer, a dropping funnel, a nitrogen inlet tube and a stirrer, and stirred under a nitrogen stream. The temperature was raised to 85 ° C. Subsequently, a mixture composed of the monomers shown in Table 2 and 0.6 part of 2,2′-azobisisobutylnitrile (polymerization initiator) was dropped at a constant rate over 2 hours from the dropping funnel. After completion of the dropping, 2,2'-
Add 0.4 parts of azobisisobutylnitrile, and add 4 parts.
After stirring for hours, polymer solutions b1 to b3 for vehicles having the characteristic values shown in Table 2 were obtained.

[0076]

[Table 2]

2. Production example of antifouling paint 2-1. Antifouling paint (A) Charge the raw materials and glass beads shown in Table 3 in a plastic container, stir and disperse with a paint shaker for 1 hour, and paint A1 to A4
I got

[0078]

[Table 3]

2-2. Antifouling paint (B) The raw materials and glass beads shown in Table 4 were charged into a plastic container, and the mixture was stirred and dispersed for 1 hour with a paint shaker.
I got

[0080]

[Table 4]

3. Example of application of composite antifouling paint film An antifouling paint B3 containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit was applied to a 100 × 300 mm steel sheet coated with an anticorrosion paint film so that the dry film thickness became 200 μm. Then, it was immersed in a raft in Hiroshima Bay at a depth of 2 m below the sea surface for 12 months, washed with water and dried to obtain an old coating film I.

Similarly, the antifouling coating film A1 and the tin polymer type antifouling coating film were immersed, washed with water, and dried to obtain an old coating film.
II, old coating film III.

[0083]

EXAMPLES 1-4, COMPARATIVE EXAMPLES 1-2 The first and second coatings shown in Table 5 were applied to the old coating film I so that the dry film thickness was 100 μm each, and 2 m below sea level on a raft in Hiroshima Bay. Immersion for 6 months to compare the antifouling performance, and at the same time, the adhesion test with the old coating film was performed according to the JIS K5400 8.5.2.
997). Table 5 shows the results of antifouling performance and adhesion.

[0084]

[Table 5]

[0085]

Examples 5 to 8 and Comparative Examples 3 to 4 The first and second coatings shown in Table 6 were applied to the old coating film II so that the dry film thickness would be 100 μm each, and 2 m below sea level on a raft in Hiroshima Bay. Immersion for 6 months to compare the antifouling performance, and at the same time, the adhesion test with the old coating film was performed according to the JIS K5400 8.5.2.
997). Table 6 shows the antifouling performance and adhesion results.

[0086]

[Table 6]

[0087]

Examples 9 to 12 and Comparative Examples 5 to 6
The first and second coatings shown in Table 2 have a dry film thickness of 100 μm each.
It was immersed in a raft in Hiroshima Bay for 2 months under the sea surface for 6 months to compare the antifouling performance. At the same time, the adhesion test with the old coating film was performed according to the JIS K5400 8.5.2. ). Table 7 shows the antifouling performance and adhesion results.

[0088]

[Table 7]

Evaluation of antifouling performance 4: No damage prevention 3: Within 5% of damage prevention area 2: 5 to 25% of damage prevention area 1: 25% or more of damage prevention area Evaluation of adhesion performance 10: Every cut is thin. Both sides are smooth and there is no separation at the intersection of the cut and the square at a glance.

8: There is a slight peeling at the intersection of the cuts, and there is no peeling at a glance of the square, and the area of the defective part is within 5% of the total square area. 6: Both sides of the cut and the intersection were peeled off, and the area of the defect was 5 to 15% of the area of the entire square. 4: The width of the peeling due to the cut is wide, and the area of the defective portion is 15 to 35% of the total square area.

2: The width of the peeling due to the cut is wider than 4 points, and the area of the defective portion is 35 to 65% of the area of the entire square. 0: Peeling area is 65% or more of the total square area.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 59/20 A01N 59/20 Z B05D 1/36 B05D 1/36 Z 5/00 5/00 H 7 / 24 302 7/24 302P C09D 133/02 C09D 133/02 143/04 143/04 D06M 15/263 D06M 15/263 (72) Inventor Yasuyuki Onishi 1 Meiji Shinkai 1 No. 1 China Paint, Otake City, Hiroshima Prefecture, Japan Co., Ltd. (72) Inventor Masashi Ono 1-7-1, Meiji-Shinkai, Otake-shi, Hiroshima Pref. DH02 DH07 DH08 4J038 CG011 CG031 CG041 CG061 CG071 CG141 CL001 GA03 GA07 GA15 GA16 HA066 HA216 HA356 HA376 HA456 HA466 HA476 JA56 JB23 JB24 JB27 JB36 JC01 JC07 JC37 JC38 KA02 KA07 P05 NA12 P L033 AC04 CA18 DA06

Claims (23)

[Claims] 1. The method according to claim 1, wherein (A) at least one antifouling coating film formed from an antifouling coating material containing a copolymer containing a polymerizable unsaturated metal carboxylate component unit has (B) polymerizable A composite antifouling coating formed by laminating at least one antifouling coating formed from an antifouling coating containing a copolymer containing an unsaturated carboxylic acid silyl ester component unit. 2. The copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit which is free of a hydroxy group bonded to a metal atom. 2. The composite antifouling coating film according to 1. 3. The copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit has a general formula [I]: R ¹ —COO-ML _n .. [I] [formula [I] Where R ¹ is CH ₂ ＣC (CH ₃ ) —, CH ₂ ＣＨ
CH-, HOOC-CH = CH-, HOOC-CH = C
(CH ₃ ) — represents an organic group containing an unsaturated bond represented by any of formulas, and —COOH may form a metal salt or an ester. M represents a metal atom, L represents an organic acid residue: —OCOR ² , R ² has a carbon number of 1 to 25, and has a chain alkyl group, an alicyclic alkyl group, an aromatic hydrocarbon group, N represents an aralkyl group, and n represents the number of the valence number of the metal M minus one. Or a copolymer having in its molecule a component unit derived from a metal salt of a polymerizable unsaturated carboxylic acid represented by the formula:
3. The composite antifouling coating film according to item 1. 4. The composite composite according to claim 1, wherein the copolymer containing a polymerizable unsaturated metal carboxylate component unit is a copolymer containing a metal (meth) acrylate component unit. Dirty coating. 5. The copolymer containing a metal salt unit of a polymerizable unsaturated carboxylic acid component is a copolymer containing a zinc salt (meth) acrylate component unit or a copolymer containing a copper (meth) acrylate component unit unit. The composite antifouling coating film according to claim 1. 6. A copolymer comprising a metal unit of a polymerizable unsaturated carboxylic acid metal salt component, which is a copolymer of a zinc (meth) acrylate or copper salt monomer (a) and this monomer (a). Other monomer (b) is copolymerized, and 2 to 60% by weight of a component unit derived from the zinc (meth) acrylate or copper salt monomer (a) can be copolymerized. A polymerizable unsaturated carboxylic acid metal salt component unit containing 40 to 98% by weight (component unit (a) + (b) = 100% by weight) of a component unit derived from another monomer (b) Claim 1 which is united
5. The composite antifouling coating film according to any one of 5. 7. The composite antifouling coating film according to claim 1, wherein the copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit is a copolymer containing a polymerizable unsaturated carboxylic acid hydroxy metal salt component unit. . 8. The copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit is represented by the following general formula [II]: R ¹ -COO-M-OH [II] [In the formula [II] , R ¹ are CH ₂ ＣC (CH ₃ ) —, CH ₂ =
CH-, HOOC-CH = CH-, HOOC-CH = C
(CH ₃ ) — represents an organic group containing an unsaturated bond represented by any of formulas, and —COOH may form a metal salt or an ester. M represents a metal atom. The composite antifouling coating film according to claim 1, wherein the copolymer has a component unit derived from a polymerizable unsaturated carboxylic acid hydroxy metal salt represented by the following formula: 9. The polymer according to claim 1, wherein said copolymer containing a polymerizable unsaturated metal carboxylate component unit is a copolymer containing a hydroxy metal (meth) acrylate component unit. Composite antifouling coating. 10. The copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit, wherein the copolymer containing a hydroxyzinc (meth) acrylate component unit or the copolymer containing a hydroxycopper (meth) acrylate component unit is used. Claim 1, which is a union
10. The composite antifouling coating film according to any one of 7, 8, and 9. 11. The polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer is represented by the following general formula [III]: R ¹ —COO—Si (L ¹ L ² L ³ ) [III] [In the formula [III], R ¹ is CH ₂ ＣC (CH ₃ ) —, CH ₂
= CH-, HOOC-CH = CH-, HOOC-CH =
C (CH ₃ ) — represents an organic group containing an unsaturated bond represented by any of formulas, and —COOH may form a metal salt or an ester. L ¹ , L ² , and L ³ may be the same or different, and each has 1 to 20 carbon atoms, and is a chain alkyl group, an alicyclic alkyl group, an aromatic hydrocarbon group, or an aralkyl group. And any of their substitutes. And a copolymer comprising a polymerizable unsaturated carboxylic acid silyl ester monomer and an unsaturated monomer copolymerizable therewith.
11. The composite antifouling coating film according to any one of items 10 to 10. 12. The above polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer is a copolymer of silyl (meth) acrylate and another unsaturated monomer copolymerizable therewith. 2 to 60% by weight of a component unit derived from (meth) acrylate, and 40 to 98% by weight of a component unit derived from another copolymerizable unsaturated monomer.
The composite antifouling coating film according to any one of claims 1 to 11, which is a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit, wherein the total amount of both component units is 100% by weight. 13. The antifouling paint containing a copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit, which forms the antifouling coating film (A), further contains copper or a copper compound. 13. The composite antifouling coating film according to any one of 12. 14. An antifouling paint containing a copolymer containing a polymerizable unsaturated metal carboxylate component unit, which forms the antifouling coating film (A), further comprises zinc oxide.
The antifouling coating film according to any one of the above. 15. An antifouling paint containing a copolymer containing a polymerizable unsaturated carboxylic acid metal salt component unit forming the antifouling coating film (A), further comprising an organic antifouling agent. 1
5. The composite antifouling coating film according to any one of 4. 16. An antifouling paint containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit, which forms the antifouling coating film (B), further contains copper or a copper compound. 15. The composite antifouling coating film according to any one of 15. 17. The antifouling paint containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit, which forms the antifouling coating film (B), further contains zinc oxide. The composite antifouling coating film according to any one of the above. 18. The antifouling paint containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit, which forms the antifouling coating film (B), further contains a dehydrating agent.
18. The composite antifouling coating film according to any one of items 17 to 17. 19. An antifouling paint containing a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit, which forms the antifouling coating film (B), further contains an organic antifouling agent. 19. The composite antifouling coating film according to any one of 18. 20. The composite antifouling coating film according to any one of claims 1 to 19, wherein the antifouling coating film (A) side of the composite antifouling coating film is in close contact with the surface of a ship or underwater structure. Alternatively, a ship or an underwater structure characterized by being opposed to each other. 21. The composite antifouling coating film according to any one of claims 1 to 19, wherein the antifouling coating film (A) side of the composite antifouling coating film is in close contact with the surface of a ship or underwater structure. Alternatively, a fishing gear or a fishing net characterized by being opposed to each other. 22. The composite antifouling coating film according to any one of claims 1 to 19, wherein the antifouling coating film (A) side of the composite antifouling coating film is in close contact with or facing the surface of a ship or underwater structure. A method of coating a surface of a ship or an underwater structure so as to cover the surface of the ship or the underwater structure. 23. The composite antifouling coating film according to any one of claims 1 to 19, wherein the antifouling coating film (A) side of the composite antifouling coating film is in close contact with or faces the surface of a fishing gear or fishing net. And a fishing net or a fishing net covering the surface thereof.