KR101994061B1 - Laminated antifouling coating film, antifouling substrate and vessel - Google Patents

Abstract

An object of the present invention is to provide a laminated antifouling coating film which can obtain excellent antifouling performance under any of high-speed conditions such as long-term high-speed, high operating rate, and inexpensive operating conditions at the initial stage of immersion such as design. The present invention also provides an antifouling substrate coated with the laminated antifouling coating film and a ship. The laminated antifouling coating film of the present invention has an upper antifouling coating film (A) formed from the upper antifouling coating composition (a) and a lower antifouling coating film (B) formed from the lower antifouling coating composition (b) a) is when the acid value of the solvent-soluble portion of the lower layer antifouling coating film (B) is laminated on the upper layer, the upper layer antifouling coating film (a) and the lower layer antifouling coating film (B) of the respective AV _a, AV _B, the following formula (1).
AV _A > AV _B (1)

Description

Laminated antifouling coating film, antifouling substrate and vessel

The present invention relates to a laminated antifouling coating film, an antifouling substrate coated with the laminated antifouling coating film, and a ship.

At present, in order to prevent fouling due to the attachment of aquatic organisms such as ships, the antifouling coating film having paint film-renewing properties, which gradually releases the component of the coating film from the surface of the coating film over time in water, Is widely used.

Generally, the antifouling coating film having such paint film-renewing properties can be obtained by using an acid or a combination of a polymer or a compound having a group which causes an acid cycle by a hydrolysis reaction to increase the hydrophilicity by hydrolysis reaction or hydration reaction in water Whereby the hydrophilic moiety gradually gets water from the surface of the coating film and is burned to exhibit paint film renewability so that the fixation of aquatic organisms adhering to the surface of the coating film can be prevented directly or the physiological activity And the antifouling agent having the antifouling agent is allowed to stand.

It is known that the antifouling coating film having the paint film-renewing property can obtain a desired coating film update speed by adjusting the composition according to the application of the antifouling coating film, the water flow intensity and the temperature to be exposed, and the like. For example, when the coating film having a high coating film renewal rate is obtained by increasing the content of the compound having an acid group, and the coating film is used in ships having navigational conditions in which coating film renewability such as low speed, low operating rate, Sufficient antifouling property can be exhibited. However, the antifouling coating film whose coating film renewal speed is adjusted so as to meet the navigational conditions hardly achieving coating film renewability is lost in a short period of time due to excessive consumption, so that the antifouling performance can not be maintained for a sufficient period of time, .

In order to solve the above problem, the following problem arises in the case where an antifouling coating film with a slow coating film renewal speed is formed. Specifically, in order to improve the production efficiency in the drying of a ship or the like, a shipboard sheath coated with the antifouling coating film is completed, and the boat is launched from a dock, moored for a long time on the quay wall, There is a process called equipment. During this designing process, since water flow is hardly applied to the coating film, the coating film renewability is not sufficiently exhibited, and there is a problem in that it is exposed to the risk of contamination by aquatic organisms.

In order to solve this problem, for example, Patent Document 1 proposes a coating composition comprising a rosin-based compound, an organic silyl ester group-containing polymer having a specific triorganosilyl group, and an antifouling agent .

Japanese Unexamined Patent Application Publication No. 2003-176442

In the conventional art including the coating composition disclosed in the above Patent Document 1, particularly in the antifouling coating film having a slow coating film renewal speed, which is designed on the assumption of the traveling condition such as high speed and high operation rate, the risk of damage due to aquatic organisms , There is a problem that sufficient antifouling property can not be exhibited and the contamination proceeds.

In view of the above problems, it is an object of the present invention to provide a laminated antifouling coating film having excellent antifouling properties even under any conditions of high-speed operation such as high-speed operation, high operating rate of the organ, and low- The purpose. It is another object of the present invention to provide an antifouling substrate and a vessel coated with the laminated antifouling coating film.

As a result of intensive studies, the present inventors have found that the aforementioned problems can be solved by using a laminated antifouling coating film having the following specific conditions, and have accomplished the present invention.

The present invention relates to the following [1] to [23].

[1] An antifouling coating film (A) comprising an upper antifouling coating film (A) formed from an upper antifouling coating composition (a) and a lower antifouling coating film (B) formed from a lower antifouling coating composition (1) is satisfied when the acid values of the solvent soluble components of the upper antifouling coating film (A) and the lower antifouling coating film (B) are respectively AV _A and AV _B , Wherein the laminated antifouling coating film is a laminated antifouling coating film.

AV _A > AV _B (1)

[2] The antifouling paint composition according to [1], wherein the upper layer antifouling paint composition (a) contains a hydrolyzable polymer (C) having a silyl ester group represented by the following formula (I) or a metal ester group represented by the following formula The laminated antifouling coating film described above.

(Wherein R ¹ to R ³ each independently represent a monovalent hydrocarbon group, preferably a methyl group, an ethyl group, an isopropyl group, a n-propyl group, an isobutyl group, a sec-butyl group, Ethylhexyl group or phenyl group, more preferably isopropyl group, n-propyl group, sec-butyl group, n-butyl group or phenyl group, more preferably all of R ¹ to R ³ represent isopropyl group, Position.)

(Wherein M represents a metal, preferably copper or zinc, more preferably zinc, and * represents a bonding position).

[3] The antifouling paint composition according to [1] or [2], wherein the lower layer antifouling paint composition (b) contains a hydrolyzable polymer (C) having a silyl ester group represented by the following formula (I) or a metal ester group represented by the following formula The laminated antifouling coating film according to [2].

(Wherein R ¹ to R ³ each independently represent a monovalent hydrocarbon group, preferably a methyl group, an ethyl group, an isopropyl group, a n-propyl group, an isobutyl group, a sec-butyl group, Ethylhexyl group or phenyl group, more preferably isopropyl group, n-propyl group, sec-butyl group, n-butyl group or phenyl group, more preferably all of R ¹ to R ³ represent isopropyl group, Position.)

(Wherein M represents a metal, preferably copper or zinc, more preferably zinc, and * represents a bonding position).

(4) The hydrolyzable polymer (C) having a silyl ester group is a (meth) acrylate compound having a silyl ester group-containing structural unit derived from a monomer having a silyl ester group and having a silyl ester group, (Meth) acrylate, tri-n-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, (Meth) acrylate, triisobutylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri (2-ethylhexyl) (meth) acrylate and phenyldiisobutylsilyl (meth) acrylate, at least one selected from the group consisting of sec-butyldimethylsilyl The laminated antifouling coating film described in [2] or [3].

[5] The positive resist composition as described in [1], wherein the hydrolyzable polymer (C) having a metal ester group has a structural unit derived from a monomer having a metal ester group and the monomer having the metal ester group is selected from the group consisting of zinc di (meth) acrylate, copper di (meth) (3-methacryloyloxy-2-methylpropionic acid) zinc, 3- (meth) acryloyloxypropionic acid (versatate), zinc At least one selected from the group consisting of zinc, (meth) acrylic acid (rosin) zinc, (meth) acrylic acid (rosin) copper, (meth) acrylic acid (naphthenic acid) zinc and (meth) acrylic acid Is a zinc (meth) acrylate and / or acrylic acid (methacrylate) zinc.

[6] The antifouling paint composition according to any one of [1] to [4], wherein the upper antifouling coating composition (a) and the lower antifouling coating composition (b) contain a hydrolysable polymer (C) having a silyl ester group represented by the following formula (I) Wherein the laminated antifouling coating film according to any one of claims 1 to 3,

(Wherein R ¹ to R ³ each independently represent a monovalent hydrocarbon group, preferably a methyl group, an ethyl group, an isopropyl group, a n-propyl group, an isobutyl group, a sec-butyl group, Ethylhexyl group or phenyl group, more preferably isopropyl group, n-propyl group, sec-butyl group, n-butyl group or phenyl group, more preferably all of R ¹ to R ³ represent isopropyl group, Position.)

It is preferable that the AV _A is 45 mgKOH / g or more, preferably 47 mgKOH / g or more, preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less and the AV _B is less than 45 mgKOH / g Is not more than 43 mgKOH / g, preferably not less than 5 mgKOH / g, more preferably not less than 10 mgKOH / g.

[6] or [6], wherein the AV _A -AV _B is not less than 4 mg KOH / g, preferably not less than 8 mg KOH / g, not more than 100 mg KOH / g, preferably not more than 80 mg KOH / g, more preferably not more than 60 mg KOH / 7. The laminated antifouling coating film according to claim 7,

[9] The laminated antifouling coating film according to any one of [1] to [5], wherein the upper antifouling coating composition (a) contains a hydrolyzable polymer (C) having a metal ester group represented by the following formula (II).

(Wherein M represents a metal, preferably copper or zinc, more preferably zinc, and * represents a bonding position).

[10] The laminated antifouling coating film according to [9], wherein the AV _A is 100 mg KOH / g or more and the AV _B is less than 100 mg KOH / g.

The lower layer antifouling paint composition (b) contains a hydrolyzable polymer (C) having a metal ester group and has an AV _A of 100 mgKOH / g or more, preferably 102 mgKOH / g or more, more preferably 104 mgKOH / g or more G, preferably not more than 200 mg KOH / g, more preferably not more than 160 mg KOH / g, more preferably not more than 120 mg KOH / g, AV _B is less than 100 mg KOH / g, preferably not more than 98 mg KOH / g, The antifouling coating film according to [9] or [10], wherein the antifouling coating film has a weight-average particle diameter of not more than 30 mgKOH / g, preferably not less than 30 mgKOH / g, more preferably not less than 50 mgKOH / g, and even more preferably not less than 80 mgKOH / g.

[12] The laminated antifouget coating composition according to [11], wherein the AV _A -AV _B is 10 mgKOH / g or more, preferably 15 mgKOH / g or more, and 100 mgKOH / g or less, preferably 50 mgKOH / g or less.

[13] The antifouling paint composition according to any one of [1] to [10], wherein the lower layer antifouling paint composition (b) contains a hydrolyzable polymer (C) having a silyl ester group and has an AV _A of 100 mgKOH / g or more, preferably 102 mgKOH / g or more, more preferably 105 mgKOH / , More preferably not less than 108 mg KOH / g, preferably not more than 200 mg KOH / g, more preferably not more than 160 mg KOH / g, still more preferably not more than 120 mg KOH / g and AV _B less than 45 mg KOH, preferably not more than 43 mg KOH / g , More preferably not more than 41 mg KOH / g, more preferably not more than 39 mg KOH / g, preferably not more than 5 mg KOH / g, more preferably not more than 10 mg KOH / g, more preferably not more than 20 mg KOH / 10. The laminated antifouling coating film according to claim 10,

[14] The laminated antifouling coating film according to any one of [2] to [13], wherein the hydrolyzable polymer (C) further has a group represented by the following formula (III).

Wherein X is a divalent hydrocarbon group having 2 to 10 carbon atoms, preferably a hydrocarbon group is an alkylene group or an arylene group, more preferably a hydrocarbon group is an alkylene group, more preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, Y is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group, and n is an integer of 1 to 4, and more preferably an ethylene group or a propylene group, An integer of 1 to 50, preferably 1, and * represents a bonding position.)

The hydrolyzable polymer (C) has a structural unit derived from a monomer having a group represented by the formula (III), wherein the monomer having a group represented by the formula (III) is an alkoxyalkyl (meth) The laminated antifouling coating film according to [14], which is a hydroxyalkyl (meth) acrylate, preferably an alkoxyalkyl (meth) acrylate, more preferably 2-methoxyethyl (meth) acrylate.

The hydrolyzable polymer (C) has a structural unit derived from a monomer having a group represented by the formula (III), and the content of a structural unit derived from a monomer having a group represented by the formula (III) The antifouling coating film according to [14] or [15], wherein the degradable polymer (C) contains 2 to 60 mass%, and preferably 4 to 40 mass%.

[17] The antifouling paint composition according to any one of [1] to [16], wherein the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains a monocarboxylic acid compound (D) and / Laminated antifouling coating film.

The monocarboxylic acid compound (D) is selected from the group consisting of a saturated or unsaturated aliphatic monocarboxylic acid having 10 to 40 carbon atoms, a saturated or unsaturated alicyclic monocarboxylic acid having 3 to 40 carbon atoms, and salts thereof The laminated antifouling coating film according to [17], which is at least one kind.

[19] The laminated antifouling coating film according to any one of [1] to [18], wherein the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains an antifouling agent (E).

Wherein the antifouling agent (E) is selected from the group consisting of copper oxide, copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin- , A borane-nitrogen-based base adduct, and medetomidine. The laminated antifouling coating film according to [19]

[21] Any one of [1] to [20], wherein the amount of the solvent soluble components in the upper antifouling coating film (A) and the lower antifouling coating film (B) is 10 to 60 mass%, and preferably 15 to 50 mass% The laminated antifouling coating film described in one.

[22] An antifouling substrate coated with the laminated antifouling coating film described in any one of [1] to [21].

[23] A ship coated with the laminated antifouling coating film described in any one of [1] to [21].

According to the present invention, it is possible to provide a laminated antifouling coating film having excellent antifouling properties under any of the conditions of high elongation at high speed, high operating conditions such as high operating rate, and inexpensive operating conditions at the initial stage of immersion, such as during the design process. Further, according to the present invention, it is possible to provide an antifouling substrate and a vessel coated with the laminated antifouling coating film.

[Laminated antifouling coating film]

The laminated antifouling coating film of the present invention has an upper antifouling coating film (A) formed from the upper antifouling coating composition (a) and a lower antifouling coating film (B) formed from the lower antifouling coating composition (b) a) is when the acid value of the solvent-soluble portion of the lower layer antifouling coating film (B) is laminated on the upper layer, the upper layer antifouling coating film (a) and the lower layer antifouling coating film (B) of the respective AV _a, AV _B, the following formula (1).

AV _A > AV _B (1)

According to the present invention, even when exposed to a high risk of contamination under low-cost conditions close to the initial stage of immersion, such as during the process of designing during shipbuilding, it exhibits excellent antifouling property, Even when exposed to a high consumption load condition (high operating condition) of the antifouling coating film, and exhibits excellent antifouling performance.

In the following description, the term " high running condition " means a high load condition such as high temperature, high running rate and high speed running, and the term " low running condition " means low temperature, low running rate, It means low consumption load condition. The upper-layer antifouling paint composition (a) and the lower-layer antifouling paint composition (b) are collectively referred to simply as "paint composition" or "antifouling paint composition".

The conventional antifouling coating film as shown in Patent Document 1 is formed with an antifouling coating film in accordance with the high treading conditions and as a result there is a problem that contamination such as adherence of aquatic organisms is generated under low-cost conditions such as during the design process period. The present inventors have intensively studied and found that the above problems can be solved by laminating an upper antifouling coating film and a lower antifouling coating film having different acid values of solvent-soluble components, thereby completing the present invention.

The detailed functional groups for obtaining the above effects are not necessarily clear, but some are estimated as follows. That is, by increasing the acid value of the solvent-soluble fraction of the upper layer antifouling coating film, the film-renewal property is high even under low-cost operating conditions and adhesion of aquatic organisms is suppressed, while the acid value of the solvent- It is presumed that the antifouling performance can be exerted for a long period of time without disappearing the antifouling coating film even under the high agitation condition.

<Acid value of solvent-soluble component>

The "acid value of the solvent-soluble component" in the present invention refers to the acid value of a mixture of components which are soluble in a specific solvent, which will be described later, in the solid content excluding the volatile component of the coating composition. The component soluble in the solvent is considered to be a component that forms a continuous phase of a coating film, such as resin, resin acid (rosin, and versatate), and the like.

Acid value is defined as the amount (mg) of potassium hydroxide (KOH) required to neutralize 1 g of the component of the object, expressed in units of mgKOH / g, and is a numerical value widely used to indicate the acid group content of the object.

The acid value of the solvent-soluble component of the coating film is obtained by measuring the acid value of the solvent-soluble component obtained by extracting the coating film with a solvent, using a method according to JIS K 5601-2-1: 1999 or the like. The solvent to be used for the extraction is generally selected from the group consisting of xylene / ethanol mixed solution (mixing ratio (mass ratio): xylene / ethanol = 70 / 30, all the same).

Specifically, the acid value of the solvent-soluble component can be measured by, for example, the following procedures (1) to (6).

(1) Take a mixture of a weighed coating film and a xylene / ethanol mixture having a mass which is about ten times its weight in a centrifuge tube.

(2) Centrifuge at 0 DEG C / 3,500 rpm for 30 minutes, remove the supernatant, and transfer to another container.

(3) Add the same volume of xylene / ethanol mixture solution as (1) to the extracted residue again, centrifuge under the same conditions, remove the supernatant, and add to the first container containing the supernatant. This operation is repeated one more time.

(4) The above supernatant is collected as an extract, and the mass% of solids of the extract is measured. The solid mass% is obtained by drying the weighed extract solution in a hot-air drier at 108 DEG C for 3 hours and measuring the mass of the remaining solid content. The mass of the solvent-soluble fraction contained in the extract can be calculated by multiplying the mass of the extract by the mass% of solids. The mass% of the solvent soluble component in the coating film is calculated by calculating the ratio of the mass of the solvent soluble component to the mass of the coating film weighed in (1).

(5) About 5 g of the above extract is put into a beaker, and the mass of the extract is measured. The mass of the solubles soluble in the sample is calculated using the mass% of the solids obtained in the above (4) . This solution is diluted with ethanol to a total volume of 50 mL.

(6) A 0.1 mol / L potassium hydroxide solution (alcoholic) (N / 10) (produced by KANTO CHEMICAL Co., Ltd.) was added to the solution containing only the ethanol diluting solution and the corresponding solvent as the blank prepared in (5) Potentiometric titration is carried out at 20 ° C using the above-described method, and the acid value AV is calculated from the following equation.

AV = {(V _{X -} V ₀ ) x f x 5.61} x

x: Mass of the sample (g)

V _X : Appropriate value of the sample (ml)

V ₀ : Proper value of blank (ml)

f: Factor of 0.1 mol / L potassium hydroxide solution used for titration

For potentiometric titration, Hirunuma automatic titrator COM-1750 (manufactured by Hiranuma Industry Co., Ltd.) is used.

On the other hand, extraction of the solvent-soluble component and measurement of its acid value can be performed not only from the formed coating film but also from the coating composition by the same method.

&Lt; Upper layer antifouling paint composition (a) and lower layer antifouling paint composition (b)

In the present invention, the upper antifouling coating film (A) is formed of the upper antifouling coating composition (a) and the lower antifouling coating film (B) is formed of the lower antifouling coating composition (b).

The upper antifouling coating composition (a) and the lower antifouling coating composition (b) each contain a hydrolyzable polymer (C), a monocarboxylic acid compound (D), an antifouling agent (E), other binder component (F) It is preferable to contain an organic solvent (H), a sag preventing agent / sedimentation preventing agent (I), a dehydrating agent (J), a plasticizer (K)

In the present invention, the upper antifouling coating composition (a) and the lower antifouling coating composition (b) preferably contain a hydrolyzable polymer (C) and, if necessary, a monocarboxylic acid compound (D) When the lower layer antifouling paint composition (a) and the lower layer antifouling paint composition (b) do not contain the monocarboxylic acid compound (D), the hydrolyzable polymer (C) preferably contains an acidic group and / or a metal salt thereof.

(Hydrolyzable polymer (C))

In the present invention, the upper layer antifouling paint composition (a) and / or the lower layer antifouling paint composition (b) is obtained by mixing the hydrolyzable polymer (C) with the hydrolyzable polymer .

The hydrolyzable polymer (C) in the present invention is a polymer having a hydrolyzable group which undergoes hydrolysis reaction in water, and examples of the hydrolyzable group include silyl ester groups and metal ester groups.

Examples of such a hydrolyzable polymer (C) include a homopolymer of a monomer (c1) having a hydrolyzable group such as a silyl ester group or a metal ester group, a monomer (c1) having the hydrolyzable group, And copolymers obtained by a polymerization reaction of other copolymerizable monomer (c2).

[Hydrolyzable polymer having silyl ester group]

In the present invention, the upper-layer antifouling coating composition (a) and / or the lower-layer antifouling paint composition (b) is preferably a hydrolyzable polymer having a silyl ester group (hereinafter also referred to as a silyl ester group-containing hydrolyzable polymer ) May be contained.

As the "silyl ester group", for example, a silyl ester group represented by the following formula (I) is preferably exemplified.

(In the formula (I), R ¹ to R ³ each independently represent a monovalent hydrocarbon group, and * represents a bonding position.)

In formula (I), examples of R ¹ to R ³ include linear, branched or cyclic alkyl groups and aryl groups, and the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, More preferably an alkyl group having 1 to 4 carbon atoms. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of R ¹ to R ³ include a methyl group, an ethyl group, an isopropyl group, a n-propyl group, an isobutyl group, a sec-butyl group, a n-butyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, n-butyl group and phenyl group, and R ¹ to R ³ are all isopropyl groups.

* In the formula (I) represents a bonding position, and indicates that it is connected to an arbitrary group, preferably an arbitrary organic group.

As the monomer (c11) having a silyl ester group in the monomer (c1) having a hydrolyzable group, a (meth) acrylate compound having a silyl ester group is preferable, and for example, trimethylsilyl (meth) (Meth) acrylate, triisopropylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, triisopropylsilyl (Meth) acrylate, n-butyldimethylsilyl (meth) acrylate, t-butyldimethylsilyl (meth) acrylate, (Meth) acrylate, and phenyldiisobutylsilyl (meth) acrylate. The hydrolysis rate of the hydrolyzable polymer (C) and the stainproofing property of the hydrolyzable polymer (C) From the viewpoint of coating film renewal persistence and water resistance of the coating film, triisopropylsilyl (meth) acrylate is more preferable.

Meanwhile, in the present invention, "(meth) acrylate" means "acrylate or methacrylate", and other similar notations mean the same.

When the hydrolyzable polymer (C) contains a constituent unit derived from the silyl ester group-containing monomer (c11), the content thereof is preferably 10 to 90 mass%, more preferably 30 to 80 mass% Is more preferable.

When the hydrolyzable polymer (C) contains a constituent unit derived from the silyl ester group-containing monomer (c11), the hydrolyzable polymer (C) can be produced, for example, in the following procedure.

A solvent was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction pipe and a heating and cooling jacket, and while keeping the temperature at 80 to 90 占 폚 under a nitrogen stream, (C11) having the silyl ester group, the other monomer (c2), a polymerization initiator, a chain transfer agent and a solvent is dropped from the reaction vessel into the reaction vessel and the polymerization reaction is carried out to obtain a hydrolyzable polymer having a silyl ester group Can be obtained.

On the other hand, the ratio of the content (mass) of each constituent unit derived from each monomer in the hydrolyzable polymer (C) can be regarded as being the same as the ratio of the input amounts (mass) of the respective monomers used in the polymerization reaction.

The polymerization initiator that can be used in the production of the hydrolyzable polymer (C) is not particularly limited, and various radical polymerization initiators can be used. Specific examples include benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2,2'-azobis (isobutyronitrile) [AIBN] Azobis (2-methylbutyronitrile) [AMBN], 2,2'-azobis (2,4-dimethylvaleronitrile) [ADVN] and tert-butyl peroctoate [TBPO] And the like. These polymerization initiators may be used alone or in combination of two or more. On the other hand, these radical polymerization initiators may be added to the reaction system only at the start of the reaction, or may be added both to the reaction system at the initiation of the reaction and during the reaction.

The amount of the polymerization initiator to be used in the production of the hydrolyzable polymer (C) is preferably from 0.1 to 20 parts by mass, more preferably from 0.3 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass, per 100 parts by mass of the sum of the respective monomers Is more preferable.

The chain transfer agent usable in the production of the hydrolyzable polymer (C) is not particularly limited and includes, for example,? -Methylstyrene dimer, thioglycolic acid, dietherphene, terpinolene,? -Terpinene; mercaptans such as tert-dodecyl mercaptan and n-dodecyl mercaptan; Halides such as carbon tetrachloride, methylene chloride, bromoform and bromotrichloroethane; And secondary alcohols such as isopropanol and glycerin. These chain transfer agents may be used alone or in combination of two or more.

When a chain transfer agent is used in the production of the hydrolyzable polymer (C), the amount of the chain transfer agent to be used is preferably 0.1 to 5 parts by mass per 100 parts by mass of the total amount of the respective monomers.

As the solvent usable for the production of the hydrolyzable polymer (C), for example, aromatic solvents such as toluene, xylene and mesitylene; Alcohols such as propanol, butanol, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; Ketones such as methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone; Esters such as ethyl acetate and butyl acetate; Water and the like. These solvents may be used alone or in combination of two or more.

When a solvent is used in the production of the hydrolyzable polymer (C), there is no particular limitation on the amount to be used, but it is preferably 5 to 150 parts by mass per 100 parts by mass of the total amount of the respective monomers.

[Hydrolyzable polymer having metal ester group]

In the present invention, the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) is preferably a hydrolyzable polymer having a metal ester group (hereinafter also referred to as a metal ester group-containing hydrolyzable polymer ) May be contained.

The above-mentioned &quot; metal ester group &quot; refers to a group formed by bonding of a metal and a carboxylic acid. The "polyvalent metal ester group" or the "divalent metal ester group" to be described later refers to a group formed by bonding of a polyvalent metal or a divalent metal and a carboxylic acid.

As the metal ester group, a polyvalent metal ester group is preferable, and a divalent metal ester group represented by the following formula (II) is more preferable.

(In the formula (II), M represents a metal and * represents a bonding position.)

Examples of the metal constituting the metal ester group include magnesium, calcium, neodymium, titanium, zirconium, iron, ruthenium, cobalt, nickel, copper, zinc and aluminum.

In the formula (II), M is a divalent metal, and a divalent metal among the metals described above can be suitably selected and used. Of these, M is preferably a metal of group 10 to 12 such as nickel, copper and zinc, more preferably selected from the group consisting of copper and zinc, and more preferably zinc.

In the formula (II), * represents a bonding position and indicates that it is connected to an arbitrary group, preferably an arbitrary organic group.

Examples of the monomer (c12) having a metal ester group in the monomer (c1) having a hydrolyzable group include zinc di (meth) acrylate, copper di (meth) acrylate, (Meth) acryloyloxypropionic acid (versatate) zinc, (meth) acrylic acid (rosin) zinc (methacryloyloxypropionic acid) (Meth) acrylic acid (rosin) copper, (meth) acrylic acid (naphthenic acid) zinc and (meth) acrylic acid (naphthenic acid) copper, and the hydrolysis rate of the hydrolyzable polymer (C) (Meth) acrylate and (meth) acrylic acid (zinc methacrylate) are preferable from the viewpoint of paint film renewal persistence and water resistance of the antifouling coating film containing the antifouling coating film (C).

When the hydrolyzable polymer (C) contains a constituent unit derived from the monomer (c12) having a metal ester group, its content is preferably 1 to 60% by mass, more preferably 5 to 30% by mass in the hydrolyzable polymer (C) Is more preferable. The content of the metal in the hydrolyzable polymer (C) is preferably 0.5 to 25% by mass, more preferably 1 to 5% by mass in the hydrolyzable polymer (C) from the viewpoint of coating film renewability and antifouling property of the antifouling coating film to be formed. To 20% by mass. The content of the metal can be measured by an X-ray diffraction apparatus or an ICP emission spectrometer, and can be suitably adjusted by the amount of the monomers used in synthesizing the hydrolyzable polymer (C).

When the hydrolyzable polymer (C) contains a constituent unit derived from the monomer (c12) having a metal ester group, the hydrolyzable polymer (C) can be produced, for example, in the following procedure.

First, a mixed solution obtained by mixing a solvent and a metal component such as zinc oxide is stirred while being heated to about 50 to 80 캜, and a mixed solution of methacrylic acid, acrylic acid, or other organic acid and water is added dropwise, To prepare a monomer (c12) having a metal ester group.

Next, a solvent is placed in a freshly prepared reaction vessel, the mixture is heated to about 80 to 120 DEG C, and a mixture of the monomer (c12) having the metal ester group, other monomer (c2), polymerization initiator, chain transfer agent, And a polymerization reaction is carried out to obtain a hydrolyzable polymer having a metal ester group.

The kind and amount of the polymerization initiator, the chain transfer agent and the solvent that can be used in the production of the hydrolyzable polymer (C) containing the constituent unit derived from the monomer (c12) having a metal ester group are not particularly limited and the silyl ester group The kind and amount as described in the production of the hydrolyzable polymer can be used.

The hydrolyzable polymer (C) may be a copolymer of the monomer (c1) having a hydrolysable group and the other monomer (c2).

Examples of the other monomer (c2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) (Meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, Alkyl (meth) acrylates or aryl (meth) acrylates such as aryl (meth) acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate;

Acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (Meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxybutyldiglycol (Meth) acrylate such as ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate and phenoxypolyethylene glycol (meth) ;

(Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyalkyl (meth) acrylates such as cyipropyl (meth) acrylate;

Glycidyl (meth) acrylate;

(Meth) acrylates containing an organo siloxane group;

And vinyl compounds such as styrene,? -Methylstyrene, vinyl acetate, vinyl benzoate, vinyl toluene, acrylonitrile, vinyl pyridine, vinyl pyrrolidone and vinyl chloride. These monomers may be used alone or in combination of two or more.

As the other monomer (c2), it is preferable to include a monomer (c21) having a group represented by the following formula (III).

(Wherein X represents a divalent hydrocarbon group of 2 to 10 carbon atoms, Y represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 30 carbon atoms, n represents an integer of 1 to 50, and * represents a bonding position.)

In the formula (III), X represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and the hydrocarbon group is preferably an alkylene group or an arylene group, and more preferably an alkylene group. X is more preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and still more preferably an ethylene group or a propylene group.

Y in the formula (III) represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 30 carbon atoms, preferably a monovalent hydrocarbon group of 1 to 4 carbon atoms, more preferably a methyl group.

In the formula (III), n is an integer of 1 to 50, preferably 1. On the other hand, when n is 2 or more, plural Xs may be the same or different.

* In the formula (III) represents a bonding position, and indicates that it is connected to an arbitrary group, preferably an arbitrary organic group.

Examples of such a monomer (c21) include alkoxyalkyl (meth) acrylate and hydroxyalkyl (meth) acrylate, preferably alkoxyalkyl (meth) acrylate, more preferably 2-methoxy Ethyl (meth) acrylate. On the other hand, "alkoxyalkyl (meth) acrylate" is a compound in which H in the hydroxyl group of the hydroxyalkyl (meth) acrylate is substituted with a hydrocarbon group, and examples of the hydrocarbon group include an alkyl group and an aryl group.

When the hydrolyzable polymer (C) contains a constitutional unit derived from such a monomer (c21), its content is preferably 2 to 60% by mass, more preferably 4 to 40% by mass in the hydrolyzable polymer (C) More preferable.

The hydrolyzable polymer (C) of the present invention can be obtained by polymerizing the polymer (c3) having two or more acid groups and the monocarboxylic acid compound (c3) described later as described in International Publication No. 2014/010702, Or a polymer obtained by reacting the metal compound (D) with a metal compound.

Examples of the polymer (c3) having two or more acid groups include a polyester polymer (c31) and an acrylic polymer (c32), and preferably a polyester polymer (c31).

The polyester-based polymer (c31) preferably has a solid acid value of 50 to 250 mgKOH / g, more preferably 80 to 200 mgKOH / g.

The polyester polymer (c31) is obtained by reacting at least one polyhydric alcohol with at least one polyvalent carboxylic acid and / or anhydride thereof, and any kind may be used in an arbitrary amount, and the acid value or viscosity thereof may be adjusted .

As such polyester polymer (c31), for example, after reacting an alcohol having three or more hydroxyl groups (c311), a dibasic acid and / or an anhydride (c312) thereof with a divalent alcohol (c313) It is preferably obtained by reacting a dibasic acid and / or an anhydride thereof (c314).

As the monocarboxylic acid compound (D) to be reacted with the polyester polymer (c31), the following ones can be used, and among them, rosin is preferably used, and examples of the metal compound include zinc oxide, Or the like can be used. Of these, zinc oxide is preferably used.

The weight average molecular weight (Mw) of the hydrolyzable polymer (C) is preferably 500 to 200,000, more preferably 3,000 to 70,000. When the weight average molecular weight (Mw) of the hydrolyzable polymer (C) is within the above range, spraying workability of the coating composition is improved and physical properties of the coating film are further improved.

The number average molecular weight (Mn) of the hydrolyzable polymer (C) is preferably 500 to 100,000, more preferably 700 to 30,000.

On the other hand, when the hydrolyzable polymer (C) is a silyl ester group-containing hydrolyzable polymer, the weight average molecular weight (Mw) is preferably 2,000 to 200,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 70,000 , More preferably 20,000 to 60,000, and the number average molecular weight (Mn) is preferably 1,000 to 100,000, and more preferably 3,000 to 30,000.

When the hydrolyzable polymer (C) is a hydrolyzable polymer having a metal ester group, the weight average molecular weight (Mw) is preferably 500 to 100,000, more preferably 2,000 to 50,000, and the number average molecular weight (Mn) , Preferably 500 to 30,000, and more preferably 700 to 25,000.

On the other hand, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the hydrolyzable polymer (C) refer to values in Gel Permeation Chromatography (GPC) measured by the method described in the Examples.

When the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) of the present invention contains the hydrolyzable polymer (C), the content thereof is preferably 3 to 90% by mass in the solid content of each coating composition , More preferably from 5 to 50 mass%, and even more preferably from 7 to 40 mass%.

When the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains two or more hydrolyzable polymers (C), the content of the hydrolyzable polymers (C) The preferable range for the total content is the same for each component to be described later.

The content of the solvent soluble components in the upper antifouling coating film (A) and the lower antifouling coating film (B) of the present invention is preferably 10 to 60 mass%, more preferably 15 to 50 mass%. When the solvent soluble components in the upper antifouling coating film (A) and the lower antifouling coating film (B) of the present invention fall within the above-mentioned ranges, it is preferable from the viewpoint that appropriate water resistance and strength can be imparted to each coating film.

The laminated antifouling coating film of the present invention is preferably any one of the following (1) to (3).

(1) The upper-layer antifouling paint composition (a) and the lower-layer antifouling paint composition (b) contain a silyl ester group-containing hydrolyzable polymer.

(2) The upper-layer antifouling paint composition (a) and the lower-layer antifouling paint composition (b) contain a metal ester group-containing hydrolyzable polymer.

(3) The upper layer antifouling paint composition (a) contains the metal ester group-containing hydrolyzable polymer and the lower layer antifouling paint composition (b) contains the silyl ester group-containing hydrolyzable polymer.

Of these, the embodiments of (1) and (3) are more preferable, and the embodiment of (1) is more preferable.

(AV _A and AV _B )

Laminating the antifouling coating film of the present invention, when the acid value of the solvent-soluble matter of the upper layer antifouling coating film (A) the AV _A, the acid value of the solvent-soluble matter in the lower layer antifouling coating film (B) to the AV _B, satisfies the following formula (1) .

AV _A > AV _B (1)

The laminated antifouling coating film of the present invention has the acid value AV _A of the solvent soluble component of the upper layer antifouling coating film (A) made larger than the acid value AV _B of the solvent soluble component of the lower layer antifouling coating film (B) , And the antifouling property can be maintained over a long period of time even under the conditions of high agitation.

When the laminated antifouling coating film of the present invention is the one of the above (1), that is, when the upper antifouling coating composition (a) and the lower antifouling coating composition (b) contain the silyl ester group- containing hydrolyzable polymer, It is preferable that AV _A is 45 mg KOH / g or more and AV _B is less than 45 mg KOH / g from the viewpoint of exhibiting adequate antifouling property under any of the conditions.

It is more preferable that AV _A is 47 mg KOH / g or more from the viewpoint of exhibiting adequate antifouling property under low-cost conditions. From the same viewpoint, the upper limit of AV _A is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less.

Further, AV _B is more preferably 43 mgKOH / g or less from the viewpoint of exhibiting antifouling property over a long period of time in a high-temperature vulcanizing condition. From the same viewpoint, the lower limit of AV _B is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more.

AV _A -AV _B is preferably 4 mg KOH / g or more, and more preferably 8 mg KOH / g or more, from the viewpoint of exhibiting antifouling properties under both low-cost and high-load conditions. From the same viewpoint, AV _A -AV _B is preferably 100 mg KOH / g or less, more preferably 80 mg KOH / g or less, and even more preferably 60 mg KOH / g or less.

On the other hand, the silyl ester group-containing hydrolyzable polymer does not have an acid value per se in the method of measuring the acid value defined in the present invention. Therefore, in the case of the above (1), the content of the monocarboxylic acid compound (D) , It is preferable to adjust the acid value of the solvent-soluble components of the upper antifouling coating film (A) and the lower antifouling coating film (B).

In the case where the laminated antifouling coating film of the present invention is the one of the above (2), that is, when the upper antifouling coating composition (a) and the lower antifouling coating composition (b) contain a metal ester- It is preferable that AV _A is 100 mgKOH / g or more and AV _B is less than 100 mgKOH / g from the viewpoint of exhibiting appropriate antifouling property under any of the conditions.

From the viewpoint of exhibiting adequate antifouling property under low-cost conditions, AV _A is more preferably 102 mg KOH / g or more, and more preferably 104 mg KOH / g or more. From the same viewpoint, the upper limit of AV _A is preferably 200 mgKOH / g or less, more preferably 160 mgKOH / g or less, and even more preferably 120 mgKOH / g or less.

Further, AV _B is more preferably 98 mgKOH / g or less, and more preferably 96 mgKOH / g or less, from the viewpoint of exhibiting antifouling property over a long term under high agitation conditions. From the same viewpoint, the lower limit of AV _B is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 80 mgKOH / g or more.

AV _A -AV _B is preferably 10 mg KOH / g or more, and more preferably 15 mg KOH / g or more, from the viewpoint of exhibiting antifouling properties under both low-cost and high-temperature conditions. From the same viewpoint, AV _A -AV _B is preferably 100 mg KOH / g or less, more preferably 50 mg KOH / g or less.

On the other hand, the acid value of the solvent-soluble component of the antifouling coating film containing the metal ester group-containing hydrolyzable polymer is preferably such that the content of the constituent unit derived from the metal ester group-containing monomer (c12) in the hydrolyzable polymer (C) Can be adjusted by the content of the carboxylic acid compound (D).

When the laminated antifouling coating film of the present invention is the one of the above (3), that is, when the upper antifouling coating composition (a) contains the metal ester-containing hydrolyzable polymer and the lower antifouling paint composition (b) contains the silyl ester group- It is preferable that AV _A is 100 mgKOH / g or more and AV _B is less than 45 mgKOH / g from the viewpoint of exhibiting adequate antifouling property under any of the low-cost and high-operating conditions.

From the viewpoint of exhibiting adequate antifouling property under low-cost conditions, AV _A is more preferably at least 102 mg KOH / g, more preferably at least 105 mg KOH / g, even more preferably at least 108 mg KOH / g. From the same viewpoint, the upper limit of AV _A is preferably 200 mgKOH / g or less, more preferably 160 mgKOH / g or less, and even more preferably 120 mgKOH / g or less.

The AV _B is more preferably 43 mg KOH / g or less, still more preferably 41 mg KOH / g or less, still more preferably 39 mg KOH / g or less, from the viewpoint of exhibiting antifouling property over a long period of time under a high vulcanization condition. From the same viewpoint, the lower limit of AV _B is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and even more preferably 20 mgKOH / g or more.

On the other hand, the acid value of the solvent-soluble component of the upper antifouling coating film (A) containing the metal ester group-containing hydrolyzable polymer is preferably such that the content of the constituent unit derived from the metal ester group-containing monomer (c12) And the amount of the monocarboxylic acid compound (D) described later. The acid value of the solvent-soluble component of the lower antifoulant coating film (B) can be adjusted by the content of the monocarboxylic acid compound (D) described below.

(Monocarboxylic acid compound (D))

In the present invention, when the antifouling coating film has water repellency in water and the antifouling coating film contains the antifouling agent (E) to be described later, the release of the antifouling agent into the water is promoted to increase the antifouling property of the antifouling coating film, (A) and / or the lower layer antifouling paint composition (b) preferably contains a monocarboxylic acid compound (D) for the purpose of imparting appropriate water resistance to the antifouling coating film.

As the monocarboxylic acid compound (D), for example, a saturated or unsaturated aliphatic hydrocarbon group having 10 to 40 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a salt thereof is preferable Do.

Among them, abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, isophthalic acid, pimaric acid, trimethylisobutentylcyclohexenecarboxylic acid, versatate, stearic acid and naphthenic acid are preferred .

In addition, rosins mainly containing abietic acid, palustric acid, isophamic acid and the like are also preferable. Examples of the rosin include rosin such as gum rosin, wood rosin and tall oil rosin, rosin derivatives such as hydrogenated rosin, disproportionated rosin and rosin metal salt, and pine tar.

Examples of the trimethylisobutenylcyclohexene carboxylic acid include the reaction products of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, which include 1,2,3 Ene-1-carboxylic acid, and 1,4,5-trimethyl-2- (2-methylpropyl) -1-en-1-yl) cyclohex-3-ene-1-carboxylic acid as a main component (85% by mass or more).

The monocarboxylic acid compound (D) in the present invention may form a salt in part and / or in whole as long as AV _A and AV _B are AV _A > AV _B.

Examples of the salt of the monocarboxylic acid compound (D) include a zinc salt and a copper salt. The salt of the monocarboxylic acid compound (D) may be formed by a reaction with other paint components during the production of the antifouling paint composition .

When the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains a hydrolyzable polymer having a silyl ester group in the present invention, as described above, in addition to the hydrolyzable polymer (C) It is preferable to contain the monocarboxylic acid compound (D).

If containing a top layer antifouling paint composition (a) and / or lower the antifouling paint composition (b) a monocarboxylic acid compound (D) of the present invention, the amount of the AVA, AV _B is any from one of AV _A> AV _B When the upper layer antifouling coating composition (a) contains a silyl ester group-containing hydrolyzable polymer, the upper layer antifouling coating composition (a) preferably contains 1 to 50 mass%, more preferably 5 to 20 mass%, of the solids content of the coating composition And is preferably 10 to 60% by mass, more preferably 15 to 50% by mass in the solvent-soluble fraction of the upper layer antifouling paint composition (a).

(Antifouling agent (E))

In the present invention, it is preferable that the upper antifouling coating composition (a) and / or the lower antifouling paint composition (b) contain antifouling agent (E) for the purpose of imparting antifouling properties to the antifouling coating film.

Examples of the antifouling agent (E) include copper oxide such as copper oxide, copper pyrithione, zinc pyrithione, copper thiocyanate, copper (copper metal), 4,5-dichloro-2- 4-isothiazolin-3-one (abbrev. DCOIT), 4-bromo-2- (4- chlorophenyl) -5- (trifluoromethyl) (+/-) - 4- [1- (2, &lt; RTI ID = 0.0 &gt; 3-dimethylphenyl) ethyl] -1H-imidazole (abbreviation: medetomidine), N, N-dimethyl-N'- (3,4- dichlorophenyl) urea, N- 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalonitrile , Bisdimethyldithiocarbamoyl zinc ethylenebisdithiocyanate, chloromethyl-n-octyldisulfide , N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthiuramdisulfide, zinc dimethyldithiocarbamate, zinc ethylene bisdithio Carbamate, 2,3-dichloro-N- (2 ', 6'-diethylphenyl) maleimide and 2,3-dichloro-N- (2'- .

On the other hand, the above-mentioned medetomidine has optical isomers, but it may be either one of them or a mixture of any ratio. As part or all of the medetomidine, an adduct of an imidazolium salt, a metal or the like may be added, or an adduct of an imidazolium salt or a metal may be formed in the antifouling paint composition or antifouling coating film.

Among them, the antifouling agent (E) is at least one selected from the group consisting of copper oxide, copper pyrithione, zinc pyrithione, DCOIT, trallopyryl, borane-nitrogen base addition adduct and medetomidine And more preferably at least one member selected from the group consisting of copper oxide, copper pyrithione, zinc pyrithione, DCOIT, trallopyril and medetomidine.

These antifouling agents (E) may be used alone or in combination of two or more.

In the present invention, when the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains the antifouling agent (E), the content thereof is preferably from 0.1 to 80% by mass based on the solid content of the respective coating composition desirable.

(Other binder component (F))

In the present invention, the upper antifouling paint composition (a) and / or the lower antifouling paint composition (b) may contain other binder component (F) for the purpose of imparting water resistance, crack resistance and strength to the antifouling coating film do.

On the other hand, the other binder component (F) does not contain a hydrolyzable group and is a binder component excluding the hydrolyzable polymer (C).

Examples of the other binder component (F) include an acrylic copolymer (acrylic resin), a vinyl copolymer, chlorinated paraffin, n-paraffin, terpene phenol resin and polyvinyl ethyl ether. Of these, acrylic copolymers, vinyl copolymers and chlorinated paraffins are preferred. As such an acrylic copolymer or a vinyl-based copolymer, those obtained by polymerizing examples of the other monomer (c2) may be used.

Such other binder component (F) may be used alone or in combination of two or more.

As the other binder component (F), a commercially available product may be used. As the acrylic copolymer (acrylic resin), for example, "Dianal BR-106" manufactured by Mitsubishi Rayon Co., Ltd., Quot; Toyoparax A-40 / A-50 / A-70 / A-145 / A-150 &quot;

When the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) of the present invention contains the other binder component (F), the content thereof is preferably 0.1 to 10 mass% in the solid content of each coating composition Do.

(Pigment (G))

In the present invention, the upper layer antifouling paint composition (a) and / or the lower layer antifouling paint composition (b) are used for the purpose of coloring the coating film or concealing the undercoat It may contain a pigment (G).

Examples of the pigment G include talc, mica, clay, feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, calcium sulfate, (Iron oxide, Fe ₂ O ₃ ), black spinach (black iron oxide, Fe ₃ O ₄ ), titanium white (titanium oxide), yellow iron oxide (FeOOH), carbon black, naphthol red , Phthalocyanine blue and the like. Of these, talc and zinc oxide are preferred. These pigments (G) may be used alone or in combination of two or more.

When the upper-layer antifouling paint composition (a) and / or the lower-layer antifouling paint composition (b) of the present invention contains the pigment (G), the content thereof is preferably determined depending on the desired viscosity depending on the application form of the coating composition, It is preferably 1 to 50% by mass in the solid content of each coating composition.

(Organic solvent (H))

In the present invention, the upper layer antifouling paint composition (a) and / or the lower layer antifouling paint composition (b) are mixed with an organic solvent ((a)) for the purpose of keeping the viscosity of the coating composition small and improving spray atomization H).

As the organic solvent (H), an aromatic hydrocarbon-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, ketone-based, ester-based, or alcohol-based organic solvent can be used, preferably an aromatic hydrocarbon-based organic solvent.

Examples of the aromatic hydrocarbon-based organic solvent include toluene, xylene, styrene, and mesitylene.

Examples of the aliphatic hydrocarbon-based organic solvent include pentane, hexane, heptane and octane.

Examples of the alicyclic hydrocarbon-based organic solvent include cyclohexane, methylcyclohexane and ethylcyclohexane.

Examples of ketone-based organic solvents include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl carbonate and the like.

Examples of the ester organic solvent include propylene glycol monomethyl ether acetate and the like.

Examples of the alcohol-based organic solvent include isopropanol, n-butanol and propylene glycol monomethyl ether.

In the present invention, when the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains the organic solvent (H), the content thereof is preferably in the range of, for example, But it is preferably 0 to 50% by mass in each coating composition. When the content is excessively large, problems such as lowering of the sag prevention property may occur.

(Anti-sagging agent / anti-settling agent (I))

In the present invention, the upper antifouling paint composition (a) and / or the lower antifouling paint composition (b) may contain a sag preventing agent / sedimentation preventing agent (I) for the purpose of adjusting the viscosity of the paint composition.

Examples of the anti-sagging agent and anti-settling agent (I) include organic clay waxes (stearate salts of Al, Ca and Zn, lecithin salts and alkylsulfonates), organic waxes (polyethylene wax, oxidized polyethylene wax, amide wax, polyamide wax , Hydrogenated castor oil free wax), a mixture of an organic clay wax and an organic wax, and synthetic fine silica.

As the anti-sagging agent and anti-settling agent (I), commercially available products may be used. For example, "Diparron 305", "Diparron 4200-20", "Diparron A630-20X" manufactured by Gusumoto Chemical Co., ASA D-120 &quot; manufactured by Ito Kyoei Co., Ltd., and the like.

In the present invention, when the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains the anti-sagging / sedimentation preventing agent (I), the content thereof is preferably 0.01 to 10 mass %, More preferably 0.1 to 3% by mass.

(Dehydrating agent (J))

In the present invention, the upper layer antifouling paint composition (a) and / or the lower layer antifouling paint composition (b) may contain a dehydrating agent (J) for the purpose of improving the storage stability of the coating composition.

Examples of the dehydrating agent (J) include alkoxysilanes, orthoesters such as zeolite, porous alumina and orthoformic acid alkyl ester known as "molecular sieves", orthoboric acid, isocyanate and the like . These dehydrating agents may be used alone or in combination of two or more.

In the present invention, when the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains a dehydrating agent (J), the content thereof is preferably 0.1 to 10% by mass in the solid content of each coating composition , And more preferably 0.2 to 2% by mass. When the content of the dehydrating agent (J) is within the above range, the storage stability of the coating composition can be maintained satisfactorily.

(Plasticizer (K))

In the present invention, the upper antifouling paint composition (a) and / or the lower antifouling paint composition (b) may contain a plasticizer (K) for the purpose of imparting plasticity to the antifouling coating film.

Examples of the plasticizer (K) include tricresyl phosphate (TCP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP) and the like. These plasticizers may be used alone or in combination of two or more.

In the present invention, when the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains the plasticizer (K), the content thereof is preferably 0.1 to 10% by mass in the solid content of each coating composition And more preferably 0.5 to 5% by mass. When the content of the plasticizer (K) is within the above range, plasticity of the antifouling coating film can be maintained satisfactorily.

(Method for producing upper-layer antifouling paint composition (a) and lower-layer antifouling paint composition (b)

In the present invention, the upper-layer antifouling coating composition (a) and / or the lower-layer antifouling coating composition (b) can be produced by using the same apparatus, means and the like as those of common general antifouling paints. Specifically, when the anticorrosion paint composition contains the hydrolyzable polymer (C), the hydrolyzable polymer (C) is prepared, then the solution of the polymer and, if necessary, other components are added at once or sequentially, Stirring, and mixing.

[Method for producing an upper antifouling coating film (A), a lower antifouling coating film (B), a laminated antifouling coating film, and an antifouling coating film with a laminate antifouling coating film]

The upper antifouling coating film (A) and the lower antifouling coating film (B) of the present invention are each obtained by applying and drying the upper antifouling coating composition (a) and the lower antifouling coating composition (b).

Specifically, the upper antifouling coating film (A) and the lower antifouling coating film (B) were coated by applying the upper antifouling coating composition (a) and the lower antifouling coating composition (b) Can be obtained. More specifically, the lower antifouling coating film (B) is applied and dried to form a lower antifouling coating film (B), then the upper antifouling coating composition (a) is applied on the lower antifouling coating film (B) It is preferable to form the upper-layer antifouling coating film (A).

Examples of the method of applying the upper-layer antifouling coating composition (a) and the lower-layer antifouling paint composition (b) include known methods such as a method using a brush, a roller and a spray.

The antifouling paint composition applied by the above-mentioned method is allowed to stand for about 0.5 to 14 days, more preferably for about 0.5 to 10 days under a condition of 25 캜, and dried to obtain a coated film. On the other hand, the coating composition may be dried while blowing under heating.

The thickness of the upper-layer antifouling coating film (A) and the lower-layer antifouling coating film (B) after drying is arbitrarily selected depending on their coating film update speed and the period in which they are used, but is preferably about 30 to 1,000 μm, for example. As a method for producing the coating film of this thickness, there is a method of applying the antifouling paint composition once to several times at a thickness of usually 10 to 300 m, preferably 30 to 200 m per application.

The laminated antifouling coating film of the present invention comprises the upper antifouling coating film (A) and the lower antifouling coating film (B), and the upper antifouling coating film (A) is laminated on the lower antifouling coating film (B).

The laminated antifouling coating film of the present invention can be produced by, for example, forming a lower antifouling coating film (B) on a coating film or a substrate by the above-described method and then optionally carrying out a cleaning process such as high-pressure water washing, , And then forming the upper antifouling coating film (A) by the above-mentioned method.

The antifouling substrate with a laminated antifouling coating film of the present invention has the laminated antifouling coating film on a substrate.

The antifouling substrate having a laminated antifouling coating film of the present invention can be produced by forming the laminated antifouling coating film on a substrate by the above-described method.

The laminated antifouling coating film of the present invention can be used for maintaining the antifouling property of the substrate for a long time in a wide range of industrial fields such as a ship, a fishery, and an offshore structure. Examples of such a substrate include ships (ships such as large steel wires such as container ships and tankers, fishing boats, FRP ships, ship hulls such as yachts, new ships or watercraft), fishery materials (ropes, Buoys, etc.), and offshore structures such as mega-floats. Among these, a ship is preferable as the base material, and it is more preferable that it is the outer shell of a large steel wire having a construction process and the like.

The base material to be formed on the surface of the laminated antifouling coating film of the present invention may have a coating film such as a primer layer already formed on the surface thereof and the kind of the coating film to which the laminated antifouling coating film of the present invention is directly touched is not particularly limited.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

On the other hand, the "solid content" of each component used in the examples refers to a component excluding the volatile component contained as a solvent in each component, and each component obtained by drying in a hot air drier at 108 ° C for 3 hours is regarded as a solid component.

[Preparation of hydrolysable polymer (C)] [

Preparation Example 1: Preparation of metal ester group-containing monomer (c12-1)

In the production of the hydrolyzable polymer (C), first the metal ester group-containing monomer (c12-1) was prepared as follows.

85.4 parts by mass of propylene glycol monomethyl ether and 40.7 parts by mass of zinc oxide were charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction pipe and a heating and cooling jacket, and the temperature was raised to 75 캜 while stirring. Subsequently, a mixture of 43.1 parts by mass of methacrylic acid, 36.1 parts by mass of acrylic acid and 5.0 parts by mass of water was added dropwise at a constant rate over a period of 3 hours from the dropping device. After completion of the dropwise addition, stirring was further continued for 2 hours, and 36.0 parts by mass of propylene glycol monomethyl ether was added to obtain a reaction solution containing the metal ester group-containing monomer (c12-1).

PREPARATION EXAMPLE 1: Preparation of Solution (C-1) of Hydrolyzable Polymer (Silylester Group-Containing Hydrolyzable Copolymer)

54.0 parts by mass of xylene was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction pipe and a heating and cooling jacket, and the mixture was heated and stirred under a nitrogen atmosphere at 85 ± 5 ° C. While maintaining the same temperature, a monomer mixture composed of 60.0 parts by mass of triisopropylsilyl acrylate and 40.0 parts by mass of methyl methacrylate and 0.75 parts by mass of 2,2'-azobisisobutyronitrile was charged into the reaction vessel from the dropping apparatus to 2 Over a period of time. Thereafter, stirring was carried out at the same temperature for 2 hours, further 0.4 part by mass of 2,2'-azobisisobutyronitrile was added, stirring was further carried out at the same temperature for 4 hours, 44.0 parts by mass of xylene was added, A solution (C-1) of a colorless transparent hydrolyzable polymer (silyl ester group-containing hydrolyzable copolymer) was prepared.

The composition of the monomer mixture used and the properties of the hydrolyzable polymer solution (C-1) and the hydrolyzable polymer contained therein, as measured by the methods described below, are shown in Table 1.

Preparation Examples 2 to 5: Preparation of Solutions (C-2) to (C-5) of Hydrolyzable Polymers (Silylester Group-Containing Hydrolyzable Copolymer)

Except that the monomer mixture having the composition shown in Table 1 was used in place of the monomer mixture used in Production Example 1 and the amount of xylene and 2,2'-azobisisobutyronitrile was appropriately adjusted , And hydrolyzable polymer solutions (C-2) to (C-5) were prepared in the same manner as in Preparation Example 1.

The composition of the monomer mixture used and the hydrolyzable polymer solutions (C-2) to (C-5) measured by the methods described below and the property values of the hydrolyzable polymers contained therein are shown in Table 1.

Preparation Example 6: Preparation of hydrolyzable polymer (metal ester group-containing hydrolyzable copolymer) solution (C-6)

15.0 parts by mass of propylene glycol monomethyl ether, 57.0 parts by mass of xylene and 4.0 parts by mass of ethyl acrylate were fed into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube and a heating and cooling jacket, And the temperature was raised to 100 ± 5 ° C. 52.0 parts by mass of the reaction solution of the metal ester group-containing monomer (c12-1) obtained in Preparation Example 1, 1.0 part by mass of methyl methacrylate, and 66.2 parts by mass of ethyl acrylate were charged into the reaction container from the dropping device while maintaining the same temperature, , 5.4 parts by mass of 2-methoxyethyl acrylate, 2.5 parts by mass of polymerization initiator 2,2'-azobisisobutyronitrile, 7.0 parts by mass of polymerization initiator 2,2'-azobis (2-methylbutyronitrile) , 1.0 part by mass of a chain transfer agent "Nopmer MSD" (trade name, α-methylstyrene dimer manufactured by Nippon Oil and Fats Co., Ltd.) and 10.0 parts by mass of xylene were added dropwise over 6 hours. After completion of the dropwise addition, 0.5 part by mass of polymerization initiator tert-butyl peroctoate (TBPO) and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. Then, 4.4 parts by mass of xylene was added, To prepare a solution (C-6) of a hydrolyzable polymer (metal ester group-containing hydrolyzable copolymer).

Preparation Example 7: Preparation of hydrolyzable polymer (metal ester group-containing hydrolyzable copolymer) solution (C-7)

15.0 parts by mass of propylene glycol monomethyl ether, 57.0 parts by mass of xylene and 4.0 parts by mass of ethyl acrylate were fed into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube and a heating and cooling jacket, The temperature was raised to 100 ± 5 ° C. 47.5 parts by mass of the reaction solution containing the metal ester group-containing monomer (c12-1) obtained in Preparation Example 1, 14.6 parts by mass of methyl methacrylate, 52.6 parts by mass of ethyl acrylate 52.6 , 7.5 parts by mass of n-butyl acrylate, 2.5 parts by mass of polymerization initiator 2,2'-azobisisobutyronitrile, 8.5 parts by mass of polymerization initiator 2,2'-azobis (2-methylbutyronitrile) , 1.0 part by mass of a chain transfer agent "Nopmer MSD" and 10.0 parts by mass of xylene were added dropwise over 6 hours. After completion of the dropwise addition, 0.5 part by mass of a polymerization initiator tert-butyl peroctoate and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. Then, 6.9 parts by mass of xylene was added to obtain a light yellow transparent hydrolyzable polymer (Metal ester group-containing hydrolyzable copolymer) solution (C-7).

PREPARATION EXAMPLE 8: Preparation of Solution (C-8) of Hydrolyzable Polymer (Metal-Ester Group-Containing Hydrolyzable Copolymer)

15.0 parts by mass of propylene glycol monomethyl ether, 60.0 parts by mass of xylene and 4.0 parts by mass of ethyl acrylate were fed into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction pipe and a heating and cooling jacket, The temperature was raised to 100 ± 5 ° C. 40.2 parts by mass of a reaction liquid containing the metal ester group-containing monomer (c12-1) obtained in Preparation Example 1, 15.0 parts by mass of methyl methacrylate, and 48.0 parts by mass of ethyl acrylate , 15.0 parts by mass of n-butyl acrylate, 2.5 parts by mass of polymerization initiator 2,2'-azobisisobutyronitrile, 6.5 parts by mass of polymerization initiator 2,2'-azobis (2-methylbutyronitrile) , 1.2 parts by mass of a chain transfer agent "Nopmer MSD" and 10.0 parts by mass of xylene was added dropwise over 6 hours. After completion of the dropwise addition, 0.5 part by mass of the polymerization initiator tert-butyl peroctoate and 7.0 parts by mass of xylene were added dropwise over 30 minutes and further stirred for 1 hour and 30 minutes. Then, 8.0 parts by mass of xylene was added to obtain a light yellow transparent hydrolyzable polymer (Metal ester group-containing hydrolyzable copolymer) solution (C-8).

The structures of the monomers used in Production Examples 6 to 8 and the hydrolyzable polymer solutions (C-6) to (C-8) measured by the methods described below and the property values of the hydrolyzable polymers contained therein were shown in Table 2 Respectively. On the other hand, Table 2 shows the theoretical compounding amount (mass part) of each monomer.

The viscosity of the obtained hydrolyzable polymer solutions (C-1) to (C-8), the zinc content of the hydrolyzable polymer solutions (C-6) to (C- The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzable polymer contained in the solution are measured as follows.

<Viscosity of Hydrolyzable Polymer Solution>

The viscosity of the hydrolyzable polymer solution at 25 캜 was measured by an E-type viscometer (manufactured by Toki Kogyo Co., Ltd.).

<Zinc Content of Hydrolyzable Polymer Solution>

The zinc content of the hydrolyzable polymer solution was measured by an X-ray diffractometer (Ultima IV, a sample horizontal type multi-purpose X-ray diffraction apparatus, Rigaku).

On the other hand, the zinc content in the hydrolyzable polymer was calculated from the measured zinc content of the hydrolyzable polymer solution and the solid content of the hydrolyzable polymer solution.

&Lt; Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw) of hydrolysable polymer >

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzable polymer were measured by GPC (gel permeation chromatography) under the following conditions.

(GPC conditions of the hydrolyzable polymers contained in the hydrolyzable polymer solutions (C-1) to (C-5)

Apparatus: &quot; HLC-8120GPC &quot; (manufactured by Tosoh Corporation)

Column: "TSKgel SuperH2000" and "TSKgel SuperH4000" were connected (all manufactured by TOSOH CORPORATION, 6 mm diameter × 15 cm length)

Eluent: tetrahydrofuran (THF)

Flow rate: 0.500 ml / min

Detector: RI

Column thermostat temperature: 40 ° C

Standard material: polystyrene

Preparation of samples: A small amount of calcium chloride was added to the polymer solutions (C-1) to (C-5) prepared in each Preparation Example to dehydrate and then filtered with a membrane filter to obtain a GPC measurement sample.

(GPC conditions of the hydrolyzable polymers contained in the hydrolyzable polymer solutions (C-6) to (C-8)

Apparatus: &quot; HLC-8320GPC &quot; (manufactured by Tosoh Corporation)

Two columns of "TSKgel SuperAWM-H" and one column of "TSKgel SuperAW2500" were connected (all manufactured by TOSOH Corporation, inner diameter 6 mm / length 15 cm)

Eluent: N, N-dimethylformamide (DMF) (20 mM lithium bromide added)

Flow rate: 0.600 ml / min

Detector: RI

Column thermostat temperature: 40 ° C

Standard material: polystyrene

Preparation of samples: A small amount of calcium chloride was added to the polymer solutions (C-6) to (C-8) prepared in each production example and dehydrated, and then filtered with a membrane filter to obtain a GPC measurement sample.

[Preparation of paint composition and laminated antifouling coating film]

· Ingredients

Table 3 shows the blending components used in the coating composition.

· Preparation of Coating Composition

(Mixing parts) shown in Tables 4 and 5 were mixed and stirred to obtain an upper layer antifouling coating composition (a) and a lower layer antifouling coating composition (b). On the other hand, the blending amounts of the respective components shown in Tables 4 and 5 indicate the blending amount as the dispersion or the solution with respect to the component having the base material of solid content, and the blending amount of the component having no base material (excluding the organic solvent) .

Tables 4 and 5 show the results of measurement of the solvent-soluble fraction (solids ratio, solid content separately measured by the above method) and the solvent-soluble dispersibility in each coating composition obtained by the above-mentioned method.

[Examples 1 to 20 and Comparative Examples 1 to 6]

· Production of laminated antifouling coating

An epoxy resin-based anticorrosive paint composition (epoxy AC paint, trade name "Banano 500", manufactured by Chugoku Kogyo Co., Ltd.) was applied to a sandblast-treated steel plate (300 mm in length × 100 mm in width × 3.2 mm in thickness) After the application, a vinyl resin binder paint composition (trade name "Silbox SQ-K", manufactured by Chugoku Kogyo Co., Ltd.) was applied so as to have a dry film thickness of 40 μm. Subsequently, the lower layer antifouling paint composition (b) prepared in accordance with Table 5 was coated once with the combination shown in Table 6 and Table 7 so as to have a dry film thickness of 200 占 퐉, and then the antifouling paint composition The upper layer antifouling paint composition (a) was applied once to a dry film thickness of 50 탆, and then dried at 25 캜 for 7 days to prepare a test plate with a laminate antifouling coating film. On the other hand, in the above four coatings, if the coating is applied one time per day, that is, when superimposed, the coating composition corresponding to the lower coating film is coated and dried at 25 ° C for at least 24 hours, The coating composition was applied.

<Antifouling property evaluation>

The test plate prepared as described above was immersed in the bay for 3 months and the area (adhered area) of the part where the antifouling coating film was adhered was measured, and the evaluation criteria of the antifouling property by the area attached with the marine life , The antifouling property of the antifouling laminated coating film at the initial stage was evaluated.

[Criteria for Estimation of Antifouling Properties by Area of Adhered Marine Species]

   5: Less than 1% of total surface area of marine creatures on test surface

   4: Between 1% and 10% of total area

   3: Bronchial area is 10% or more and less than 30% of the whole

   2: 30% or more and less than 70% of total area

   1: 70% or more of the whole area

Thereafter, the immersion plate was pulled up and fixed to the inner wall of the cylinder which gave a rotating water flow at a speed of 10 knots at a surface speed, and placed in a dynamic immersion environment for 6 months in 40 ° C seawater. The area (area of attachment) of the part of the antifouling coating film attached with the marine life was measured, and the antifouling property after the long-term dynamic immersion of the antifouling laminated coating film was measured according to the above- I appreciated.

The results are shown in Tables 6 and 7.

As is apparent from the results of Examples and Comparative Examples, according to the present invention, it is possible to provide a laminated antifouling coating film capable of maintaining a sufficient antifouling performance over a long period of time even in stationary immersion and subsequent dynamic immersion, and a laminated antifouling coating film A substrate can be provided.

Claims (15)

An upper antifouling coating film (A) formed from the upper antifouling coating composition (a), and
Layer antifouling coating film (B) formed from the lower-layer antifouling paint composition (b)
The upper antifouling coating film (A) is laminated on the upper antifouling coating film (B)
Layer antifouling coating film (A) and the lower-layer antifouling coating film (B) as AV _A and AV _B , respectively, satisfy the following formula (1)
Wherein the total amount of the solvent-soluble components in the upper antifouling coating film (A) and the lower antifouling coating film (B) is 10 to 60 mass%.
AV _A > AV _B (1) The method according to claim 1,
Wherein the upper antifouling paint composition (a) contains a hydrolyzable polymer (C) having a silyl ester group represented by the following formula (I) or a metal ester group represented by the following formula (II)

(Wherein R ¹ to R ³ each independently represent a monovalent hydrocarbon group, and * represents a bonding position.)

(Wherein M represents a metal and * represents a bonding position). The method according to claim 1,
Wherein the lower layer antifouling paint composition (b) contains a silyl ester group represented by the following formula (I) or a hydrolyzable polymer (C) having a metal ester group represented by the following formula (II).

(Wherein R ¹ to R ³ each independently represent a monovalent hydrocarbon group, and * represents a bonding position.)

(Wherein M represents a metal and * represents a bonding position). The method according to claim 1,
Wherein the upper antifouling coating composition (a) and the lower antifouling coating composition (b) contain a hydrolyzable polymer (C) having a silyl ester group represented by the following formula (I).

(Wherein R ¹ to R ³ each independently represent a monovalent hydrocarbon group, and * represents a bonding position.) 5. The method of claim 4,
Wherein the AV _A is 45 mgKOH / g or more and the AV _B is less than 45 mgKOH / g. The method according to claim 1,
Wherein the upper antifouling coating composition (a) contains a hydrolyzable polymer (C) having a metal ester group represented by the following formula (II).

(Wherein M represents a metal and * represents a bonding position). The method according to claim 6,
Wherein the AV _A is 100 mgKOH / g or more and the AV _B is less than 100 mg KOH / g. 3. The method of claim 2,
Wherein the hydrolyzable polymer (C) further has a group represented by the following formula (III).

(Wherein X represents a divalent hydrocarbon group of 2 to 10 carbon atoms, Y represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 30 carbon atoms, n represents an integer of 1 to 50, and * represents a bonding position.) The method according to claim 1,
Wherein the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains a monocarboxylic acid compound (D) and / or a metal salt thereof. 10. The method of claim 9,
Wherein the monocarboxylic acid compound (D) is at least one selected from the group consisting of a saturated or unsaturated aliphatic monocarboxylic acid having 10 to 40 carbon atoms, a saturated or unsaturated alicyclic monocarboxylic acid having 3 to 40 carbon atoms, Laminated antifouling coating film. The method according to claim 1,
Wherein the upper antifouling coating composition (a) and / or the lower antifouling coating composition (b) contains an antifouling agent (E). 12. The method of claim 11,
Wherein the antifouling agent (E) is selected from the group consisting of copper oxide, copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin- - a nitrogen-based base adduct, and at least one selected from the group consisting of medetomidine. An antifouling substrate coated with the laminated antifouling coating film according to any one of claims 1 to 12. A ship coated with the laminated antifouling coating film according to any one of claims 1 to 12. delete