JP6638958B2 - Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, method for producing the same, and antifouling method - Google Patents

Description

  The present invention relates to an antifouling coating composition, an antifouling coating film, a substrate with an antifouling coating film using the same, a method for producing the same, and an antifouling method.

At present, as a method for preventing pollution by aquatic organisms such as ships, a method using a hydrolyzable polymer having a property of renewing a coating film from the surface in water is widely used.
The antifouling coating film using such a hydrolyzable polymer as a binder is hydrophilized from the surface with the progress of hydrolysis in water, and the hydrophilized portion is polished by a water flow to exhibit renewability of the coating film. As a typical example, a silyl ester polymer is widely used.
As the silyl ester polymer, a copolymer obtained by polymerizing a monomer containing a trialkylsilyl ester group, which is a hydrolyzable group, and another combined monomer is generally used. Since the renewal speed and antifouling property of the polymer are greatly affected by the kind and amount of the combined monomer used in combination, researches on the method are actively conducted.
In recent years, as such a combination monomer, a monomer having an organopolysiloxane structure has been studied for the purpose of improving the antifouling property of a coating film.
For example, Patent Document 1 discloses an antifouling paint composition containing a hydrolyzable resin containing a structural unit derived from a silicon-containing polymerizable monomer and a structural unit derived from triorganosilyl (meth) acrylate. Is disclosed.

International Publication No. 2011/046087

However, although the antifouling paint composition disclosed in Patent Document 1 exhibits good antifouling properties for a long period of time when left standing in water, it is presumed to be derived from the water permeability of organopolysiloxane. The subject that the antifouling property and the topcoat adhesion (recoating property) deteriorate when exposed to a high-speed water stream for a long period of time due to deterioration of the internal state of the coating film has been found.
In view of such problems, the present invention can exhibit antifouling performance for a long period of time even under a high-speed water flow environment, has excellent antifouling properties even in a dry / wet alternating portion, and further has an antifouling coating film having excellent recoating properties. It is an object to provide the obtained antifouling paint composition. Further, another object of the present invention is to provide an antifouling coating film, a substrate with an antifouling coating film, a method for producing the same, and an antifouling method using the antifouling coating composition.

As a result of intensive studies by the present inventors, they have found that the above problem can be solved by using the following antifouling paint composition, and have completed the present invention.
The gist of the present invention is as follows.

The present invention relates to the following [1] to [25].
[1] A silyl ester-based copolymer (A) is contained, wherein the silyl ester-based copolymer (A) is derived from (i) a trialkylsilyl methacrylate (a1) structural unit, and (ii) a compound represented by the following formula: An antifouling paint composition comprising a structural unit derived from the compound (a2) represented by (I).

（式（Ｉ）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、一価の炭化水素基を示し、Ｘはそれぞれ独立に、（メタ）アクリロイルオキシアルキル基又はメルカプトアルキル基を示し、ｍ及びｎはそれぞれ独立に０以上であり、ｐ及びｑはそれぞれ独立に０又は１であり、ｎ＋ｐ＋ｑは１以上である。）

(In the formula (I), R ¹ , R ² and R ³ each independently represent a monovalent hydrocarbon group, X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and m And n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.)

[2] The method according to [1], wherein the silyl ester-based copolymer (A) contains 20 to 80% by mass, preferably 40 to 70% by mass of a structural unit derived from a trialkylsilyl methacrylate (a1). Antifouling paint composition.
[3] [1] or [2], wherein the silyl ester-based copolymer (A) contains 1 to 30% by mass, preferably 1.5 to 15% by mass of a structural unit derived from the compound (a2). 3. The antifouling coating composition according to item 1.
[4] The antifouling coating composition according to any one of [1] to [3], wherein the trialkylsilyl methacrylate (a1) is triisopropylsilyl methacrylate.
[5] The compound (a21), wherein n is 0, p is 1 and q is 0 in the formula (I), wherein the silyl ester-based copolymer (A) is Is 0, and p and q are 1 and a structural unit derived from at least one compound selected from the group consisting of a compound (a23) in which n is 1 or more in the formula (I). The antifouling paint composition according to any one of [1] to [4], having:
[6] Any one of [1] to [5], wherein the silyl ester-based copolymer (A) further has one or more structural units derived from (iii) another monomer (a3). 3. The antifouling coating composition according to item 1.
[7] The antifouling coating composition according to [6], wherein the other monomer (a3) contains a monomer (a31) represented by the following formula (II).

（式（II）中、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は水素原子又は一価の炭化水素基を示し、Ｒ^６は二価の炭化水素基を示し、ｓは１〜６の整数を示す。）

(In the formula (II), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group, R ⁶ represents a divalent hydrocarbon group, and s represents 1 to 6 Represents an integer.)

[8] The antifouling coating composition according to [7], wherein in the formula (II), R ⁴ is a hydrogen atom.
[9] In the formula (II), R ⁵ is a monovalent hydrocarbon group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group Group, propyl group, butyl group), and more preferably a methyl group, the antifouling coating composition according to [7] or [8].
[10] In the formula (II), R ⁶ is an alkylene group having 2 to ⁶ carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an ethylene group or a propylene group. -The antifouling coating composition according to any one of [9].
[11] The antifouling coating composition according to any one of [7] to [10], wherein in formula (II), s is an integer of 1 to 3, preferably 1.
[12] The silyl ester-based copolymer (A) contains 10 to 35% by mass, preferably 15 to 30% by mass of a structural unit derived from the monomer (a31) represented by the formula (II). , [7]-The antifouling coating composition according to any one of [11].
[13] The antifouling coating composition according to any one of [7] to [12], wherein the other monomer (a3) contains methyl methacrylate.
[14] The silyl ester copolymer (A) contains 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0% by mass of a structural unit derived from an unsaturated fatty acid. %. The antifouling coating composition according to any one of [1] to [13].
[15] Any of [1] to [14], wherein the weight average molecular weight of the silyl ester copolymer (A) is from 3,000 to 70,000, preferably from 10,000 to 50,000. The antifouling paint composition according to the above.
[16] The solid content of the antifouling coating composition contains 5 to 50% by mass, preferably 10 to 35% by mass, more preferably 10 to 20% by mass of the silyl ester-based copolymer (A). The antifouling coating composition according to any one of 1) to [15].
[17] The antifouling coating composition according to any one of [1] to [16], further comprising an antifouling agent (B).
[18] The antifouling paint composition according to [17], wherein the antifouling agent (B) contains cuprous oxide (B1).
[19] The composition according to [18], wherein the solid content of the antifouling coating composition contains 20 to 80% by mass, preferably 40 to 70% by mass, more preferably 50 to 65% by mass of the cuprous oxide (B1). The antifouling paint composition according to the above.
[20] The antifouling coating composition according to any one of [1] to [19], further comprising a monocarboxylic acid compound (C).
[21] Further, from the group consisting of other binder components (D), pigments (E), organic solvents (F), anti-sagging agents and anti-settling agents (G), dehydrating agents (H), and plasticizers (I). The antifouling paint composition according to any one of [1] to [20], containing at least one selected from the group consisting of:
[22] An antifouling coating film formed from the antifouling coating composition according to any one of [1] to [21].
[23] A substrate with an antifouling coating film coated with the antifouling coating film according to [22].
[24] A step (1) of coating or impregnating a substrate with the antifouling coating composition according to any one of [1] to [21] to obtain a coated body or impregnated body, and the coated body or impregnated body A method for producing a substrate with an antifouling coating film, comprising a step (2) of drying the body.
[25] An antifouling method using the antifouling coating film according to [22].

  ADVANTAGE OF THE INVENTION According to this invention, antifouling performance can be exhibited for a long period of time even in a high-speed water flow environment, antifouling properties are excellent even in a dry / wet alternating portion, and further, an antifouling coating film having excellent recoating properties is obtained. A coating composition can be provided. Further, according to the present invention, an antifouling coating film, a substrate with an antifouling coating film using the antifouling coating composition, a method for producing the same, and an antifouling method can be provided.

Hereinafter, the antifouling coating composition, the antifouling coating film, the substrate with the antifouling coating film, the production method thereof, and the antifouling method according to the present invention will be described in detail.
In the following description, “(meth) acryloyl”, “(meth) acrylic acid” and “(meth) acrylate” are “acryloyl or methacryloyl”, “acrylic acid or methacrylic acid”, and “acrylate or methacrylate”, respectively. Means.
[Antifouling paint composition]
The antifouling paint composition of the present invention (hereinafter, also simply referred to as “paint composition”) contains a silyl ester copolymer (A), and the silyl ester copolymer (A) contains (i) ) A structural unit derived from a trialkylsilyl methacrylate (a1) and (ii) a structural unit derived from a compound (a2) represented by the following formula (I).

（式（Ｉ）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、一価の炭化水素基を示し、Ｘはそれぞれ独立に、（メタ）アクリロイルオキシアルキル基又はメルカプトアルキル基を示し、ｍ及びｎはそれぞれ独立に０以上であり、ｐ及びｑはそれぞれ独立に０又は１であり、ｎ＋ｐ＋ｑは１以上である。）

(In the formula (I), R ¹ , R ² and R ³ each independently represent a monovalent hydrocarbon group, X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and m And n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.)

ADVANTAGE OF THE INVENTION According to this invention, antifouling performance can be exhibited for a long period of time even in a high-speed water flow environment, antifouling properties are excellent even in a dry / wet alternating portion, and further, an antifouling coating film having excellent recoating properties is obtained. A coating composition can be provided.
The antifouling coating composition described in Patent Document 1 exhibits good antifouling properties for a long period of time in a immersion state of standing in water, but the inside of the coating film which is presumed to be derived from the water permeability of organopolysiloxane. When exposed to a high-speed water stream for a long period of time due to deterioration of the state, there is a problem that the antifouling property and the adhesion to the top coat (recoat property) are reduced. The present invention provides an antifouling paint composition which contains a specific silyl ester copolymer (A), thereby maintaining an antifouling property for a long time and forming an antifouling coating film having excellent recoating properties. It is found that it is done. Further, as an unpredictable effect, an antifouling coating film having excellent antifouling properties was obtained even in the dry / wet alternating portion.

Although the detailed mechanism of action for obtaining the above-mentioned effects is not necessarily clear, some of them are presumed as follows. That is, by containing the specific silyl ester-based copolymer (A), the antifouling coating film is provided with appropriate water resistance and renewability of the coating film from the surface in water, and the antifouling property is maintained for a longer period of time. It is considered that, while being maintained, due to appropriate water resistance, deterioration of the internal state of the coating film was suppressed, and an antifouling coating film having excellent recoating properties was obtained.
Hereinafter, each component contained in the antifouling coating composition of the present invention will be described in detail.

<Silyl ester copolymer (A)>
In the present invention, the silyl ester-based copolymer (A) is derived from (i) a structural unit derived from a trialkylsilyl methacrylate (a1), and (ii) a compound derived from the compound (a2) represented by the above formula (I). Having the following structural unit. The silyl ester copolymer (A) optionally has a structural unit derived from (iii) another monomer (a3), and (iii) a structural unit derived from another monomer (a3). It preferably has units.
In the present invention, the “copolymer having a structural unit derived from A” means a copolymer in which A is introduced by a polymerization reaction or a chain transfer reaction. Therefore, when the compound represented by the formula (I) has a mercaptoalkyl group, the silyl ester is formed in such a form that the radical polymerization terminal extracts H of —SH and the generated —S ^· (S radical) initiates polymerization. The silyl ester copolymer (A) is introduced into the copolymer (A). In such a case, the silyl ester copolymer (A) has a structural unit derived from the compound represented by the formula (I). .
Hereinafter, each structural unit will be described.

[(I) Structural unit derived from trialkylsilyl methacrylate (a1)]
Trialkylsilyl methacrylate (a1) is a monomer represented by the following formula (III).

（式（III）中、Ｒ^７、Ｒ^８、及びＲ^９はそれぞれ独立に、一価の炭化水素基を示す。）

(In the formula (III), R ⁷ , R ⁸ , and R ⁹ each independently represent a monovalent hydrocarbon group.)

In the formula (III), R ⁷ , R ⁸ and R ⁹ each independently represent a monovalent hydrocarbon group, and examples thereof include a linear, branched or cyclic alkyl group, and an aryl group. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8, and still more preferably 1 to 4. The aryl group preferably has 6 to 14, more preferably 6 to 10 carbon atoms.
From the viewpoint that the silyl ester-based copolymer (A) is hydrolyzed in water at an appropriate rate, R ^{7 to} R ⁹ are methyl, ethyl, isopropyl, n-propyl, isobutyl, sec-butyl. Group, n-butyl group, 2-ethylhexyl group, phenyl group and the like, and among them, selected from the group consisting of isopropyl group, n-propyl group, sec-butyl group, n-butyl group, and phenyl group. It is more preferable that all of R ^{7 to} R ⁹ are isopropyl groups.

The content of the structural unit derived from the trialkylsilyl methacrylate (a1) in the silyl ester-based copolymer (A) is 100 parts by mass in view of the fact that the formed antifouling coating film has an appropriate coating film renewal speed. Parts by weight, preferably 20 to 80 parts by weight, more preferably 40 to 70 parts by weight.
In the present invention, the ratio of each content (mass) of the structural unit derived from each monomer or the like in the silyl ester copolymer (A) depends on the above-mentioned each monomer or the like used in the polymerization reaction. It can be regarded as the same as the ratio of the charged amount (mass) of the raw material).

  The present invention has one feature in using a trialkylsilyl methacrylate instead of a trialkylsilyl acrylate. In the polymerization of the silyl ester copolymer (A), a trialkyl having high polymerizability is considered due to the difficulty of uniform polymerization which is considered to be caused by the low solubility of the compound (a2) represented by the formula (I). It was common to use silyl acrylate. In the present invention, the use of trialkylsilyl methacrylate having low polymerizability darely finds a silyl ester copolymer (A) capable of obtaining an antifouling coating film exhibiting favorable coating film properties and antifouling properties, The present invention has been completed.

[(Ii) Structural unit derived from compound (a2) represented by formula (I)]
In the present invention, the silyl ester copolymer (A) has a structural unit derived from a compound (a2) represented by the following formula (I).

（式（Ｉ）中、Ｒ^１、Ｒ^２、及びＲ^３はそれぞれ独立に、一価の炭化水素基を示し、Ｘはそれぞれ独立に、（メタ）アクリロイルオキシアルキル基又はメルカプトアルキル基を示し、ｍ及びｎはそれぞれ独立に０以上であり、ｐ及びｑはそれぞれ独立に０又は１であり、ｎ＋ｐ＋ｑは１以上である。）

(In the formula (I), R ¹ , R ² , and R ³ each independently represent a monovalent hydrocarbon group, X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, m and n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.)

In the formula (I), R ¹ , R ² , and R ³ each independently represent a monovalent hydrocarbon group, and examples thereof include groups similar to R ⁷ , R ⁸ , and R ⁹ . From the viewpoint, an alkyl group is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, and a butyl group is further preferable.
In the formula (I), Xs each independently represent a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and from the viewpoint of uniform polymerization progress, a (meth) acryloyloxyalkyl group is preferable, and the viscosity of the polymer to be formed is From the viewpoint of reducing the amount and facilitating handling, a mercaptoalkyl group is also preferable.
The (meth) acryloyloxyalkyl group is represented by the following formula (VI).

（式（ＶＩ）中、Ｒ^１１は水素原子又はメチル基を示し、Ｒ^１２はアルキレン基を示し、＊はＳｉとの結合位置を示す。）

(In the formula (VI), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group, and * represents a bonding position to Si.)

R ¹² represents an alkylene group, and preferably has 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4 carbon atoms from the viewpoint of reactivity.

  The mercaptoalkyl group is represented by the following formula (VII).

（式(VII)中、Ｒ^１３はアルキレン基を示し、＊はＳｉとの結合位置を示す。）

(In the formula (VII), R ¹³ represents an alkylene group, and * represents a bonding position to Si.)

R ¹³ represents an alkylene group, and preferably has 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4 carbon atoms from the viewpoint of reactivity.

  Examples of such X include a (meth) acryloyloxyethyl group, a (meth) acryloyloxypropyl group, a (meth) acryloyloxybutyl group, a mercaptomethyl group, a mercaptoethyl group, a mercaptopropyl group, and a mercaptobutyl group.

In the formula (I), m and n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.
Incidentally, m and n are each _^(SiR 2 2 O), which means an average addition mole number of (SiXR ³ O).
In the formula (I), m + n is preferably 2 or more. That is, the compound represented by the formula (I) preferably has a polyorganosiloxane moiety.
In addition, in this specification, when two or more different repeating units are described in parallel between [], those repeating units are repeated in any of random, alternating, and block shapes and orders. Indicates that you may. That is, for example, the formula _{- [Y 3 -Z 3] -} ( wherein, Y, Z represents a repeating unit), the in random form, such as -YYZYZZ-, in alternate form, such as -YZYZYZ-, - It may be in a block shape such as YYZZZZ- or -ZZZYYY-.

In one embodiment, the silyl ester copolymer (A) has a structural unit derived from the compound (a21) in which n is 0, p is 1, and q is 0 in the formula (I). Is preferred.
The antifouling coating composition containing the silyl ester copolymer (A) having a structural unit derived from the compound (a21) is capable of forming an antifouling coating film having particularly excellent antifouling properties. preferable.
In such a compound (a21), m is preferably from 3 to 200, and more preferably from 5 to 70, from the viewpoint of easiness of polymerization and the like.
As such a compound (a21), commercially available ones can be used. For example, FM-0711 (methacryloyloxyalkyl-modified organopolysiloxane at one end, average molecular weight Mn = 1,000) manufactured by JNC Co., Ltd., FM -0721 (one-terminal methacryloyloxyalkyl-modified organopolysiloxane, average molecular weight Mn = 5,000), FM-0725 (one-terminal methacryloyloxyalkyl-modified organopolysiloxane, average molecular weight Mn = 10,000), Shin-Etsu Chemical Co., Ltd. X-22-174ASX (methacryloyloxyalkyl-modified organopolysiloxane at one end, functional group equivalent 900 g / mol), KF-2012 (methacryloyloxyalkyl-modified organopolysiloxane at one end, functional group equivalent 4,600 g / mol) , X 22-2426 (one terminal methacryloyloxy alkyl-modified organopolysiloxane, functional group equivalent 12,000 g / mol) and the like.

In one embodiment, the silyl ester-based copolymer (A) may have a structural unit derived from the compound (a22) in which n is 0 and p and q are 1 in the formula (I). preferable.
The antifouling coating composition containing the silyl ester-based copolymer (A) having the structural unit derived from the compound (a22) is preferable in that the formed coating film has good overcoat adhesion.
In such a compound (a22), m is preferably from 3 to 200, and more preferably from 5 to 70, from the viewpoint of easiness of polymerization and the like.
As such a compound (a22), commercially available ones can be used. For example, FM-7711 (methacryloyloxyalkyl-modified organopolysiloxane at both ends, average molecular weight Mn = 1,000) manufactured by JNC Co., Ltd., FM -7721 (methacryloyloxyalkyl-modified organopolysiloxane at both ends, average molecular weight Mn = 5,000), FM-7725 (methacryloyloxyalkyl-modified organopolysiloxane at both ends, average molecular weight Mn = 10,000), Shin-Etsu Chemical Co., Ltd. X-22-164 (methacryloyloxyalkyl-modified organopolysiloxane at both ends, functional group equivalent 190 g / mol) and X-22-164AS (both-terminal methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 450 g / mol) , X-2 X-164A (methacryloyloxyalkyl-modified organopolysiloxane at both ends, functional group equivalent 860 g / mol), X-22-164B (methacryloyloxyalkyl-modified organopolysiloxane at both ends, functional group equivalent 1630 g / mol), X-22-164C (Methacryloyloxyalkyl-modified organopolysiloxane at both ends, functional group equivalent 2,370 g / mol), X-22-164E (methacryloyloxyalkyl-modified organopolysiloxane at both terminals, functional group equivalent 3,900 g / mol), X-22 -167B (mercaptoalkyl-modified organopolysiloxane at both ends, functional group equivalent: 1,670 g / mol).

Further, as one embodiment, it is preferable that the silyl ester copolymer (A) has a structural unit derived from the compound (a23) in which n is 1 or more in the formula (I).
It is preferable that the silyl ester-based copolymer (A) has a structural unit derived from such a compound (a23) because the viscosity is low and the handling is easy.
In such a compound (a23), m is preferably from 50 to 1,000, and n is preferably from 1 to 30.
As such a compound (a23), a commercially available compound can be used. For example, KF-2001 (side-chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent: 1,900 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd. , KF-2004 (side-chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent 30,000 g / mol).

  The content of the structural unit derived from the compound (a2) in the silyl ester-based copolymer (A) depends on the antifouling performance of the antifouling coating film under alternate dry and wet conditions, water resistance, and substrate adhesion. The amount is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 1.5 to 15 parts by mass with respect to 100 parts by mass.

[(Iii) Structural unit derived from other monomer (a3)]
In the present invention, the silyl ester copolymer (A) preferably has a structural unit derived from another monomer (a3).
As the other monomer (a3), a monomer copolymerizable with the monomer (a1) and the compound (a2) can be used without limitation. Among these, the other monomer (a3) is preferably an ethylenically unsaturated compound.
Examples of the other monomer (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). A) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) Acrylate, alkyl (meth) acrylates such as benzyl (meth) acrylate or aryl (meth) acrylates;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 3-methoxy-n-propyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2- Butoxyethyl (meth) acrylate, isobutoxybutyldiglycol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, Alkoxyalkyl (meth) acrylates such as phenoxy polyethylene glycol (meth) acrylate or aryloxyalkyl (meth) acrylates;
Hydroxy such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate Alkyl (meth) acrylates;
Glycidyl (meth) acrylates;
A metal ester group-containing unsaturated monomer (a32) described below;
Examples include vinyl compounds such as styrene, α-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.

  The other monomer (a3) preferably includes a monomer (a31) represented by the following formula (II).

（式（II）中、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は水素原子又は一価の炭化水素基を示し、Ｒ^６は二価の炭化水素基を示し、ｓは１〜６の整数を示す。）

(In the formula (II), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group, R ⁶ represents a divalent hydrocarbon group, and s represents 1 to 6 Represents an integer.)

In the formula (II), R ⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of ease of polymerization, and is preferably a methyl group from the viewpoint of water resistance of a formed coating film. preferable.
In the formula (II), R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group, and from the viewpoints of stability of the antifouling coating composition and physical properties of the formed coating film, an alkyl group having 1 to 6 carbon atoms. And more preferably an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, and a butyl group), and further preferably a methyl group.
In the formula (II), R ⁶ represents a divalent hydrocarbon group, preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, still more preferably ethylene. Or a propylene group.
In the formula (II), s represents an integer of 1 to 6, preferably 1 to 3, and more preferably 1. When s is an integer of 1 to 6, appropriate hydrophilicity is imparted to the coating film formed by the antifouling coating composition containing the silyl ester copolymer (A), and the antifouling agent has excellent water resistance. It is preferable because a coating film can be obtained.

Examples of such a monomer (a31) include the above-mentioned alkoxyalkyl (meth) acrylate, preferably 2-methoxyethyl (meth) acrylate, and more preferably 2-methoxyethyl methacrylate.
When the silyl ester-based copolymer (A) has a structural unit derived from such a monomer (a31), the monomer (a31) is preferred in view of the antifouling performance, water resistance, and hardness of the antifouling coating film. The content of the structural unit derived from a31) is preferably 5 to 40 parts by mass, more preferably 10 to 35 parts by mass, and more preferably 100 parts by mass of all the structural units of the silyl ester copolymer (A). Preferably it is 15 to 30 parts by mass.

In the present invention, it is preferable to have a structural unit derived from methyl methacrylate as a structural unit derived from the other monomer (a3). In particular, when the silyl ester-based copolymer (A) has a structural unit derived from the monomer (a31), it preferably has a structural unit derived from methyl methacrylate.
The content of the structural unit derived from methyl methacrylate is preferably 0.5 to 40 parts by mass, more preferably 1 to 35 parts by mass, based on 100 parts by mass of all the structural units of the silyl ester copolymer (A). And more preferably 3 to 30 parts by mass. When the content of the structural unit derived from methyl methacrylate is within the above range, an antifouling coating film having excellent coating film strength and thus excellent antifouling performance can be obtained.

In the present invention, as the other monomer (a3), the content of the unsaturated fatty acid, that is, the monomer having an ethylenically unsaturated group and a carboxy group is preferably small. Specifically, examples of unsaturated fatty acids include methacrylic acid and acrylic acid.
The content of these unsaturated fatty acids is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass, based on 100 parts by mass of all the structural units of the silyl ester copolymer (A). Parts by mass, more preferably 0 parts by mass, that is, do not contain.
When the content of the unsaturated fatty acid is within the above range, coating workability and storage stability tend to be excellent.

The silyl ester copolymer (A) can be produced, for example, by the following procedure.
A solvent is charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating / cooling jacket, and is heated and stirred under a nitrogen stream at a temperature of 80 to 90 ° C. While maintaining the same temperature, the monomer (a1), the compound (a2), and optionally the monomer (a3), a polymerization initiator, a chain transfer agent, a solvent, etc. The silyl ester copolymer (A) can be obtained by dropping a mixed solution of the above and performing a polymerization reaction.

The polymerization initiator that can be used for the production of the silyl ester copolymer (A) is not particularly limited, and various radical polymerization initiators can be used. Specifically, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2,2′-azobis (isobutyronitrile) [AIBN], 2,2 '-Azobis (2-methylbutyronitrile) [AMBN], 2,2'-azobis (2,4-dimethylvaleronitrile) [ADVN], tert-butyl peroctoate [TBPO] and the like. These polymerization initiators may be used alone or in combination of two or more. These radical polymerization initiators may be added to the reaction system only at the start of the reaction, or may be added to the reaction system both at the start of the reaction and during the reaction.
The amount of the polymerization initiator used in the production of the silyl ester copolymer (A) is preferably from 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of the above-mentioned monomers and the like (reaction raw materials).

The chain transfer agent that can be used in the production of the silyl ester copolymer (A) is not particularly limited, and includes, for example, α-methylstyrene dimer, thioglycolic acid, diterpene, terpinolene, γ-terpinene; tert-dodecyl Mercaptans such as 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 silyl ester-based copolymer (A), the amount of the chain transfer agent used is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of each monomer and the like (reaction raw materials). preferable.

  Examples of the solvent that can be used for producing the silyl ester copolymer (A) include aromatic solvents such as toluene, xylene, and mesitylene; propanol, butanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like. Alcohols; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as ethyl acetate and butyl acetate; and water.

The weight average molecular weight (Mw) of the silyl ester copolymer (A) is preferably from 3,000 to 70,000 from the viewpoint of coating workability of the coating composition, strength of the antifouling coating film, and the like, More preferably, it is 10,000 to 50,000.
The weight average molecular weight (Mw) of the silyl ester copolymer (A) refers to the value of gel permeation chromatography (GPC) measured by the method described in Examples.
The polydispersity (Mw / Mn) of the silyl ester-based copolymer (A) is not particularly limited, but is preferably 20 or less, more preferably 10 or less, from the viewpoint of obtaining a uniform coating composition.

The content of the silyl ester copolymer (A) in the antifouling coating composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 35% by mass, and still more preferably the solid content of the coating composition. Is 10 to 20% by mass.
In the present invention, when the antifouling coating composition contains two or more silyl ester copolymers (A), the above content is preferable as the total content of the silyl ester copolymer (A). And the same applies to each component described later.

<Optional components>
The antifouling paint composition of the present invention may contain, if necessary, an antifouling agent (B), a monocarboxylic acid compound (C), other binder components (D), a pigment (E), an organic solvent (F), an anti-sagging agent. It may contain an antisettling agent (G), a dehydrating agent (H), a plasticizer (I) and the like.

[Antifouling agent (B)]
In the present invention, the antifouling coating composition of the present invention may contain an antifouling agent (B) for the purpose of imparting antifouling properties to the antifouling coating film.
Examples of the antifouling agent (B) include, for example, cuprous oxide, copper pyrithione, zinc pyrithione, copper thiocyanate (copper rhodan), copper (metallic copper), 4,5-dichloro-2-n-octyl-4-isothiazoline. -3-one (alias: DCOIT), 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (alias: tralopyryl), borane-nitrogen base addition (Pyridine triphenylborane, 4-isopropylpyridinediphenylmethylborane, etc.), (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole (alias: medetomidine), N, N-dimethyl-N '-(3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert -Butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalonitrile, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, chloromethyl-n-octyl disulfide, N ', N'-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthiuram disulfide, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 2,3-dichloro-N- (2', 6 '-Diethylphenyl) maleimide and 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide. These may be used alone or in combination of two or more. May be.
Among the antifouling agents, cuprous oxide (B1) is used as the antifouling agent (B) from the viewpoint of improving the antifouling properties of the formed antifouling coating film, particularly against aquatic organisms of animal species, and water resistance. ) Is preferable.

The cuprous oxide (B1) preferably contains one having a number average particle diameter of about 1 to 30 μm, and from the viewpoint of improving the antifouling property and water resistance of the formed antifouling coating film, from 2 to 10 μm It is more preferred to include
The cuprous oxide (B1) is preferably surface-treated with glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil, or the like, from the viewpoint of long-term stability during storage.
As such cuprous oxide (B1), commercially available ones can be used. For example, NC-301 (manufactured by NC Tech, Inc., number average particle diameter: 2 to 4 μm), NC-803 ( N.Tech Co., Ltd., number average particle size: 6 to 10 μm), Red Cop97N Premium (manufactured by AMERICA CHEMET Co.), Purple Cop (manufactured by AMERICA CHEMET Co.), LoLoTint97 (manufactured by AMERICAN CHEMET Co.), and the like. Can be

  When the coating composition contains cuprous oxide (B1), the content is determined from the viewpoint of the coating workability of the antifouling coating composition and the antifouling performance and water resistance of the antifouling coating film in the present invention. In the solid content of the coating composition, it is preferably 20 to 80% by mass, more preferably 40 to 70% by mass, and still more preferably 50 to 65% by mass.

Among the antifouling agents, it is also preferable to include copper pyrithione from the viewpoint of improving the antifouling property of the formed antifouling coating film, especially against aquatic micro-organisms.
When the coating composition contains copper pyrithione, the content is from the viewpoint of the coating workability of the antifouling coating composition and the antifouling performance and water resistance of the antifouling coating film of the present invention, In the solid content, it is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass.

In addition to the above, the antifouling agent may further include zinc pyrithione, DCOIT, tralopyryl, borane-nitrogen base adduct (pyridine triphenylborane, 4-isopropylpyridine diphenylmethylborane, etc.), and medetomidine. Is preferred in that it has excellent antifouling properties.
From the viewpoint of antifouling properties against aquatic organisms such as barnacles, the antifouling coating composition of the present invention also preferably contains medetomidine as the antifouling agent (B). Medetomidine is (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole and is represented by the following formula (IV).

Although medetomidine has optical isomerism, it may be only one of them or a mixture of any ratio.
Further, as part or all of medetomidine, an adduct to an imidazolium salt, a metal, or the like may be blended, or an addition to an imidazolium salt, a metal, or the like in an antifouling paint composition or an antifouling coating film. An object may be formed.

  When the antifouling coating composition of the present invention contains medetomidine, its content is preferably from 0.01 to 10% in the solid content of the antifouling coating composition from the viewpoint of maintaining high antifouling properties over a long period of time. %, More preferably 0.03 to 5% by mass, even more preferably 0.05 to 3% by mass.

[Monocarboxylic acid compound (C)]
In the present invention, the monocarboxylic acid compound (C) promotes the renewability of the antifouling coating film containing the same from the surface in water, and when the antifouling coating film contains an antifouling agent. Is to enhance the antifouling property of the antifouling coating by promoting the release of the antifouling agent into water, and further has a function of imparting appropriate water resistance to the antifouling coating.
As the monocarboxylic acid compound (C), for example, a compound in which a saturated or unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms is substituted with one carboxy group, or a saturated or unsaturated having 3 to 40 carbon atoms A compound in which a single carboxy group is substituted on the alicyclic hydrocarbon or a compound in which one modified carboxy group is substituted on a modified aliphatic hydrocarbon or alicyclic hydrocarbon is preferred.
Among these, abietic acid, neoabietic acid, dehydroabietic acid, parastolic acid, isopimaric acid, pimaric acid, trimethylisobutenylcyclohexenecarboxylic acid, versatic acid, stearic acid, naphthenic acid and the like are preferable.
Rosins containing abietic acid, parastolic acid, isopimaric acid and the like as main components are also preferable. Examples of the rosins include rosins such as gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, rosin derivatives such as rosin metal salt, and pine tar.
Examples of trimethylisobutenylcyclohexenecarboxylic acid include, for example, a reaction product of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, which is 1,2,3-trimethyl- 5- (2-methylprop-1-en-1-yl) cyclohex-3-en-1-carboxylic acid and 1,4,5-trimethyl-2- (2-methylprop-1-en-1-yl) It has cyclohex-3-ene-1-carboxylic acid as a main component (85% by mass or more).
The monocarboxylic acid compound (C) may be used alone or in combination of two or more.

  A part or all of the monocarboxylic acid compound (C) in the present invention may form a salt. Examples of the salt of the monocarboxylic acid (C) include a zinc salt and a copper salt. Even if the salt is formed in advance before the preparation of the antifouling paint composition, other paints may be used during the preparation of the antifouling paint composition. It may be formed by reaction with a component.

  When the antifouling paint composition of the present invention contains the monocarboxylic acid compound (C), the content is preferably 1 to 50% by mass, more preferably 2 to 30% by mass in the solid content of the antifouling paint composition. %, More preferably 2 to 20% by mass, even more preferably 3 to 12% by mass. In addition, from the viewpoint that the antifouling property and physical properties of the formed coating film are good, the content is preferably 10 to 150 parts by mass, more preferably 20 parts by mass, based on 100 parts by mass of the solid content of the silyl ester copolymer (A). To 100 parts by mass, more preferably 20 to 50 parts by mass, even more preferably 20 to 30 parts by mass.

[Other binder components (D)]
In the present invention, the antifouling coating composition of the present invention is other than the silyl ester-based copolymer (A) for the purpose of imparting standing antifouling property, water resistance, crack resistance and strength to the antifouling coating film. And other binder components (D).
Other binder components (D) include, for example, acrylic copolymers (acrylic resins), vinyl polymers, chlorinated paraffins, n-paraffins, terpene phenols, polyvinyl ethyl ether, and the like. Or two or more of them may be used in combination.

As the acrylic copolymer, those obtained by polymerizing the other monomer (a3) and optionally the compound (a21) and / or (a22) may be used.
The acrylic copolymer preferably contains a structural unit derived from the monomer (a31) or the metal ester group-containing unsaturated monomer (a32) from the viewpoint of standing soil resistance.
The “metal ester group” refers to a group formed by bonding a metal and a carboxylic acid. Further, the “polyvalent metal ester group” or “divalent metal ester group” described later refers to a group formed by bonding 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 (V) is more preferable.

（式（Ｖ）中、Ｍは金属を示し、＊は結合位置を示す。）

(In the formula (V), 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 (V), M is a divalent metal, and a divalent metal can be appropriately selected and used from the above-described metals. Among these, M is preferably a metal of Groups 10 to 12 such as nickel, copper, and zinc, more preferably selected from the group consisting of copper and zinc, and zinc is even more preferable.
Examples of such a monomer (a32) include zinc di (meth) acrylate, copper di (meth) acrylate, zinc acrylate (methacrylic acid), copper acrylate (methacrylic acid), and di (3-acryloyl). Zinc oxypropionate, copper di (3-acryloyloxypropionate), zinc (meth) acrylate (naphthenate), copper (meth) acrylate (naphthenate), and the like.

  As the other binder component (D), commercially available products may be used. For example, "Dianal BR-106" (acrylic polymer) manufactured by Mitsubishi Rayon Co., Ltd., and "Toyoparax A-40 / A" manufactured by Tosoh Corporation. -50 / A-70 / A-145 / A-150 "(chlorinated paraffin).

As the other binder component (D) in the invention, in addition to the above, for example, a polymer (d1) containing two or more acid groups (hereinafter referred to as “acid group”) described in WO 2014/010702. Polymer (d1) "), the monocarboxylic acid compound (C), and a metal compound.
Examples of such an acid group-containing polymer (d1) include a polyester polymer (d11) and an acrylic polymer (d12), and preferably a polyester polymer (d11).
As such a polyester polymer (d11), those having a solid content acid value of 50 to 250 mgKOH / g are preferable, and those having an acid value of 80 to 200 mgKOH / g are more preferable.
Such a polyester polymer (d11) is obtained by reacting one or more polyhydric alcohols with one or more polyhydric carboxylic acids and / or anhydrides, and any kind may be used in any amount. The acid value and the viscosity can be adjusted by the combination.
As such a polyester polymer (d11), for example, a trihydric or higher alcohol (d111), a dibasic acid and / or its anhydride (d112), and a dihydric alcohol (d113) are reacted. After that, those obtained by further reacting an alicyclic dibasic acid and / or an anhydride thereof (d114) are preferable.
As the monocarboxylic acid compound (C) to be reacted with such a polyester-based polymer (d11), those described above can be used. Among them, rosins are preferable, and as the metal compound, for example, zinc oxide And a metal oxide such as cuprous oxide, and among them, zinc oxide is preferable.

[Pigment (E)]
In the present invention, the antifouling coating composition of the present invention may contain the pigment (E) for the purpose of coloring the coating film or hiding the base, and for the purpose of adjusting the coating film strength to an appropriate level. Good.
Examples of the pigment (E) include talc, mica, clay, potassium feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, and zinc sulfide. Extenders, red iron oxide (red iron oxide), titanium white (titanium oxide), yellow iron oxide, carbon black, naphthol red, phthalocyanine blue, and the like. Among them, talc and zinc oxide are preferable. These pigments may be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains the pigment (E), the content is determined by the desired viscosity according to the concealing property required for the antifouling coating film to be formed and the application form of the coating composition. The preferred amount is determined depending on the amount, but the amount is preferably 1 to 50% by mass in the solid content of each coating composition.

[Organic solvent (F)]
In the present invention, the antifouling coating composition may contain an organic solvent (F) for the purpose of keeping the viscosity of the coating composition low and improving spray atomization.
As the organic solvent (F), aromatic hydrocarbon-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, ketone-based, ester-based, or alcohol-based organic solvents can be used, and aromatic hydrocarbons are preferred. It is a system organic solvent.
Examples of the aromatic hydrocarbon-based organic solvent include toluene, xylene, styrene, mesitylene and the like.
Examples of the aliphatic hydrocarbon-based organic solvent include pentane, hexane, heptane, octane and the like.
Examples of the alicyclic hydrocarbon-based organic solvent include cyclohexane, methylcyclohexane, ethylcyclohexane and the like.
Examples of the ketone-based organic solvent include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate.
Examples of the ester-based organic solvent include propylene glycol monomethyl ether acetate and the like.
Examples of the alcohol-based organic solvent include isopropanol, n-butanol, propylene glycol monomethyl ether and the like.
The organic solvent (F) may be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains an organic solvent (F), the desired content in the coating composition is determined by the desired viscosity according to the coating form of the coating composition and the like. -50 mass%, more preferably 10-40 mass%, even more preferably 20-35 mass%. If the content is too large, problems such as a decrease in anti-sagging properties may occur.

<Anti-sagging agent / Anti-settling agent (G)>
In the present invention, for the purpose of adjusting the viscosity of the antifouling coating composition, the antifouling coating composition may contain an anti-sagging agent / anti-settling agent (G).
Examples of anti-sagging agents and anti-settling agents (G) include organoclay waxes (such as Al, Ca, and Zn stearate salts, lecithin salts, and alkyl sulfonate salts), and organic waxes (polyethylene wax, polyethylene oxide wax, and amide). Wax, polyamide wax, hydrogenated castor oil wax, etc.), a mixture of an organoclay wax and an organic wax, and synthetic finely divided silica.
A commercially available product may be used as the anti-sagging agent / anti-settling agent (G). For example, "DISPARON 305", "DISPARON 4200-20", "DISPARON A630-20X", "DISPARON" manufactured by Kusumoto Kasei Co., Ltd. 6900-20X "and" AS-AD-120 "manufactured by Ito Oil Co., Ltd. The anti-sagging agent / anti-settling agent (G) may be used alone or in combination of two or more.
When the antifouling paint composition of the present invention contains an anti-sagging agent / anti-settling agent (G), its content is preferably from 0.01 to 10% by mass in the solid content of the antifouling paint composition. Preferably it is 0.1 to 3% by mass, more preferably 0.5 to 2% by mass.

[Dehydrating agent (H)]
In the present invention, the antifouling coating composition may contain a dehydrating agent (H) for the purpose of improving the storage stability of the coating composition.
Examples of the dehydrating agent (H) include alkoxysilane, zeolite known under the general name of "molecular sieve", porous alumina, orthoesters such as alkyl orthoformate, orthoboric acid, and isocyanate. Of these, alkoxysilanes are preferred from the viewpoints of easy availability and improved storage stability. These dehydrating agents may be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains a dehydrating agent (H), its content is preferably 0.1 to 10% by mass, more preferably 0.2 to 2% by mass in the solid content of the coating composition. %, More preferably 0.5 to 1% by mass. If the content of the dehydrating agent (H) is within the above range, the storage stability of the coating composition can be kept good.

[Plasticizer (I)]
The antifouling coating composition of the present invention may contain a plasticizer (I) for the purpose of imparting plasticity to the antifouling coating film.
Examples of the plasticizer (I) 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.
When the antifouling coating composition of the present invention contains a plasticizer (I), the content is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass in the solid content of the coating composition. %. When the content of the plasticizer (I) is within the above range, the plasticity of the antifouling coating film can be kept good.

[Method for producing antifouling paint composition]
Each of the antifouling paint compositions of the present invention can be prepared using the same apparatus, means, and the like as known general antifouling paints. Specifically, after preparing the silyl ester-based copolymer (A), a solution of this polymer and other additives as needed are added at once or sequentially, followed by stirring and mixing. Can be manufactured.

[Anti-fouling coating film, substrate with anti-fouling coating film, method for producing the same, and anti-fouling method]
The antifouling coating film of the present invention is obtained by drying the antifouling coating composition.
In addition, the antifouling method of the present invention uses the above-described antifouling coating film, and by providing an antifouling coating film to various substrates using the antifouling coating composition of the present invention. It is a method of antifouling.
As a method of forming the antifouling coating film, specifically, for example, after applying the antifouling coating composition of the present invention on a coating film or a substrate, the antifouling coating film can be obtained by drying. .
Examples of the method for applying the coating composition of the present invention include known methods such as a method using a brush, a roller, and a spray.
The antifouling coating composition applied by the method described above is dried, for example, by leaving it at 25 ° C., preferably for about 0.5 to 14 days, more preferably for about 1 to 7 days to obtain a coating film. be able to. The drying of the antifouling coating composition may be performed while blowing air under heating.

  The thickness of the antifouling coating film after drying is arbitrarily selected depending on the renewal speed of the antifouling coating film, the period of use, and the like. Examples of a method for producing a coating film having this thickness include a method in which the coating composition is applied once to a plurality of times, preferably 10 to 300 μm, more preferably 30 to 200 μm per application. Can be

The substrate with an antifouling paint composition of the present invention has a substrate coated with an antifouling coating formed by the antifouling coating composition, and has the antifouling coating on the substrate. .
The substrate with an antifouling coating film of the present invention can be produced by forming the antifouling coating film on a substrate by the method as described above.
The method for producing the substrate with an antifouling coating film of the present invention is not particularly limited. For example, a step (1) of applying or impregnating a substrate with the antifouling coating composition of the present invention to obtain a coated body or an impregnated body. And a step of drying the coated body or the impregnated body (2).
In the step (1), the coating method described above can be adopted as a method of applying the coating composition to the substrate. The method of impregnation is not particularly limited, and the impregnation can be performed by immersing the base material in a sufficient amount of the coating composition for impregnation. Further, there is no particular limitation on the method of drying the coated body or the impregnated body, and the coating body or the impregnated body can be dried by the same method as that for producing the antifouling coating film.

The substrate with an antifouling coating film of the present invention comprises a step (1 ′) of forming a coating film obtained by drying the antifouling coating composition of the present invention, and a step of attaching the coating film to the substrate ( 2 ').
There is no particular limitation on the method of forming the coating film in the step (1 ′), and the coating film can be produced by the same method as that for producing the antifouling coating film.
There is no particular limitation on the method of attaching the coating film to the substrate in step (2 ′), and for example, it can be applied by the method described in JP-A-2013-129724.

The antifouling paint composition of the present invention can be used in a wide range of industrial fields such as ships, fisheries, and marine structures to maintain the antifouling property of a base material for a long period of time. Such base materials include, for example, ships (large steel boats such as container ships and tankers, fishing boats, FRP boats, wooden boats, boat hulls such as yachts, these newly built or repaired ships, etc.), fishing materials (ropes) , Fishing nets, fishing gear, floats, buoys, etc.), oil pipelines, water pipes, circulating water pipes, diver suits, underwater glasses, oxygen cylinders, swimwear, torpedoes, underwater structures such as water supply / drainage outlets for thermal and nuclear power plants, and the sea floor Examples include cables, seawater utilization equipment (seawater pumps and the like), megafloats, gulf roads, submarine tunnels, port facilities, and various structures for marine civil engineering work in canals and waterways. Among these, the substrate is preferably selected from the group consisting of ships, underwater structures, and fishing materials, more preferably selected from the group consisting of ships and underwater structures, and is preferably a ship. More preferred.
In addition, the substrate on which the antifouling coating composition of the present invention is formed on the surface, the surface treated with another treatment agent such as a rust preventive agent, or a coating film such as a primer is already formed on the surface. The antifouling coating composition according to the present invention may be applied to a surface already coated with the antifouling coating composition of the present invention. Not something.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. In the following, "part" means "part by mass" unless specifically contradicting the purpose.
The “solid content” of each component used in the examples refers to a component excluding a volatile component contained as a solvent in each component, and is obtained by drying each component in a hot air dryer at 108 ° C. for 3 hours. Are regarded as solids.

[Production of silyl ester copolymer (A)]
<Production Example 1: Production of silyl ester-based copolymer solution (A-1)>
43 parts by mass of xylene, 10 parts by mass of triisopropylsilyl methacrylate, FM-0711 (manufactured by JNC, one end) in a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen inlet tube, and heating / cooling jacket. 2 parts by mass of methacrylate-modified organopolysiloxane, average molecular weight Mn = 1,000) were charged, and heated and stirred under a temperature of 80 ± 5 ° C. under a nitrogen stream. While maintaining the same temperature, 40 parts by mass of triisopropylsilyl methacrylate and FM-0711 (manufactured by JNC, methacrylate-modified organopolysiloxane at one end, average molecular weight Mn = 1,000) were introduced into the reaction vessel from the dropping device. A mixture consisting of 20 parts by mass of 2-methoxyethyl methacrylate, 20 parts by mass of methyl methacrylate, and 1.1 parts by mass of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. Then, after stirring at the same temperature for 2 hours, 0.4 parts by mass of 2,2′-azobisisobutyronitrile was further added, and the temperature was raised to 105 ° C. over 3 hours. Was added to obtain a colorless and transparent silyl ester copolymer solution (A-1).
Table 1 shows the constitution of the monomer mixture used and the characteristic values of the silyl ester-based copolymer solution (A-1).

<Production Examples 2 to 11: Production of Silyl Ester Copolymer Solutions (A-2) to (A-11)>
A silyl ester-based copolymer solution was prepared in the same manner as in Production Example 1, except that the charging ratio of the monomer mixture used in Production Example 1 and the type and amount of the polymerization initiator used for dropping were changed as shown in Table 1. (A-2) to (A-11) were prepared.
Table 1 shows the composition of the monomer mixture used, and the characteristic values of the silyl ester-based copolymer solutions (A-2) to (A-11) and the copolymers contained therein measured by the method described below. Show.

Each component in Table 1 is as follows.
* 1 FM-0711: methacryloyloxyalkyl-modified organopolysiloxane at one end, manufactured by JNC Corporation, average molecular weight Mn = 1,000
* 2 FM-0721: methacryloyloxyalkyl-modified organopolysiloxane at one end, manufactured by JNC Corporation, average molecular weight Mn = 5,000
* 3 FM-0725: methacryloyloxyalkyl-modified organopolysiloxane at one end, manufactured by JNC Corporation, average molecular weight Mn = 10,000
* 4 FM-7711: manufactured by JNC, methacryloyloxyalkyl-modified organopolysiloxane at both ends, average molecular weight Mn = 1,000
* 5 KF-2001: manufactured by Shin-Etsu Chemical Co., Ltd., side-chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent = 1,900 g / mol

The methods for measuring the viscosities of the obtained polymer solutions (A-1) to (A-11) and the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer contained therein are as follows.
<Viscosity of polymer solution>
The viscosity of the polymer solution at 25 ° C. was measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
<Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw) of polymer>
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer were measured using GPC (gel permeation chromatography) under the following conditions.
GPC conditions Apparatus: "HLC-8120GPC" (manufactured by Tosoh Corporation)
Column: "SuperH2000 + H4000" (Tosoh Corporation, 6 mm (inner diameter), each 15 cm (length))
Eluent: tetrahydrofuran (THF)
Flow rate: 0.500 ml / min
Detector: RI
Column bath temperature: 40 ° C
Standard substance: polystyrene Sample preparation method: A small amount of calcium chloride was added to the polymer solution prepared in each of the production examples to dehydrate it, and then filtered through a membrane filter to obtain a filtrate, which was used as a GPC measurement sample.

[Examples 1 to 16 and Comparative Examples 1 and 2: Production of antifouling paint composition and antifouling coating film]
Table 2 shows the components used in the antifouling paint composition.

<Manufacture of antifouling paint composition>
The components described in Table 3 (parts by mass) were mixed and stirred to obtain an antifouling paint composition. In addition, the compounding amount of each component described in Table 3 shows the compounding amount in a tangible state. For example, in Example 1, the amount (as a whole) of the fatty acid amide in the form (as a whole) is 2.0 parts by mass and the solid content is 20%. Is 0.4 parts by mass.

<Manufacture of antifouling coating film>
An epoxy resin-based rust-preventive paint composition (Epoxy AC paint, trade name "Banno 500", made by Chugoku Paint Co., Ltd.) is applied to a sandblasted steel sheet (300 mm in length x 100 mm in width x 3.2 mm in thickness). After coating to a thickness of 150 μm, a vinyl resin-based binder coating composition (trade name “SILVACS SQ-K”, manufactured by China Paint Co., Ltd.) was applied to a dry film thickness of 40 μm. Subsequently, the antifouling coating composition shown in Table 3 was applied once so that the dry film thickness became 200 μm, and dried at 25 ° C. for 7 days to prepare a test plate with an antifouling coating film. . The three coatings were performed once a day.
A plurality of antifouling test plates were prepared for each coating composition for use in each evaluation described below.

<Evaluation>
(Semi-immersion antifouling property)
The test plate with the antifouling coating film prepared as described above, so that the test surface is perpendicular to the sea surface in Hiroshima Bay, and the draft line where the test surface and the sea surface intersect is near the center of the test surface In addition, the immersion line was immersed in such a manner that the waterline moving up and down due to the vertical movement of the wave was within the range of the upper end and the lower end of the test surface. Six months after the start of immersion under these conditions, the area of marine organisms including slime on the antifouling coating film was measured, and the antifouling coating was performed according to the following (fouling resistance evaluation criteria). The membrane was evaluated for anti-fouling properties by immersion in submerged water. Table 3 shows the results.
(Stain resistance evaluation standard)
5: The area where marine organisms adhered on the test surface is less than 1% of the whole 4: The same area is 1% or more and less than 10% of the whole 3: The same area is 10% or more and less than 30% of the whole 2: The same area is the whole 30% or more and less than 70% of 1: The same area is 70% or more of the whole

(Stain resistance after long-term dynamic immersion)
The test plate with the antifouling coating film prepared as described above was fixed to the inner wall of a cylinder where a rotating water flow was generated at a surface speed of 10 knots, and was dynamically immersed in seawater at 30 ° C. for 6 months. I put it down. By this treatment, the antifouling coating film is exposed to a water stream at a high temperature, so that the antifouling coating film becomes a coating state close to that when exposed to a long-term water flow. Thereafter, the test surface was immersed in Tokyo Bay at a position about 2 meters below the water surface in such a direction that the test surface was perpendicular to the water surface. Six months after the start of immersion under these conditions, the area of marine organisms on the antifouling coating film was measured, and after a long-term dynamic immersion of the antifouling coating film according to the following (fouling resistance evaluation criteria). The fouling was evaluated. Table 3 shows the results.
(Stain resistance evaluation standard)
5: The area where marine organisms adhered on the test surface is less than 1% of the whole 4: The same area is 1% or more and less than 10% of the whole 3: The same area is 10% or more and less than 30% of the whole 2: The same area is the whole 30% or more and less than 70% of 1: The same area is 70% or more of the whole

(Overcoat adhesion)
After immersing the test plate with the antifouling coating film prepared as described above in seawater at 50 ° C. for 3 months, the same antifouling coating composition was applied once so that the dry film thickness became 200 μm. Then, after drying at 25 ° C. for 7 days, it was further immersed in seawater at 50 ° C. for one month. According to JIS K 5400 8.5.2 (cross-cut tape method), this laminated coating film cuts through the coating film on the test plate and reaches the substrate with a cut of 4 mm at intervals of 25 squares. A cellophane adhesive tape was stuck on the grid and peeled off, and the following evaluation was performed based on the number of squares where peeling occurred between the substrate and the coating film or the laminated coating film. It was evaluated according to the standard. Table 3 shows the results.
(Evaluation criteria for top coat adhesion)
5: There is no square where peeling occurred. 4: 1 to 3 squares where peeling occurred. 3: 4 to 10 squares where peeling occurred 2: 11 squares where peeling occurred. 20 pieces 1: 21 or more squares where peeling occurred

As is clear from the results of the examples and comparative examples, according to the present invention, the anti-fouling property in the dry-wet alternate portion in a semi-submerged state is excellent, and the anti-fouling property is maintained even after being placed under a dynamic water flow for a long time. Soil performance can be maintained, and an antifouling coating film further excellent in top coat adhesion, an antifouling coating composition capable of forming the coating film, a substrate with an antifouling coating film having the same on a substrate, and the same A production method and an antifouling method using the antifouling coating film can be provided.

Claims (16)

Containing a silyl ester-based copolymer (A),
The silyl ester copolymer (A) is (i) a structural unit derived from a trialkylsilyl methacrylate (a1), and (ii) a structural unit derived from a compound (a2) represented by the following formula (I). Characterized by having
Antifouling paint composition.

(In the formula (I), R ¹ , R ² and R ³ each independently represent a monovalent hydrocarbon group, X each independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and m And n are each independently 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.)   The antifouling paint composition according to claim 1, wherein the silyl ester-based copolymer (A) contains 20 to 80% by mass of a structural unit derived from a trialkylsilyl methacrylate (a1).   The antifouling paint composition according to claim 1, wherein the silyl ester-based copolymer (A) contains 1 to 30% by mass of a structural unit derived from the compound (a2).   The antifouling composition according to any one of claims 1 to 3, wherein the silyl ester copolymer (A) further has one or more structural units derived from (iii) another monomer (a3). Paint composition. The antifouling coating composition according to claim 4, wherein the other monomer (a3) contains a monomer (a31) represented by the following formula (II).

(In the formula (II), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group, R ⁶ represents a divalent hydrocarbon group, and s represents 1 to 6 Represents an integer.)   The antifouling paint composition according to claim 5, wherein the silyl ester-based copolymer (A) contains 10 to 35% by mass of a structural unit derived from the monomer (a31) represented by the formula (II). object.   The antifouling paint composition according to any one of claims 4 to 6, wherein the other monomer (a3) contains methyl methacrylate.   The antifouling paint composition according to any one of claims 1 to 7, wherein the solid content of the antifouling paint composition contains 5 to 50% by mass of the silyl ester-based copolymer (A).   The antifouling paint composition according to any one of claims 1 to 8, further comprising an antifouling agent (B).   The antifouling paint composition according to claim 9, wherein the antifouling agent (B) contains cuprous oxide (B1).   The antifouling paint composition according to claim 10, wherein the solid content of the antifouling paint composition contains 20 to 80% by mass of the cuprous oxide (B1).   The antifouling paint composition according to any one of claims 1 to 11, further comprising a monocarboxylic acid compound (C).   An antifouling coating film formed from the antifouling coating composition according to claim 1.   A substrate with an antifouling coating film coated with the antifouling coating film according to claim 13. A step (1) of applying or impregnating a substrate with the antifouling paint composition according to any one of claims 1 to 12 to obtain an applied body or an impregnated body, and a step of drying the applied body or the impregnated body. Having (2),
A method for producing a substrate with an antifouling coating film. An antifouling method using the antifouling coating film according to claim 13.