WO2018221641A1

WO2018221641A1 - Multilayer antifouling coating, multilayer antifouling coating-equipped substrate and method for producing same, coating material kit for forming multilayer antifouling coating, top-layer antifouling coating material composition, and antifouling method

Info

Publication number: WO2018221641A1
Application number: PCT/JP2018/020920
Authority: WO
Inventors: 聡一郎谷野
Original assignee: 中国塗料株式会社
Priority date: 2017-06-01
Filing date: 2018-05-31
Publication date: 2018-12-06
Also published as: JP6948390B2; KR20200003000A; JPWO2018221641A1; KR102340449B1; KR102340449B9; CN110691826A

Abstract

A multilayer antifouling coating obtained by layering an underlayer antifouling coating (X) and a top-layer antifouling coating (Y), wherein the underlayer antifouling coating (X) contains a polymer (B1) and an organic antifouling agent (C1), the polymer (B1) is a polymer having a constituent unit derived from a monomer having an unsaturated double bond, and the top-layer antifouling coating (Y) contains a hydrolyzable polymer (A2).

Description

Laminated antifouling coating film, substrate with laminated antifouling coating film and production method thereof, laminated antifouling coating film forming coating kit, upper antifouling coating composition, and antifouling method

The present invention relates to a laminated antifouling coating, a substrate with a laminated antifouling coating and a method for producing the same, a coating kit for forming a laminated antifouling coating, an upper antifouling coating composition, and an antifouling method.

Articles used underwater such as ships, underwater structures and fishing nets are required to prevent attachment of aquatic organisms so as not to impair their functions. So far, for the purpose of preventing this biofouling, synthesis and evaluation studies of many organic compounds having biocidal properties and biorepellency, that is, organic antifouling agents have been made. As a typical example of such an organic antifouling agent, for example, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as Patent Document 1) And 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (also known as DCOIT) described in Patent Document 2.
On the other hand, in order to make use of the effect of such an antifouling agent, use of a self-polishing antifouling coating film using a hydrolyzable polymer has been studied. The self-polishing antifouling coating film has a coating film surface continuously formed by a process in which the hydrolyzable polymer undergoes a hydrolysis reaction on the coating film surface in contact with water, and the hydrophilic layer is cleaned by water flow. It is a renewed coating film. Antifouling agents such as those mentioned above gradually diffuse into the water from the surface of the coating, so the concentration on the surface of the coating decreases, but this problem can be improved by combining with this self-polishing antifouling coating. Can do. For example, Patent Document 3 discloses an antifouling coating composition containing two or more types of antifouling agents containing tralopyryl and an acrylic resin having a specific group in the side chain.

International Publication No. 95/5739 International Publication No. 95/32862 International Publication No. 2011/158358

However, the antifouling coating composition containing such an antifouling agent and a hydrolyzable polymer, particularly when the antifouling agent is an organic antifouling agent that is soluble in a solvent usually contained in the antifouling coating composition. When an antifouling coating composition is applied and dried to form an antifouling coating film, the antifouling agent is unevenly distributed near the surface of the coating film in the case of drying in the external environment, particularly at a high temperature. There was a problem that occurred. The exact cause of this is unknown, but if the antifouling agent is unevenly distributed near the surface of the paint film, in addition to malfunctions such as abnormal appearance of the paint film, a major problem is the renewal of the paint film at the initial stage of use of the paint film. Many of the antifouling agents in the paint film are consumed by this, and in the subsequent use of the antifouling paint film, there is a risk that the antifouling agent concentration will be lower than the design and the long-term antifouling property will be reduced. was there.

In view of such a problem, the present invention has no problem such as poor appearance due to uneven distribution of the antifouling agent on the surface of the coating film, and can exhibit a high antifouling performance for a long time even under a high fouling load. An object is to provide an antifouling coating, a substrate with a laminated antifouling coating using the laminated antifouling coating, a method for producing the same, and an antifouling method. It is another object of the present invention to provide a laminate antifouling coating film forming coating kit and an upper antifouling coating composition that are used in the production of the antifouling coating film.

As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by using a laminated antifouling coating film having the specific conditions shown below, and the present invention has been completed.

The present invention relates to the following [1] to [18].
[1] A laminated antifouling coating film in which a lower antifouling coating film (X) and an upper antifouling coating film (Y) are laminated. The lower antifouling coating film (X) is a polymer (B1). ) And an organic antifouling agent (C1), and the polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond, and the upper antifouling coating film (Y) is a laminated antifouling coating film containing a hydrolyzable polymer (A2).
[2] The laminated antifouling coating film according to [1], wherein the lower antifouling coating film (X) further contains a hydrolyzable polymer (A1).
[3] In [1] or [2], the total amount of the polymer (B1) and the hydrolyzable polymer (A1) in the lower antifouling coating film (X) is 1 to 90% by mass. The laminated antifouling coating film described.
[4] The hydrolyzable polymer (A1) and / or the hydrolyzable polymer (A2) has structural units derived from the silyl ester group-containing monomer (a11). The laminated antifouling coating film according to any one of the above.
[5] The laminated antifouling coating film according to [4], wherein the silyl ester group-containing monomer (a11) is represented by the following formula (1-1).

(In formula (1-1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² , R ¹³ and R ¹⁴ each independently represents a monovalent hydrocarbon group.)

[6] The hydrolyzable polymer (A1) and / or the hydrolyzable polymer (A2) includes structural units derived from the metal ester group-containing monomer (a12). The laminated antifouling coating film according to any one of the above.
[7] The metal ester group-containing monomer (a12) includes a monomer (a121) represented by the following formula (1-2) and a monomer (a122 represented by the following formula (1-3): The antifouling coating film according to [6], which contains at least one of

(In formula (1-2), each R ²¹ independently represents a monovalent group containing a terminal ethylenically unsaturated group, and M represents a metal.)

(In the formula (1-3), R ³¹ represents a monovalent group containing a terminal ethylenically unsaturated group, and R ³² is a monovalent organic group having 1 to 30 carbon atoms which does not contain a terminal ethylenically unsaturated group. And M represents a metal.)

[8] The lower antifouling coating film (X) is used as the organic antifouling agent (C1) as 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbohydrate. The laminated antifouling coating according to any one of [1] to [7], which contains at least one selected from nitrile and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one film.
[9] A substrate with a laminated antifouling coating film coated with the laminated antifouling coating film according to any one of [1] to [8].
[10] The substrate with a laminated antifouling coating film according to [9], wherein the substrate is an underwater structure, a ship, or a fishing gear.
[11] An antifouling method using the laminated antifouling coating film according to any one of [1] to [8].
[12] Applying the lower layer antifouling coating composition (x) on the substrate to form the lower layer antifouling coating (X); and the upper layer antifouling coating on the lower layer antifouling coating (X) It has the process of apply | coating a composition (y) and forming an upper layer antifouling coating film (Y), The said lower layer antifouling coating composition (x) is a polymer (B1) and an organic antifouling agent (C1). The polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond, and the upper antifouling paint composition (y) is hydrolyzable. The manufacturing method of a base material with a lamination | stacking antifouling coating film containing a polymer (A2) and an organic solvent (D2).
[13] The laminate according to [12], wherein the organic solvent (D2) is soluble in the polymer (B1) and the organic antifouling agent (C1) contained in the lower layer antifouling coating composition (x). Manufacturing method of base material with antifouling coating film.
[14] In the above [12] or [13], the organic solvent (D2) contains one or more selected from the group consisting of hydrocarbon solvents, alcohol solvents, ketone solvents, and ester solvents. The manufacturing method of the base material with a laminated antifouling coating film of description.
[15] The upper antifouling coating composition (y) contains an organic antifouling agent (C2), and the content (mass%) of the organic antifouling agent (C2) in the upper antifouling coating composition (y). The antifouling paint according to any one of [12] to [14], which is lower than the content (% by mass) of the organic antifouling agent (C1) in the lower layer antifouling coating composition (x) The manufacturing method of a base material with a film.
[16] The laminated antifouling coating film according to any one of [12] to [15], wherein the upper antifouling coating composition (y) contains substantially no organic antifouling agent (C2) A method for producing a substrate.
[17] Lower layer antifouling paint composition (x) containing polymer (B1) and organic antifouling agent (C1), and upper layer containing hydrolyzable polymer (A2) and organic solvent (D2) A coating kit for forming a laminated antifouling coating film comprising an antifouling coating composition (y), wherein the polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond. A coating for forming a laminated antifouling coating film, wherein the polymer (B1) and the organic antifouling agent (C1) contained in the lower antifouling coating composition (x) are soluble in the organic solvent (D2) kit.
[18] An upper antifouling paint composition to be coated on the surface of the lower antifouling coating film (X) containing the polymer (B1) and the organic antifouling agent (C1), wherein the polymer (B1) A polymer having a structural unit derived from a monomer having an unsaturated double bond, wherein the upper antifouling coating composition contains a hydrolyzable polymer (A2) and an organic solvent (D2), and the organic The upper layer antifouling coating composition in which the solvent (D2) is soluble in the polymer (B1) and the organic antifouling agent (C1) contained in the lower layer antifouling coating film (X).

According to the present invention, there is no problem such as poor appearance due to uneven distribution of the antifouling agent on the surface of the coating film, and a laminated antifouling coating film that exhibits high antifouling performance over a long period even under a high fouling load, Provided are a substrate with a laminated antifouling coating using the laminated antifouling coating, a method for producing the same, and an antifouling method. Furthermore, according to the present invention, there are provided a laminated antifouling coating film forming coating kit and an upper antifouling coating composition used for the production of the antifouling coating film.

[Laminated antifouling coating film, substrate with laminated antifouling coating film, and method for producing the same]
The laminated antifouling coating film of the present invention is a laminated antifouling coating film (X) and an upper antifouling coating film (Y) laminated together, and the lower antifouling coating film (X ) Contains a polymer (B1) and an organic antifouling agent (C1), and the polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond. The upper antifouling coating film (Y) contains a hydrolyzable polymer (A2).
Moreover, the base material with a laminated antifouling coating film of the present invention is formed by coating the base material with the laminated antifouling coating film of the present invention.
Furthermore, the manufacturing method of the base material with a lamination | stacking antifouling coating film of this invention apply | coats a lower layer antifouling coating composition (x) on a base material, and forms the lower layer antifouling coating film (X), and The lower antifouling coating composition (x) has a step of applying an upper antifouling coating composition (y) on the lower antifouling coating (X) to form an upper antifouling coating (Y). Contains a polymer (B1) and an organic antifouling agent (C1), and the polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond, The upper antifouling paint composition (y) contains a hydrolyzable polymer (A2) and an organic solvent (D2).
The substrate with a laminated antifouling coating film of the present invention is preferably produced by the method for producing a substrate with a laminated antifouling coating film of the present invention. Moreover, the laminated antifouling coating film of the present invention is formed by the lower antifouling coating composition (x) and the upper antifouling coating composition (y) used in the method for producing a substrate with the laminated antifouling coating. It is preferable.

When an antifouling coating film is formed using conventional antifouling paints as shown in Patent Documents 1 to 3, there is a problem that organic antifouling agents are unevenly distributed near the surface of the coating film depending on the external environment. There was a case. As a result of intensive studies, the present inventors have found that the lower antifouling coating film (X) contains a specific polymer (B1) and an organic antifouling agent (C1), and further on the lower antifouling coating film (X). In addition, by forming the upper antifouling coating film (Y) containing the hydrolyzable polymer (A2), uneven distribution of the organic antifouling agent in the vicinity of the surface of the laminated antifouling coating film is suppressed, resulting in poor appearance, etc. The present inventors have found that high antifouling performance is exhibited over a long period of time even under conditions where the fouling load is high and the present invention has been completed.
Although the detailed mechanism of action for obtaining the above effect is not necessarily clear, a part is estimated as follows. That is, the organic antifouling agent (C1) contained in the lower antifouling coating film (X) was unevenly distributed near the surface of the lower antifouling coating film (X) when forming the lower antifouling coating film (X). Even in the case, by providing the upper antifouling coating film (Y) on the lower antifouling coating film (X), the organic antifouling agent (C1) as a whole laminated antifouling coating film is brought close to the surface. It is considered that uneven distribution is suppressed and occurrence of appearance defects is suppressed.
Further, in the laminated antifouling coating film, since the organic antifouling agent (C1) is continuously supplied from the lower antifouling coating film (X) in the upper antifouling coating film (Y), the initial stage Therefore, it is estimated that high antifouling performance can be exhibited over a long period of time. In addition, since the upper layer antifouling coating film (Y) contains the hydrolyzable polymer (A2), the antifouling property is exhibited also by the coating film renewability of the upper layer antifouling coating film (Y). In particular, the upper antifouling coating composition (y) for forming the upper antifouling coating film (Y) contains the organic solvent (D2), and the organic solvent (D2) is the lower antifouling coating film (X). When the upper layer antifouling coating composition (y) is applied to the lower layer antifouling coating film (X), the polymer (B1) and the organic antifouling agent (C1) contained in Since the organic antifouling agent (C1) is extracted in the coating composition (y) and an appropriate amount of the organic antifouling agent (C) is supplied into the upper antifouling coating film (Y), it is high from the beginning. It is estimated that antifouling performance can be exhibited.
Further, in the general antifouling coating film, the organic antifouling agent is uniformly distributed, or compared with the antifouling coating film that is unevenly distributed toward the surface layer, the laminated antifouling coating of the present invention The film is considered to have a concentration gradient state in which the concentration of the organic antifouling agent (C1) increases toward the lower layer, and the upper layer in terms of disappearance due to diffusion of the organic antifouling agent from the coating film in water. It is also presumed that the antifouling performance is improved because the concentration of the organic antifouling agent (C1) can be kept high when the coating film renewal toward the lower layer reaches the lower layer.
Hereinafter, the lower antifouling coating film (X), the lower antifouling coating composition (x) suitable for forming the lower antifouling coating (X), the upper antifouling coating (Y), and the upper antifouling coating The upper antifouling paint composition (y) suitable for forming the dirty coating film (Y) will be described.
In the following description, the lower layer antifouling paint composition (x) and the upper layer antifouling paint composition (y) are collectively referred to as an antifouling paint composition or a paint composition. Further, the hydrolyzable polymer contained in the lower layer antifouling paint composition (x) is a hydrolyzable polymer (A1), and the hydrolyzable polymer contained in the upper layer antifouling paint composition (y) is hydrolysable. Like the polymer (A2), each component contained in the lower layer antifouling paint composition (x) includes 1 after the alphabet representing the component, and each component contained in the upper layer antifouling paint composition (y). In addition, 2 is added after the alphabet representing the component, and when these are collectively referred to, they are described without a numeral as in the hydrolyzable polymer (A).

<Lower antifouling coating film (X) and lower antifouling coating composition (x), and upper antifouling coating film (Y) and upper antifouling coating composition (y)>
The laminated antifouling coating film of the present invention is formed by laminating a lower antifouling coating film (X) and an upper antifouling coating film (Y). The lower antifouling coating film (X) and the upper antifouling coating film (Y) are preferably adjacent layers.
The lower layer antifouling coating film (X) contains a polymer (B1) and an organic antifouling agent (C1). The lower layer antifouling coating film (X) may further contain a hydrolyzable polymer (A1).
Moreover, the lower layer antifouling coating composition (x) suitably used for forming the lower layer antifouling coating film (X) contains the polymer (B1) and the organic antifouling agent (C1), and further contains an organic solvent. It is preferable to contain (D1). Moreover, in addition to the said component, you may contain a hydrolysable polymer (A1).
The upper antifouling coating film (Y) contains a hydrolyzable polymer (A2).
Further, the upper antifouling coating composition (y) suitably used for forming the upper antifouling coating film (Y) may contain an organic solvent (D2) in addition to the hydrolyzable polymer (A2). preferable.
Hereinafter, each component used for an antifouling coating film and an antifouling coating composition is demonstrated.

(Hydrolyzable polymer (A1) and hydrolyzable polymer (A2))
In the present invention, the upper antifouling coating film (Y) may contain a hydrolyzable polymer (A2), and the lower antifouling coating film (X) may contain a hydrolyzable polymer (A1). Here, as described above, the hydrolyzable polymer (A1) and the hydrolyzable polymer (A2) are collectively referred to as a hydrolyzable polymer (A).
When the upper antifouling coating film (Y) contains the hydrolyzable polymer (A2), the upper antifouling coating film (Y) is given antifouling properties due to appropriate water resistance and coating film renewability. . Moreover, when the lower layer antifouling coating film (X) contains the hydrolyzable polymer (A1), appropriate water resistance and coating film renewability are imparted to the lower layer antifouling coating film (X).

The hydrolyzable polymer (A) has a structural unit derived from (i) a hydrolyzable group-containing monomer (a1), and (ii) a structure derived from another monomer (a2). It is preferable to have a unit.
In the present invention, the “polymer having a structural unit derived from a” means a polymer in which a is introduced by a polymerization reaction or chain transfer. Thus, for example, when the monomer (a2) has a mercapto group, the hydrolyzable polymer is such that the radical polymerization terminal pulls out H of —SH and the generated —S ^· (S radical) starts polymerization. In such a case, the hydrolyzable polymer (A) also has a structural unit derived from the other monomer (a2).
Hereinafter, each structural unit will be described.

[(I) Structural Unit Derived from Hydrolyzable Group-Containing Monomer (a1)]
The hydrolyzable polymer (A) has a structural unit derived from (i) the hydrolyzable group-containing monomer (a1).
Preferred examples of the hydrolyzable group-containing monomer (a1) include a silyl ester group-containing monomer (a11) or a metal ester group-containing monomer (a12).
The upper layer antifouling paint composition (y) contains the hydrolyzable polymer (A2) having a structural unit derived from the silyl ester group-containing monomer (a11). It is preferable from the viewpoint of improving the antifouling property and the interlayer adhesion between the upper antifouling coating film (Y) and the lower antifouling coating film (X).
In addition, it is also possible that the upper layer antifouling coating composition (y) contains a hydrolyzable polymer (A2) having a structural unit derived from the metal ester group-containing monomer (a12). This is preferable from the viewpoint of improving the antifouling property of the film and the physical properties of the antifouling coating film.
The content of the structural unit derived from the hydrolyzable monomer (a1) in the hydrolyzable polymer (A) is preferably 3 to 3 when the total structural unit of the hydrolyzable polymer is 100 parts by mass. 80 parts by mass, more preferably 5 to 70 parts by mass.

—Silyl ester group-containing monomer (a11) —
The silyl ester group-containing monomer (a11) preferably contains a compound represented by the following formula (1-1).

In formula (1-1), R ¹¹ represents a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of improving the long-term antifouling property and water resistance of the antifouling coating film.
In the formula (1-1), R ¹² , R ¹³ and R ¹⁴ each independently represent a monovalent hydrocarbon group, and examples of such hydrocarbon groups include linear, branched or cyclic alkyl groups. , And aryl groups. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. From the viewpoint of imparting appropriate hydrolyzability to the antifouling coating film to improve long-term antifouling properties and water resistance, R ¹² to R ¹⁴ are isopropyl group, n-propyl group, sec-butyl group, It is preferably selected from an n-butyl group and a phenyl group, more preferably all of R ¹² to R ¹⁴ are isopropyl groups.
That is, as the silyl ester group-containing monomer (a11), triisopropylsilyl (meth) acrylate is particularly preferable, and triisopropylsilyl methacrylate is most preferable.

When the hydrolyzable polymer (A) has a structural unit derived from the monomer (a11), the amount of the structural unit derived from the monomer (a11) with respect to 100 parts by mass of all the structural units is antifouling coating. From the viewpoint of improving the water resistance of the membrane, it is preferably 10 to 90 parts by mass, more preferably 40 to 80 parts by mass, still more preferably 45 to 70 parts by mass, and even more preferably 45 to 65 parts by mass.
In addition, the ratio of each content (mass) of the structural unit derived from each monomer etc. in a hydrolyzable polymer (A) is the preparation amount of each said monomer etc. (reaction raw material) used for a polymerization reaction. It can be regarded as the same as the ratio of (mass).

-Metal ester group-containing monomer (a12)-
In the present invention, the hydrolyzable group-containing monomer (a1) preferably contains a metal ester group-containing monomer (a12), and the metal ester group-containing monomer is represented by the following formula (1-2): It is preferable to contain at least one of a monomer (a121) represented by the formula (1) and a monomer (a122) represented by the following formula (1-3).

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 (1-2), M is a divalent metal, and a divalent metal can be appropriately selected from the metals described above. Of these, Group 10-12 metals such as nickel, copper, and zinc are preferred, copper and zinc are more preferred, and zinc is even more preferred.

In the formula (1-2), R ²¹ represents a monovalent group containing a terminal ethylenically unsaturated group (CH ₂ ═C <), and the carbon number of R ²¹ is preferably 2 to 50, more preferably Is 2 to 30, more preferably 2 to 10, and still more preferably 2 to 6. R ²¹ only needs to have a terminal ethylenically unsaturated group, and may have an ethylenically unsaturated group other than the terminal, but may have an ethylenically unsaturated group only at the terminal. More preferred.
R ²¹ is preferably an unsaturated aliphatic hydrocarbon group containing a terminal ethylenically unsaturated group, and the unsaturated aliphatic hydrocarbon group has an ester bond, an amide bond, or an ether bond in the carbon chain. You may have. Specific examples of R ²¹ include acrylic acid (2-propenoic acid), methacrylic acid (2-methyl-2-propenoic acid), 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, 3- (meth) Examples thereof include a group obtained by removing a carboxy group from an aliphatic unsaturated monocarboxylic acid having a terminal ethylenically unsaturated group such as acryloyloxypropionic acid and 3- (meth) acryloyloxy-2-methylpropionic acid. Moreover, the group remove | excluding one carboxy group from the aliphatic unsaturated dicarboxylic acid containing terminal ethylenically unsaturated groups, such as itaconic acid, is illustrated.
Among these, R ²¹ is preferably a group obtained by removing a carboxy group from an aliphatic unsaturated monocarboxylic acid containing a terminal ethylenically unsaturated group, and includes acrylic acid, methacrylic acid, and (meth) acryloyloxyalkyl. A group obtained by removing a carboxy group from a carboxylic acid is more preferred, and a group obtained by removing a carboxy group from acrylic acid or methacrylic acid is more preferred.

Such a monomer (a121) is preferably a monomer (a121 ') represented by the following formula (1-2').

(In the formula (1-2 ′), R ²² each independently represents a hydrogen atom or a methyl group, and M ′ represents copper or zinc.)

As the monomer (a121) represented by the formula (1-2), zinc diacrylate, zinc dimethacrylate, zinc acrylate (methacrylic acid), zinc di (3-acryloyloxypropionate), di (3 -Methacryloyloxypropionic acid) zinc, di (3- (meth) acryloyloxy-2-methylpropionic acid) zinc, copper diacrylate, copper dimethacrylate, acrylic acid (methacrylic acid) copper, di (3-acryloyloxypropion) Acid) copper, di (3-methacryloyloxypropionic acid) copper, and di (3- (meth) acryloyloxy-2-methylpropionic acid) copper.

In the formula (1-3), R ³¹ represents a monovalent group containing a terminal ethylenically unsaturated group. Examples of R ³¹ include the same groups as R ²¹ in formula (1-2), and preferred embodiments are also the same.
In the formula (1-3), R ³² represents a monovalent organic group having 1 to 30 carbon atoms that does not contain a terminal ethylenically unsaturated group. R ³² includes an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and an aromatic hydrocarbon having 6 to 30 carbon atoms, which does not contain a terminal ethylenically unsaturated group. Examples are groups. These groups may have a substituent. Examples of the substituent include a hydroxyl group.
The aliphatic hydrocarbon group may be linear or branched, and may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. When R ³² is an unsaturated aliphatic hydrocarbon group, R ³² does not contain a terminal ethylenically unsaturated group. The aliphatic hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 28 carbon atoms, more preferably 1 to 26 carbon atoms, and still more preferably 1 to 24 carbon atoms. The aliphatic hydrocarbon group may be further substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
The alicyclic hydrocarbon group may be a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group. The alicyclic hydrocarbon group has 3 to 30, preferably 4 to 20, more preferably 5 to 16, and still more preferably 6 to 12 carbon atoms. The alicyclic hydrocarbon group may be further substituted with an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aromatic hydrocarbon group has 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may be further substituted with an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

R ³² is preferably an organic acid residue formed from a monobasic acid, specifically, versatic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, Examples thereof include a group in which a carboxy group is removed from an organic acid selected from the group consisting of neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, and naphthenic acid.
Among these, a group obtained by removing a carboxy group from abietic acid, versatic acid, and naphthenic acid is preferable, and a group obtained by removing a carboxy group from abietic acid and versatic acid is more preferable.

Such a monomer (a122) is preferably a monomer (a122 ') represented by the following formula (1-3').

(In the formula (1-3 ′), R ³³ represents a hydrogen atom or a methyl group, R ³⁴ represents a monovalent organic group having 1 to 30 carbon atoms that does not contain a terminal ethylenically unsaturated group, and M ′ represents (Indicates copper or zinc.)

Examples of the monomer (a122) represented by the formula (1-3) include 3- (meth) acryloyloxypropionic acid (rosin) zinc, 3- (meth) acryloyloxypropionic acid (versaic acid) zinc, ) Zinc acrylic acid (rosin), (meth) acrylic acid (versaic acid) zinc, (meth) acrylic acid (naphthenic acid) zinc, 3- (meth) acryloyloxypropionic acid (rosin) copper, 3- (meth) acryloyl Examples include oxypropionic acid (versaic acid) copper, (meth) acrylic acid (rosin) copper, (meth) acrylic acid (versatic acid) copper, and (meth) acrylic acid (naphthenic acid) copper.
When the hydrolyzable polymer (A) has a structural unit derived from the monomer (a122) represented by the formula (1-3), the hydrolyzable polymer (A) is represented by the formula (1-3 It is preferable to have a structural unit obtained by polymerization of only the terminal ethylenically unsaturated group in the polymerizable compound represented by (monomer (a122)).
When hydrolyzable polymer (A) has a structural unit derived from monomer (a121) or (a122), a structure derived from monomers (a121) and (a122) with respect to 100 parts by mass of all structural units The total content of units is preferably 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, from the viewpoint of improving the antifouling performance and water resistance of the antifouling coating film.

[(Ii) Structural units derived from other monomers (a2)]
In the present invention, the hydrolyzable polymer (A) preferably has a structural unit derived from (ii) another monomer (a2).
As said other monomer (a2), the monomer copolymerizable with the said monomer (a1) can be used without a restriction | limiting. Among these, it is preferable that another monomer (a2) is an ethylenically unsaturated compound.
Examples of the other monomer (a2) include:
Polyorganosiloxane block-containing monomer (a21);
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-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 Alkyl (meth) acrylates such as lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, or Reel (meth) acrylate;
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, isobutoxybutyl diglycol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, Alkoxyalkyl (meth) acrylates such as phenoxypolyethylene glycol (meth) acrylate;
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) acrylate;
Examples include vinyl compounds such as styrene, α-methylstyrene, vinyl acetate, vinyl benzoate, vinyl toluene, acrylonitrile, vinyl pyridine, vinyl pyrrolidone, and vinyl chloride. The organosiloxane block-containing monomer (a21) is preferably included. These monomers may be used alone or in combination of two or more.

The polyorganosiloxane block-containing monomer (a21) is a monomer having a polyorganosiloxane block and a chain transfer reactive group such as a polymerizable unsaturated group and / or a thiol group. A polyorganosiloxane block is introduced into the degradable polymer (A), which is particularly preferable in terms of improving antifouling performance such as slime resistance.
The polyorganosiloxane block-containing monomer (a21) is preferably represented by the following formula (2).

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

In formula (2), R ¹ , R ² , and R ³ each independently represent a monovalent hydrocarbon group, and the hydrocarbon group is a linear, branched, or cyclic alkyl group, and an aryl group. Etc. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. R ¹ , R ² , and R ³ are preferably alkyl groups such as a methyl group and a butyl group from the viewpoint of ease of polymerization.
In formula (2), each X independently represents a (meth) acryloyloxyalkyl group or a mercaptoalkyl group, and is preferably a (meth) acryloyloxyalkyl group from the viewpoint of uniform polymerization, and the viscosity of the polymer to be formed Mercaptoalkyl groups are also preferred from the standpoint of reducing the amount and facilitating handling. Examples of such X include (meth) acryloyloxyethyl group, (meth) acryloyloxypropyl group, (meth) acryloyloxybutyl group, mercaptomethyl group, mercaptoethyl group, mercaptopropyl group, mercaptobutyl group and the like. .
In formula (2), m is 1 or more, n is 0 or more, p and q are each independently 0 or 1, and n + p + q is 1 or more.
In addition, m and n mean the average number of repetitions of (SiR ² ₂ O) and (SiXR ³ O), respectively.
In formula (2), m + n is preferably 2 or more.

In addition, in this specification, when two or more different repeating units are described in parallel between [], these repeating units are respectively repeated in any form and order of random, alternating or block. Indicates that it may be. That is, for example, in the formula-[Y ₃ -Z ₃ ]-(where Y and Z represent repeating units), in a random form such as -YYZYZZ-, in an alternating form such as -YZYZYZ-, A block shape such as YYYZZZZ- or -ZZZYYY- may be used.

As one certain form, a hydrolyzable polymer (A) is a structural unit derived from the monomer (a211) whose n is 0, p is 1, and q is 0 in Formula (2). It is preferable to have.
The antifouling coating composition containing the hydrolyzable polymer (A) having a structural unit derived from such a monomer (a211) can form an antifouling coating film having particularly excellent antifouling properties. Is preferable.
In such a monomer (a211), m is preferably from 3 to 200, more preferably from 5 to 70, from the viewpoint of ease of polymerization and the like.
As such a monomer (a211), a commercially available product can be used. For example, FM-0711 (single terminal methacryloyloxyalkyl-modified organopolysiloxane, number average molecular weight Mn = 1, manufactured by JNC Corporation). 000), FM-0721 (one-end methacryloyloxyalkyl-modified organopolysiloxane, number average molecular weight Mn = 5,000), FM-0725 (one-end methacryloyloxyalkyl-modified organopolysiloxane, number-average molecular weight Mn = 10,000) X-22-174ASX (single terminal methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 900 g / mol), KF-2012 (single terminal methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent, manufactured by Shin-Etsu Chemical Co., Ltd. 4,600g / m l), X-22-2426 (one terminal methacryloyloxy alkyl-modified organopolysiloxane, functional group equivalent 12,000 g / mol) and the like.

Moreover, as one certain form, a hydrolyzable polymer (A) has a structural unit derived from the monomer (a212) whose n is 0 and p and q are 1 in Formula (2). Is also preferable.
The antifouling coating composition containing the hydrolyzable polymer (A) having a structural unit derived from such a monomer (a212) tends to have good interlayer adhesion of the laminated antifouling coating film to be formed. This is preferable.
In such a monomer (a212), m is preferably from 3 to 200, more preferably from 5 to 70, from the viewpoint of ease of polymerization and the like.
As such a monomer (a212), a commercially available product can be used. For example, FM-7711 (both terminal methacryloyloxyalkyl-modified organopolysiloxane, number average molecular weight Mn = 1, manufactured by JNC Corporation). 000), FM-7721 (both ends methacryloyloxyalkyl-modified organopolysiloxane, number average molecular weight Mn = 5,000), FM-7725 (both ends methacryloyloxyalkyl modified organopolysiloxane, number average molecular weight Mn = 10,000) X-22-164 (both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 190 g / mol), X-22-164AS (both ends methacryloyloxyalkyl-modified organopolysiloxane, functional, manufactured by Shin-Etsu Chemical Co., Ltd. Group equivalent 450 g / mol X-22-164A (both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 860 g / mol), X-22-164B (both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 1630 g / mol), X -22-164C (both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 2,370 g / mol), X-22-164E (both ends methacryloyloxyalkyl-modified organopolysiloxane, functional group equivalent 3,900 g / mol) X-22-167B (both terminal mercaptoalkyl-modified organopolysiloxane, functional group equivalent 1,670 g / mol).

Further, as one form, the hydrolyzable polymer (A) has a structural unit derived from a monomer (a213) in which X is a mercaptoalkyl group and n is 1 or more in the formula (2). It is also preferable.
It is preferable that the hydrolyzable polymer (A) has a structural unit derived from such a monomer (a213) because the viscosity is low and the handling is easy.
In such a monomer (a213), m is preferably 50 to 1,000 and n is preferably 1 to 30 from the viewpoint of ease of polymerization and the like.
As such a monomer (a213), a commercially available product can be used. For example, KF-2001 (side chain mercaptoalkyl-modified organopolysiloxane manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent 1,900 g) / Mol), KF-2004 (side chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent 30,000 g / mol).

The content of the structural unit derived from the monomer (a21) in the hydrolyzable polymer (A) is all from the viewpoints of antifouling performance, water resistance and interlayer adhesion under alternating wet and dry conditions of the antifouling coating film. The amount is preferably 0.5 to 60 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 2 to 50 parts by mass, and still more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the structural unit.

The hydrolyzable polymer (A) can be obtained by synthesizing the hydrolyzable group-containing monomer (a1) and, if necessary, another monomer (a2) by a known method.
For example, when the hydrolyzable group-containing monomer (a1) contains the monomer (a121) or (a122), for example, an inorganic metal compound (preferably an oxide or hydroxide of copper or zinc, Chloride, etc.) and an organic acid such as methacrylic acid or acrylic acid or an esterified product thereof are synthesized by a known method such as heating at a temperature below the decomposition temperature of the metal salt in the presence of an organic solvent and water and stirring. be able to.
More specifically, 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 ° C., and this is mixed with an organic acid such as methacrylic acid or acrylic acid or its A monomer (a121) or (a122) is prepared by dropping a mixed liquid of an ester body and water and stirring the mixture.
Next, a solvent is placed in a newly prepared reaction vessel and heated to about 80 to 120 ° C., and the monomer (a121) or (a122) and other monomers (a2), a polymerization initiator, A metal ester group-containing hydrolyzable polymer (A) can be obtained by dropping a mixed liquid of a chain transfer agent and a solvent and conducting a polymerization reaction.

There is no restriction | limiting in particular as a polymerization initiator which can be used for manufacture of a hydrolysable polymer (A), 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 Examples include '-azobis (2-methylbutyronitrile) [AMBN], 2,2'-azobis (2,4-dimethylvaleronitrile) [ADVN], and tert-butyl peroctoate [TBPO]. 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 hydrolyzable polymer (A) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the monomers.

The chain transfer agent that can be used for the production of the hydrolyzable polymer (A) is not particularly limited, and examples thereof include α-methylstyrene dimer, thioglycolic acid, diterpene, terpinolene, γ-terpinene; tert-dodecyl mercaptan. And mercaptans such as n-dodecyl mercaptan; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as isopropanol and glycerin; and the like. These chain transfer agents may be used individually by 1 type, and may use 2 or more types together.
When a chain transfer agent is used in the production of the hydrolyzable polymer (A), the amount used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the above monomers.

Examples of the solvent that can be used for the production of the hydrolyzable polymer (A) include aromatic solvents such as toluene, xylene, and mesitylene; propanol, butanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like. Examples include 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 number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzable polymer (A) are the viscosity and storage stability of the antifouling coating composition, the dissolution rate (upgradability) of the resulting antifouling coating film, etc. Therefore, it is preferable to adjust appropriately.
The number average molecular weight (Mn) is preferably 1,000 to 100,000, more preferably 1,500 to 30,000. The weight average molecular weight (Mw) is preferably 2,000 to 200,000, more preferably 3,000 to 60,000.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are determined by measuring with gel permeation and converting with standard polystyrene.

A hydrolyzable polymer (A) may be used individually by 1 type, and may use 2 or more types together.
The content of the hydrolyzable polymer (A) in the lower layer antifouling paint composition (x) and the upper layer antifouling paint composition (y) depends on the coating workability of the antifouling paint and the antifouling coating film in the present invention. From the viewpoint of improving the antifouling property, the solid content of the antifouling coating composition is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass. % Or less, more preferably 90% by mass or less, and still more preferably 88% by mass or less.
In the present invention, when the lower layer antifouling coating composition (x) or the upper layer antifouling coating composition (y) contains two or more hydrolyzable polymers (A), the above content is hydrolysable. This is a preferable range as the total content of the polymer (A), and the same applies to each component described later.

When the hydrolyzable polymer (A) has a structural unit derived from the silyl ester group-containing monomer (a11), the solid content of the lower layer antifouling paint composition (x) or the upper layer antifouling paint composition (y) The content of the hydrolyzable polymer (A) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 12 to 40% by mass.
When the hydrolyzable polymer (A) has a structural unit derived from a metal ester group-containing monomer, preferably the monomer (a121) and / or the monomer (a122), the lower layer antifouling paint composition The content of the hydrolyzable polymer (A) in the solid content of the product (x) or the upper layer antifouling coating composition (y) is preferably 10 to 99% by mass, more preferably 15 to 95% by mass, The content is preferably 20 to 90% by mass, and more preferably 25 to 88% by mass.

In the present invention, when the hydrolyzable polymer (A) has a structural unit derived from the polyorganosiloxane block-containing monomer (a21), the slime resistance, which is estimated to be due to the contribution of the polyorganosiloxane block, is increased. It is preferable to increase the content ratio of the hydrolyzable polymer (A) in the antifouling coating film.
In the present invention, when the coating composition contains two or more hydrolyzable polymers (A), the above content is a preferable range as the total content of the hydrolyzable polymer (A), which will be described later. The same applies to each component.

(Polymer (B1))
In the present invention, the lower layer antifouling coating film (X) and the lower layer antifouling coating composition (x) contain a polymer (B1). The lower layer antifouling coating film (X) and the lower layer antifouling coating composition (x) may contain the hydrolyzable polymer (A1) described above in addition to the polymer (B1).
In addition, a polymer (B1) is a polymer which has a structural unit derived from the monomer which has an unsaturated double bond, and is a polymer except the hydrolyzable polymer (A) mentioned above. Therefore, even if it has a structural unit derived from a monomer having an unsaturated double bond, it is derived from the silyl ester group-containing monomer (a11) and / or the metal ester group-containing monomer (a12). The polymer having a structural unit does not correspond to the polymer (B1).
That is, the polymer (B1) does not contain a structural unit derived from the hydrolyzable group-containing monomer (a1).

In the present invention, the polymer (B1) is preferably soluble in the organic solvent (D2) contained in the upper antifouling coating composition (y). In the present invention, “soluble” means that the solubility at 23 ° C. is 1 g / L or more.
More preferably, the polymer (B1) has a solubility in the organic solvent (D2) at 23 ° C. of 10 g / L or more. When such a polymer (B1) is used, the organic antifouling agent (C1) can be efficiently supplied to the upper antifouling coating film (Y) formed from the upper antifouling coating composition (y). Moreover, the interlayer adhesion between the upper antifouling coating film (Y) and the lower antifouling coating film (X) can be improved.

The polymer (B1) is preferably a thermoplastic resin. When the polymer (B1) is a thermoplastic resin, good adhesion to the substrate is obtained, and good solubility in the organic solvent (D2) contained in the upper antifouling coating composition (y) is obtained. Easy to obtain.
Specific examples of such a polymer (B1) include chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene and chlorinated polypropylene; (meth) methyl acrylate copolymers, (meth) ethyl acrylate copolymers. Acrylic resins such as polymers, (meth) propyl acrylate copolymers, (meth) butyl acrylate copolymers, (meth) cyclohexyl cyclohexyl copolymers; vinyl chloride-vinyl acetate copolymers, Vinyl chloride resins (vinyl chloride copolymer) such as vinyl chloride-vinyl propionate copolymer, vinyl chloride-isobutyl vinyl ether copolymer, vinyl chloride-isopropyl vinyl ether copolymer, vinyl chloride-ethyl vinyl ether copolymer; styrene Aromatic petroleum resin; Aliphatic petroleum resin; Urea aldehyde condensation resin; Ketone resin It can gel.

The polymer (B1) preferably contains a structural unit derived from vinyl chloride from the viewpoints of adhesion of the lower antifouling coating film (X) to the substrate and excellent coating properties. Moreover, in addition to the structural unit derived from vinyl chloride, you may have the structural unit derived from vinyl acetate, the structural unit derived from vinyl alcohol, and the structural unit derived from alkyl vinyl ether (for example, isobutyl vinyl ether etc.).
Furthermore, as another preferable aspect of the polymer (B1), a homopolymer or copolymer (hereinafter also referred to as (meth) acrylic polymer) of (meth) acrylic acid and / or (meth) acrylic acid ester. ).
In the present invention, the polymer (B1) may be used singly or in combination of two or more. As a preferred embodiment, the polymer having a structural unit derived from vinyl chloride described above, The combined use of a (meth) acrylic polymer is mentioned.
The weight average molecular weight of the polymer (B1) is preferably in the range of 5,000 to 100,000.

As such a polymer (B1), a commercially available product can be used. For example, “Laroflex MP25” (a copolymer of vinyl chloride and isobutyl vinyl ether) manufactured by BASF, Nissin Chemical Industry Co., Ltd. “Solvine C” (copolymer of vinyl chloride and vinyl acetate), “Solvain AL” (copolymer of vinyl chloride, vinyl acetate, and vinyl alcohol), “Dianal BR-106” manufactured by Mitsubishi Rayon Co., Ltd. (Acrylic copolymer (acrylic resin)) and the like.

In the solid content of the lower layer antifouling coating composition (x), that is, the content of the polymer (B1) in the lower layer antifouling coating film (X), from the viewpoint of the antifouling property and physical properties of the laminated antifouling coating film, The amount is preferably 5 to 90% by mass, more preferably 10 to 50% by mass.
Further, the total content (total content) of the polymer (B1) and the hydrolyzable polymer (A1) in the solid content of the lower layer antifouling coating composition (x), that is, the lower layer antifouling coating film (X). From the viewpoint of antifouling properties and physical properties of the laminated antifouling coating film, it is preferably 1 to 90% by mass, more preferably 5 to 60% by mass, and more preferably 10 to 50% by mass.
The upper antifouling coating composition (y) may optionally contain the polymer (B2), but preferably does not contain the polymer (B2) from the viewpoint of coating film renewability.

(Organic antifouling agent (C1))
In the present invention, the lower antifouling coating film (X) and the lower antifouling coating composition (x) contain an organic antifouling agent (C1).
In this invention, an organic antifouling agent (C1) is a compound which has antifouling property and does not contain a metal element. Note that boron, which is a semimetal, does not correspond to a metal element.
Specific examples of the organic antifouling agent (C1) include 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as tralopyryl), 4,5 -Borane-nitrogen base adducts such as dichloro-2-n-octyl-4-isothiazolin-3-one (also known as DCOIT), pyridinetriphenylborane, 4-isopropylpyridinediphenylmethylborane, (+/-)- 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole (also known as medetomidine), N, N-dimethyl-N ′-(3,4-dichlorophenyl) urea (also known as diuron), N— (2,4,6-trichlorophenyl) maleimide, 2,4,5,6-tetrachloroisophthalonitrile, 2-methylthio-4-tert-butylamino No-6-cyclopropylamino-1,3,5-triazine (also known as sibutrin), chloromethyl-n-octyl disulfide, N, N′-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide ( Also known as: dichlorofluanide), tetraalkylthiuram disulfide (also known as TMTD), 2,3-dichloro-N- (2 ', 6'-diethylphenyl) maleimide, 2,3-dichloro-N- (2'-ethyl) Examples include -6′-methylphenyl) maleimide.
In addition, in the antifouling paint composition or in the antifouling coating film, it does not exclude the case where the organic antifouling agent forms a salt, even if the salt is formed as such. It falls under the organic antifouling agent.

In the present invention, the organic antifouling agent (C1) is soluble in the organic solvent (D2) described later contained in the upper antifouling coating composition (y), that is, the solubility at 23 ° C. is 1 g / The organic antifouling agent (C1) preferably has a solubility in an organic solvent (D2) at 23 ° C. of 10 g / L or more, and more preferably 100 g / L or more.

The organic antifouling agent (C1) preferably contains at least one selected from tralopyril and DCOIT from the viewpoint of imparting excellent antifouling properties to the laminated antifouling coating film, and is particularly antifouling against barnacle species. It is more preferable to contain tralopyril from the viewpoint of improving the odor, and it is preferable to include DCOIT from the viewpoint of improving the antifouling property against slime, which is a cell secretion.

An organic antifouling agent (C1) may be used individually by 1 type, and may use 2 or more types together.
The total content of the organic antifouling agent (C1) in the lower layer antifouling paint composition (x) can be arbitrarily selected according to the efficacy and cost of the compound used, but the antifouling property excellent in the laminated antifouling coating film. From the viewpoint of imparting properties and physical properties, the solid content of the lower layer antifouling coating composition (x) is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and still more preferably 3 to 20% by mass. It is. The content of the organic antifouling agent (C1) in the lower antifouling coating film (X) is the organic content of the upper antifouling coating composition (y) when the upper antifouling coating film (Y) is formed. Fluctuates with dissolution in solvent (D2) and supply of organic antifouling agent (C1) from lower antifouling coating (X) to upper antifouling coating (Y) in the laminated antifouling coating . Therefore, it is most appropriate to define the content of the organic antifouling agent (C1) by the content in the solid content of the lower layer antifouling coating composition (x).

When the lower layer antifouling paint composition (x) contains tralopyril as the organic antifouling agent (C1), from the viewpoint of improving the antifouling properties and coating film properties of the laminated antifouling coating film and interlayer adhesion, The content of is preferably 1 to 30% by mass, more preferably 3 to 20% by mass in the solid content of the lower layer antifouling coating composition (x).
When the lower layer antifouling paint composition (x) contains DCOIT as the organic antifouling agent (C1), from the same viewpoint, the content of DCOIT is determined based on the solid content of the lower layer antifouling paint composition (x). The content is preferably 0.5 to 15% by mass, more preferably 1 to 12% by mass, and still more preferably 2 to 10% by mass.

The upper antifouling coating composition (y) may optionally contain an organic antifouling agent (C2) as long as it does not hinder the problem to be solved by the present invention. When the upper antifouling coating composition (y) contains the organic antifouling agent (C2), the antifouling performance of the laminated antifouling coating film can be further improved. When the upper layer antifouling paint composition (y) contains the organic antifouling agent (C2), the above-mentioned ones can be used. From the viewpoint of resource saving, the upper layer antifouling paint composition (y) The organic antifouling agent (C2) content of the organic antifouling agent (C2) in the upper antifouling coating (Y) is the same as the organic antifouling agent (X) in the lower antifouling coating (X). It is preferable that the amount is lower than the content of C). Moreover, when the upper-layer antifouling paint composition (y) contains an organic antifouling agent (C2), from the viewpoint of preventing precipitates from forming on the surface of the antifouling coating film, the organic antifouling agent (C2 as described above) is used. It is also preferable that substantially no tralopyryl and DCOIT are contained among the compounds of
In the present invention, “the coating composition does not substantially contain the object” means that the concentration of the object in the solid content of the coating composition is less than 0.1% by mass, preferably It is 0.05 mass% or less, More preferably, it is 0.03 mass% or less, More preferably, it is 0.01 mass% or less.

In particular, when the upper-layer antifouling coating composition (y) contains the hydrolyzable copolymer (A2) having a structural unit derived from the silyl ester group-containing monomer (a11), Combined use of borane-nitrogen base adducts such as phenylborane and 4-isopropylpyridinediphenylmethylborane and nitrogen-containing heterocyclic organic antifouling agents such as medetomidine may cause problems such as thickening of coating compositions over time. Therefore, it is particularly preferable that these are not substantially contained.
When the upper layer antifouling paint composition (y) contains the organic antifouling agent (C2), the content thereof is preferably 0.1% by mass to 10% in the solid content of the upper layer antifouling paint composition (y). % By mass, more preferably 0.3% by mass to 5% by mass.

(Organic solvent (D2))
In the present invention, the upper antifouling coating composition (y) is obtained by extracting the organic antifouling agent (C1) from the lower antifouling coating film (X), and the viscosity of the upper antifouling coating composition (y). It is preferable to contain an organic solvent (D2) for the purpose of adjusting. The upper antifouling paint composition (y) may contain the solvent used when preparing the hydrolyzable polymer (A2) as the organic solvent (D2). When mixing A2) and other components as necessary, a separately added solvent may be contained.
In this invention, it is preferable to select what the organic antifouling agent (C1) and polymer (B1) mentioned above are soluble as an organic solvent (D2). In the present invention, “soluble” means that the solubility at 23 ° C. is 1 g / L or more.
The organic solvent (D2) preferably contains an organic antifouling agent (C1) having a solubility at 23 ° C. of 10 g / L or more, more preferably 100 g / L or more.
Moreover, as an organic solvent (D2), it is preferable that the thing in which the solubility in 23 degreeC of a polymer (B1) is 10 g / L or more is included, and it is more preferable that what is 100 g / L or more is included.
The solubility can be determined, for example, by the following method.
After 100 g of the solute for measuring the solubility and 1 L of the solvent are sufficiently stirred in the container to obtain a uniform suspension, the concentration of the medium in the supernatant can be determined by measuring with a measuring method such as HPLC. When the mixture becomes a uniform solution, the solubility is 100 g / L or more.

Organic solvents (D2) include hydrocarbon organic solvents such as xylene, toluene, and ethylbenzene; methyl ethyl ketone, cyclohexanone, 4-methyl-2-pentanone (also known as methyl isobutyl ketone), 2-heptanone (also known as methyl amyl ketone) Ketone organic solvents such as ethanol; aliphatic organic solvents such as ethanol, isopropyl alcohol, n-butanol, isobutanol, propylene glycol monomethyl ether, ethylene glycol, etc. (carbon number 1 to 10, preferably 2 to 5); acetic acid Examples include ester organic solvents such as ethyl, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate. From the viewpoints of volatilization rate, ease of handling, availability of raw materials, etc., xylene, n- Butanol, isobutanol, propylene Glycol monomethyl ether acetate n- butyl, isobutyl acetate, 2-heptanone is preferred.

As the organic solvent (D2) contained in the upper antifouling coating composition (y), the organic antifouling agent (C1) contained in the lower antifouling coating (X) to the upper antifouling coating (Y) is used. From the viewpoint of making the supply effective, the above-mentioned ester organic solvent or ketone organic solvent is preferably contained, and an ester organic solvent is more preferably contained.
When the upper layer antifouling paint composition (y) contains an ester organic solvent or a ketone organic solvent as the organic solvent (D2), the content thereof is 1 to 50 in the upper layer antifouling paint composition (y). The mass is preferably 2, and more preferably 2 to 30% by mass.

The organic antifouling agent (C1) contained in the lower antifouling coating film (X) is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as : Tralopyril), in addition to the above-mentioned viewpoint, from the viewpoint of supply of tralopyril to the upper antifouling coating film (Y), in particular, an alcohol organic solvent, an ester organic solvent or a ketone organic solvent as described above is used. In particular, from the viewpoint of reducing the viscosity of the upper antifouling coating composition (y) and facilitating coating workability, it is preferable to include an ester organic solvent. When the lower layer antifouling coating film (X) contains tralopyril and the upper layer antifouling coating composition (y) contains an alcohol organic solvent, an ester organic solvent or a ketone organic solvent, the content is the upper antifouling agent. The content in the coating composition (y) is preferably 2 to 50% by mass, and more preferably 5 to 30% by mass.

An organic solvent (D2) may be used individually by 1 type, and may use 2 or more types together.
In the present invention, the organic solvent (D2) contained in the upper antifouling coating composition (y) is an organic antifouling agent (C1) contained in the lower antifouling coating film (X) and the lower antifouling coating composition (x). ) Is preferably soluble. Here, the organic solvent (D2) is soluble in the organic antifouling agent (C1). When the organic solvent (D2) contains two or more organic solvents, (i) the organic solvent (D2) Among them, the organic compound contained in the upper antifouling coating composition (y), which is soluble in an organic solvent having the largest content (mass%), or (ii) is a mixed liquid of two or more organic solvents It means satisfy | filling at least any one of being soluble with respect to the whole solvent (D2). As described above, “soluble” means that the solubility at 23 ° C. is 1 g / L or more, preferably 10 g / L or more, and more preferably 100 g / L or more. preferable.

In the present invention, the content of the organic solvent (D2) in the upper-layer antifouling coating composition (y) is selected from the viewpoints of coating workability of the upper-layer coating composition (y), drying properties of the coating film, environmental discharge, and the like. From the viewpoint of supplying the organic antifouling agent (C1) from the lower antifouling coating film (X) into the upper antifouling coating film (Y), preferably 5 to 90% by mass, more preferably 10 to 90% by mass, The amount is preferably 20 to 80% by mass, and more preferably 40 to 70% by mass.

In the present invention, the lower layer antifouling paint composition (x) may also contain an organic solvent (D1). Examples of the organic solvent (D1) are the same as the organic solvent (D2) contained in the upper antifouling coating composition (y).
Further, the content of the organic solvent (D1) in the lower layer antifouling coating composition (x) is preferably 5 to 90% by mass, more preferably 10 to 70% by mass.

(Other ingredients)
In the present invention, the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) may contain other components in addition to the components described above.
[Other antifouling agents (E)]
The coating composition of the present invention may further contain another antifouling agent (E) for the purpose of further improving the antifouling property of the coating film to be formed. In the present invention, the other antifouling agent (E) is an antifouling agent other than the organic antifouling agent (C), and contains a metal element. The organic antifouling agent (C) and the other antifouling agent (E) are also collectively referred to as an antifouling agent.
As described above, the laminated antifouling coating film of the present invention exhibits excellent antifouling properties by optimal use of the organic antifouling agent (C1) derived from the lower antifouling coating film (X). When the coating composition (y) contains the other antifouling agent (E), the antifouling performance can be further improved. In one aspect, the present invention can reduce such an antifouling agent that is originally required to obtain an antifouling performance that can cope with a highly fouling environment. The effect that emission can be reduced can be obtained.
Moreover, when the lower layer coating composition (x) contains the other antifouling agent (E), the coating film exhibits good antifouling properties in a situation where the coating film needs antifouling properties.

Other antifouling agents (E) include, for example, cuprous oxide, copper oxide, copper (metal copper), copper thiocyanate (also known as rhodan copper), copper pyrithione and zinc pyrithione, and other metal pyrithions, bisdimethyldithiocarbamoyl Zinc ethylene bisdithiocarbamate (also known as polycarbamate), zinc dimethyldithiocarbamate (also known as diram), zinc ethylene bisdithiocarbamate, etc. It is preferable to do.
Of these, the average particle size of cuprous oxide is preferably about 0.1 to 30 μm for exhibiting long-term antifouling properties, and the surface is made of glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil, etc. What is processed is preferable in terms of long-term stability during storage. Examples of such commercially available cuprous oxide include NC-301 (manufactured by NC Tech Co., Ltd.), NC-803 (manufactured by NC Tech Co., Ltd.), Red Copp 97N Premium (manufactured by AMERICA CHEMET Co.), Purple. Examples include Copp (manufactured by AMERICA CHEMET Co.) and LoLoTint 97 (manufactured by AMERICA CHEMET Co.).

In addition, antifouling agent (E) may be used individually by 1 type, and may use 2 or more types together.
In the present invention, when the antifouling coating composition contains other antifouling agent (E), the total content thereof can be arbitrarily selected from the viewpoint of the effect of the compound used and the availability, but the laminate to be formed From the viewpoint of improving the antifouling property and physical properties of the antifouling coating film and reducing the environmental load, it is preferably 0.1 to 90% by mass in the solid content of each antifouling coating composition.
When the lower layer antifouling coating composition (x) or the upper layer antifouling coating composition (y) contains cuprous oxide or rhodan copper, the total content is preferably in the solid content of each coating composition. Is 10 to 80% by mass, more preferably 30 to 70% by mass.
When the lower layer antifouling coating composition (x) or the upper layer antifouling coating composition (y) contains zinc pyrithione or copper pyrithione, respectively, the total content is preferably in the solid content of each coating composition. 0.5 to 30% by mass, more preferably 1 to 20% by mass.

[Other pigments (F)]
The coating composition of the present invention contains other pigments (F) other than the antifouling agent for the purpose of coloring the coating film and concealing the base, and for the purpose of adjusting to an appropriate coating film strength. Also good.
Other pigments (F) include, for example, zinc oxide, talc, mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, sulfide. Examples include extender pigments such as zinc, and colored pigments such as petals (red iron oxide), titanium white (titanium oxide), yellow iron oxide, carbon black, naphthol red, and phthalocyanine blue, including zinc oxide and talc. Is preferred. These other pigments (F) may be used alone or in combination of two or more.
When the coating composition of the present invention contains other pigment (F), the content is determined by the hiding property required for the antifouling coating film to be formed and the viscosity of the antifouling coating composition. However, it is preferably 1 to 60% by mass in the solid content of the coating composition.

[Monocarboxylic acid compound (G)]
The coating composition of the present invention may contain a monocarboxylic acid compound (G).
In the present invention, the monocarboxylic acid compound (G) improves the renewability of the formed coating film from the surface in water, and when the coating film contains an antifouling agent, It promotes release into water to enhance the antifouling property of the coating film, and also has a function of imparting appropriate water resistance to the coating film.
Examples of the monocarboxylic acid compound (G) include, when the monocarboxylic acid compound is represented by R—COOH, R is a saturated or unsaturated aliphatic hydrocarbon group having 10 to 40 carbon atoms, or 3 carbon atoms. It is preferably a ˜40 saturated or unsaturated alicyclic hydrocarbon group or a substituted product thereof.

Specifically, abietic acid, neoabietic acid, dehydroabietic acid, parastrinic acid, isopimaric acid, pimaric acid, trimethylisobutenylcyclohexene carboxylic acid, versatic acid, stearic acid, naphthenic acid and the like are preferable.
Also preferred are rosins whose main components are abietic acid, parastrinic acid, isopimaric acid and the like. Examples of rosins include rosins such as gum rosin, wood rosin and tall oil rosin, hydrogenated rosin, disproportionated rosin, rosin derivatives such as rosin metal salts, and pine tar.
Examples of trimethylisobutenylcyclohexene carboxylic acid include 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) The main component (85% by mass or more) of cyclohex-3-ene-1-carboxylic acid.

A part or all of the monocarboxylic acid compound (G) in the present invention may form a metal ester. Examples of the metal ester include zinc ester and copper ester. The metal ester may be formed in advance before the preparation of the coating composition or may be formed by reaction with other coating components at the time of preparing the coating composition.

Monocarboxylic acid compound (G) and / or its metal ester may be used individually by 1 type, and may use 2 or more types together.
When the coating composition of the present invention contains the monocarboxylic acid compound (G) and / or a metal ester thereof, the content is determined from the viewpoint of coating workability of the coating composition and water resistance of the antifouling coating film. The amount is preferably 0.1 to 50% by mass, more preferably 1 to 20% by mass in the solid content of the composition.

[Dehydrating agent (H)]
The coating composition of the present invention may contain a dehydrating agent (H) for the purpose of improving its storage stability. Examples of the dehydrating agent (H) include synthetic zeolite, anhydrous gypsum (calcium sulfate) and hemihydrate gypsum (also called calcined gypsum) as inorganic dehydrating agents, and tetramethoxysilane and tetraethoxysilane as organic dehydrating agents. Examples thereof include alkoxysilanes such as tetrabutoxysilane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and trimethylethoxysilane or condensates thereof, and orthoformate alkyl esters such as methyl orthoformate and ethyl orthoformate. . A dehydrating agent (H) may be used individually by 1 type, and may use 2 or more types together.
When the coating composition of the present invention contains a dehydrating agent (H), the content thereof is preferably 0.1 to 20% by mass in the solid content of the coating composition, more preferably 0.00. The amount is 2 to 15% by mass.

[Plasticizer (I)]
The 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 coating composition of the present invention contains the plasticizer (I), the content thereof is preferably 0.1 to 10% by mass in the solid content of the coating composition, more preferably 0. The amount is 5 to 10% by mass. When the content of the plasticizer (I) is within the above range, the plasticity of the coating film can be kept good.

[Anti-sagging agent, anti-settling agent (J)]
The coating composition of the present invention may contain an anti-sagging agent / anti-settling agent (J) for the purpose of adjusting the viscosity of the coating composition.
Anti-sagging agents and anti-settling agents (J) include organic clay waxes (such as Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonates), organic waxes (polyethylene wax, polyethylene oxide wax, amide). Waxes, polyamide waxes, hydrogenated castor oil waxes, etc.), mixtures of organic clay waxes and organic waxes, synthetic finely divided silica and the like.
Commercially available products may be used as the anti-sagging agent / anti-settling agent (J), such as “DISPARON 305”, “DISPARON 4200-20”, “DISPARON A630-20X”, “DISPARON” manufactured by Enomoto Kasei Co., Ltd. 6900-20X "," ASA D-120 "manufactured by Ito Oil Co., Ltd., and the like.

The anti-sagging agent / anti-settling agent (J) may be used alone or in combination of two or more.
When the coating composition of the present invention contains an anti-sagging agent / anti-settling agent (J), the content thereof is preferably 0.1 to 10% by mass in the solid content of the coating composition, More preferably, the amount is 0.2 to 5% by mass.

[Binder component (K)]
The coating composition of the present invention may contain a binder component (K) for the purpose of imparting water resistance, crack resistance and strength to the antifouling coating film to be formed.
Examples of the binder component (K) include chlorinated paraffins, n-paraffins, polyester polymers, terpene phenol resins, petroleum resins, and ketone resins. Among these, chlorinated paraffin, polyester polymer, and petroleum resins are preferable.
A binder component (K) may be used individually by 1 type, and may use 2 or more types together.

The chlorinated paraffin may have a linear or branched molecular structure, and may be liquid or solid (eg, powder) at room temperature (eg, 23 ° C.).
The chlorinated paraffin preferably has an average carbon number of 8 to 30 and more preferably 10 to 26 in one molecule. An antifouling coating composition containing such a chlorinated paraffin can form an antifouling coating film with less cracks and peeling. In addition, when the said average carbon number is less than 8, the effect which suppresses generation | occurrence | production of a crack in a coating film may be insufficient.
The viscosity (unit poise, measurement temperature 25 ° C.) of the chlorinated paraffin is preferably 1 or more, more preferably 1.2 or more, and the specific gravity (25 ° C.) is preferably 1.05 to 1.80 g. / Cm ³ , more preferably 1.10 to 1.70 g / cm ³ .
The chlorination rate (chlorine content) of the chlorinated paraffin is usually 35 to 70 parts by mass, preferably 35 to 65 parts by mass when the chlorinated paraffin is 100 parts by mass. A coating composition containing a chlorinated paraffin having such a chlorination rate can form a coating film with few cracks, cracks, and the like.

The polyester polymer is obtained by reaction of one or more polyhydric alcohols with one or more polyvalent carboxylic acids and / or anhydrides thereof, and optionally other components, and uses any kind in any amount. The hydroxyl value / acid value and viscosity can be adjusted by the combination.
Examples of the polyhydric alcohol include propylene glycol, glycerin, ethylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane (TMP), pentaerythritol, sorbitol; polyalkylene glycols such as diethylene glycol; Among them, propylene glycol, ethylene glycol, neopentyl glycol, glycerin, and TMP are preferable because of easy availability of raw materials. These polyhydric alcohols may be used in combination of two or more.
Examples of the polyvalent carboxylic acid and / or anhydride thereof include malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and 1,9-nonamethylenedicarboxylic acid. Acid, 1,10-decamethylene dicarboxylic acid, 1,11-undecamethylene dicarboxylic acid, 1,12-dodecamethylene dicarboxylic acid, cyclohexane dicarboxylic acid, decahydronaphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, hexa Examples include hydrophthalic acid, succinic acid, and the like, and anhydrides thereof, and phthalic anhydride, adipic acid, isophthalic acid, and hexahydrophthalic anhydride are preferable.
The polyester polymer preferably has a solid content hydroxyl value of 50 to 150 mgKOH / g, and 80 to 120 mgKOH from the viewpoint of imparting storage stability of the coating composition, antifouling property of the coating film, and appropriate hydrophilicity. / G is more preferable.
The polyester polymer may be dissolved in a solvent and used as a solution (hereinafter also referred to as a polyester polymer solution). As the solvent, those mentioned as the organic solvent (D2) can be used.
The viscosity of the polyester polymer solution is preferably 3,000 mPa · s or less, more preferably 1,000 mPa · s or less at 25 ° C., from the viewpoint of reducing the viscosity of the coating composition.
The polyester polymer solution may contain unreacted raw materials.
Examples of the petroleum resins include C5 series, C9 series, styrene series, dichloropentadiene series, and hydrogenated products thereof.

Commercially available products may be used as the binder component (K). For example, as the chlorinated paraffin, Toyoparax C-70 / A-50 / A-70 / A-145 / A-150 / manufactured by Tosoh Corporation 150 ”etc., as the polyester polymer,“ Tesrack 2474 ”manufactured by Hitachi Chemical Co., Ltd., and as the petroleum resins,“ Quinton 1500 ”and“ Quinton 1700 ”(all manufactured by Nippon Zeon Co., Ltd.) And the like.
When the coating composition of the present invention contains the binder component (K), the content thereof is preferably 0.1 to 10% by mass in the solid content of the coating composition.

[Epoxy resin (L)]
The coating composition of the present invention, particularly the lower layer antifouling coating composition (x), may contain an epoxy resin (L).
The epoxy resin (L) is a reactive curable resin that has two or more epoxy groups in one molecule and can be cured by reaction with a curing agent.
The epoxy resin (L) also functions as a stabilizer by trapping chlorine when the vinyl chloride polymer is contained as the polymer (B1) in the lower layer antifouling paint composition (x).
Examples of the epoxy resin (L) include a bisphenol type, a novolac type, and an aliphatic type, and a bisphenol type epoxy resin is preferable from the viewpoint of workability and rust prevention.
The bisphenol type epoxy resin preferably has an epoxy equivalent of 160 to 500, and more preferably 180 to 500.

Examples of such bisphenol type epoxy resins include bisphenol A type and bisphenol F type epoxy resins, dimer acid-modified and polysulfide-modified bisphenol type epoxy resins, and hydrogenated products of these bisphenol type epoxy resins. Among these, bisphenol A type epoxy resins are preferable.
Examples of the bisphenol A type epoxy resin include bisphenol A diglycidyl ether, bisphenol A polypropylene oxide diglycidyl ether, bisphenol A ethylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A propylene oxide diglycidyl ether. Examples of the bisphenol A type diglycidyl ether include bisphenol F type diglycidyl ether such as bisphenol F diglycidyl ether.

As a commercial product of bisphenol A type epoxy resin, “jER 828” manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 184 to 194, viscosity 12,000 to 15,000 mPa · s / 25 ° C., solid content is liquid at normal temperature) , “JER 834-90X” (epoxy equivalent 230-270, solid content is semi-solid at normal temperature), “jER 1001-75X” (epoxy equivalent 450-500, solid content is solid at normal temperature), etc. it can.

These epoxy resins may be used alone or in combination of two or more.
In the present invention, when the lower layer antifouling paint composition (x) contains the epoxy resin (L), the content thereof is the antifouling property, anticorrosive property, curability, coating film physical property, etc. of the laminated antifouling coating film. From the viewpoint of improvement, the solid content of the lower layer antifouling coating composition (x) is preferably 1 to 60% by mass, and more preferably 3 to 50% by mass.
In the present invention, when the lower antifouling coating film (X) requires antifouling performance, it is preferable that the epoxy resin (L) is not practically contained from the viewpoint of improving the antifouling property.
The upper-layer antifouling coating composition (y) of the present invention may also contain an epoxy resin (L), but is preferably not substantially contained from the viewpoint of antifouling properties and renewability of the coating film.

[Curing agent for epoxy resin (M)]
The coating composition of the present invention, especially the lower layer antifouling coating composition (x), may contain an epoxy resin curing agent (M), and when the coating composition contains the epoxy resin (L). It is preferable to contain the epoxy resin curing agent (M).
When the coating composition contains both the epoxy resin (L) and the epoxy resin curing agent (M), the epoxy resin (L) and the epoxy resin curing agent (M) are cured to form a coating film. Good coating film physical properties and adhesion to the substrate can be imparted.
When the coating composition contains both the epoxy resin (L) and the epoxy resin curing agent (M), the coating composition is preferably prepared as a multi-component kit containing them in different components. It is preferable to use the composition after mixing immediately before use.

Examples of the epoxy resin curing agent (M) include amine-based curing agents, mercapto-based curing agents, acid anhydride-based curing agents, etc., which have good reactivity at room temperature and are easy to handle. A curing agent is usually used. Examples of the amine curing agent include bifunctional or higher amines such as aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines, and modified products thereof.
Examples of the aliphatic amine include diethylenetriamine, dipropylenetriamine, tetraethylenepentamine, bis (cyanoethyl) diethylenetriamine, bishexamethylenetriamine, and m-xylylenediamine (MXDA).
Examples of the alicyclic amines include 4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, norbornanediamine (NBDA / 2,5- and 2,6-bis (aminomethyl) -bicyclo [2,2, 1) heptane), isophoronediamine (IPDA / 3-aminomethyl-3,5,5-trimethylcyclohexylamine) and the like.
Examples of the aromatic amine include phenylenediamine, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, and the like.
Examples of the heterocyclic amine include N-methylpiperazine.
Examples of modified amines include polyamides of amines and modified products thereof, epoxy adducts to which an epoxy compound is added, Mannich modified products, and the like, and epoxy adducts from the viewpoint of curability of coating compositions. Polyamide and modified products thereof are preferable in terms of corrosion resistance and adhesion.

The active hydrogen equivalent of such an amine curing agent is preferably 40 to 1,000 g / eq, more preferably 80 to 600 g / eq, from the viewpoint of the balance between curability and adhesion of the coating composition. .
Specific examples of the amine curing agent include polyamides such as “RACAMIDE N-153”, “RACAMIDE TD-966” manufactured by DIC Corporation, and “SANMIDE 315” manufactured by Sanwa Chemical Industry Co., Ltd. As a modified product of polyamide, “PA-23” manufactured by Akira Otake Shin Chemical Co., Ltd., which is an epoxy adduct obtained by adding an epoxy compound to polyamide, “ADEKA” manufactured by ADEKA, a modified Mannich product of modified polyamide. Hardener EH-350 "and the like.

These epoxy resin curing agents (M) may be used singly or in combination of two or more.
When the coating composition contains an epoxy resin (L) and a curing agent for epoxy resin (M), and an amine curing agent is used as the curing agent for epoxy resin (M), the epoxy resin (L) has an epoxy. An amount such that the equivalent ratio of the component to the amine component (epoxy equivalent: active hydrogen equivalent) is preferably 1: 0.25 to 1: 0.9, more preferably 1: 0.3 to 1: 0.8 It is preferable to use in. When the curing agent for epoxy resin (M) is used in such an amount, there is a tendency that a coating film excellent in drying property, corrosion resistance, and upper layer compatibility can be obtained. In other words, in the present invention, the curing agent for epoxy resin (M) is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the epoxy resin in the coating composition. Used in the amount of.
The upper layer antifouling paint composition (y) of the present invention may also contain an epoxy resin curing agent (M), but it is preferably not substantially contained from the viewpoint of the antifouling property of the coating film.

[Curing accelerator for epoxy resin (N)]
The coating composition of the present invention, particularly the lower layer antifouling coating composition (x), may contain an epoxy resin curing accelerator (N), and the coating composition is used for the epoxy resin (L) and the epoxy resin. When the curing agent (M) is contained, it is preferable that the curing accelerator for epoxy resin (N) is contained because the coating film exhibits good curability even at a low temperature.
The epoxy resin curing accelerator (N) includes tertiary amine compounds such as tri (dimethylaminomethyl) phenol (TAP), diazabicycloundecene (DBU), diazabicyclononene (DBN); 2-ethyl- Examples include imidazole compounds such as 4-methylimidazole; compounds such as phosphine and phosphonium salt compounds. Among them, tertiary amine compounds are preferable and TAP is more preferable from the viewpoint of reaction acceleration and availability.
When the coating composition contains the epoxy resin curing agent (M) and the epoxy resin curing accelerator (N), the epoxy resin curing accelerator (N) is 100 masses of the epoxy resin curing agent (M). From the viewpoint of curability of the coating composition and coating workability, it is preferably contained in an amount of 1 to 10% by mass relative to%.
The upper-layer antifouling coating composition (y) of the present invention may also contain an epoxy resin curing accelerator (N), but is preferably not substantially contained from the viewpoint of the antifouling property of the coating film.

(Production method of lower layer antifouling paint composition (x) and upper layer antifouling paint composition (y))
The lower-layer antifouling paint composition (x) and the upper-layer antifouling paint composition (y) of the present invention can be prepared using the same devices and means as those of known general paints, respectively.
Specifically, in the case of the upper-layer antifouling coating composition (y), after preparing the hydrolyzable polymer (A2), the solution of the hydrolyzable polymer (A2) and the organic solvent (D2), and If necessary, other additive components can be added at once or sequentially, and stirred and mixed to produce.

(Preferable combination of lower layer antifouling paint composition (x) and upper layer antifouling paint composition (y))
In the present invention, the lower layer antifouling paint composition (x) and the upper layer antifouling paint composition (y) may be any of the following aspects (i) to (viii). Further, the lower layer antifouling paint composition (x) or the upper layer antifouling paint composition (y) has a hydrolyzable polymer (A) having a structural unit derived from a silyl ester group-containing monomer. You may contain both the polymer and the hydrolyzable polymer which has a structural unit derived from a metal ester group containing monomer.
(I) The lower layer antifouling coating composition (x) does not contain a hydrolyzable polymer (A1).
(Ii) The lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) contain a hydrolyzable polymer (A), and both the hydrolyzable polymer (A) are silyl It has a structural unit derived from the ester group-containing monomer (a11).
(Iii) The lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) contain a hydrolyzable polymer (A), and both the hydrolyzable polymer (A) are metal It has a structural unit derived from the ester group-containing monomer (a12).
(Iv) The lower layer antifouling coating composition (x) contains the hydrolyzable polymer (A1), and the hydrolyzable polymer (A1) is derived from the silyl ester group-containing monomer (a11). The hydrolyzable polymer (A2) having a structural unit and contained in the upper antifouling paint composition (y) has a structural unit derived from the metal ester group-containing monomer (a12).
(V) The lower layer antifouling coating composition (x) contains the hydrolyzable polymer (A1), and the hydrolyzable polymer (A1) is derived from the metal ester group-containing monomer (a12). The hydrolyzable polymer (A2) having a structural unit and contained in the upper antifouling paint composition (y) has a structural unit derived from the silyl ester group-containing monomer (a11).

The lower-layer antifouling paint composition (x) and the upper-layer antifouling paint composition (y) have particularly preferred embodiments described in the following (vi) to (viii).
(Vi) The lower layer antifouling coating composition (x) is used as an organic antifouling agent (C1) as 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbohydrate. The hydrolyzable polymer (A2) containing the nitrile and contained in the upper antifouling coating composition (y) has a structural unit derived from the metal ester group-containing monomer (a12).
(Vii) The lower-layer antifouling paint composition (x) contains 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one as the organic antifouling agent (C1), and the upper-layer antifouling paint The hydrolyzable polymer (A2) contained in the composition (y) has a structural unit derived from the metal ester group-containing monomer (a12).
(Viii) The lower-layer antifouling paint composition (x) contains 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one as the organic antifouling agent (C1), and the upper-layer antifouling paint The hydrolyzable polymer (A2) contained in the composition (y) has a structural unit derived from the silyl ester group-containing monomer (a11).

In any of the above aspects, as described above, from the viewpoint of suppressing the appearance defect of the upper antifouling coating film (Y), the upper antifouling coating composition (y) substantially contains the organic antifouling agent (C2). It is preferable not to contain, and it is more preferable not to contain.

(Method for producing substrate with laminated antifouling coating)
The manufacturing method of a base material with a laminated antifouling coating film comprises a step of applying a lower antifouling coating composition (x) on a base material to form a lower antifouling coating film (X), and a lower antifouling coating film (X) It has the process of apply | coating upper-layer antifouling-coating composition (y), and forming an upper-layer antifouling coating film (Y).
As the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y), the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y) described above are used.

It does not specifically limit as a method of apply | coating a lower layer antifouling paint composition (x) on a base material, What is necessary is just to apply | coat on a base material by well-known methods, such as the method of using a brush, a roller, and a spray.
The applied lower layer antifouling coating composition (x) is dried and / or cured to form the lower layer antifouling coating film (X). The lower layer antifouling coating composition (x) applied by the above-mentioned method is dried and / or left by standing, for example, at 25 ° C., preferably for about 1 hour to 14 days, more preferably for about 1 to 7 days. It hardens | cures and can obtain a lower layer antifouling coating film (X). The lower layer antifouling paint composition (x) may be dried and / or cured while blowing with heating.

The thickness of the lower antifouling coating film (X) is arbitrarily selected according to the anticorrosion performance required for the lower antifouling coating film (X), the coating film strength, the period of use, etc., preferably 10 to 1, Although it is about 000 μm, it is more preferably 50 to 400 μm, still more preferably 70 to 200 μm, from the viewpoint of the antifouling property of the laminated antifouling coating film, ease of coating film formation, and resource saving.
As a method of producing the lower layer antifouling coating film (X) having the above-mentioned thickness, the lower layer antifouling coating composition (x) is preferably applied at a thickness of 10 to 300 μm per application, The method of apply | coating several times is mentioned. In addition, when the lower layer antifouling paint composition (x) is applied a plurality of times to form the lower layer antifouling coating film (X), two or more layers having different compositions are laminated as the lower layer antifouling paint composition (x). May be.

In addition, the base material to which the lower layer antifouling paint composition (x) is applied may have a surface on which a coating film such as a primer layer has already been formed, and surface roughening treatment such as sandblasting treatment may be performed. The kind of coating film which the lower layer antifouling coating film (X) is in direct contact with is not particularly limited.

In the method for producing a substrate with a laminated antifouling coating film of the present invention, an upper antifouling coating composition (y) is applied on the lower antifouling coating film (X) formed on the substrate, and an upper layer is formed. It has the process of forming an antifouling coating film (Y).
The method for applying the upper antifouling paint composition (y) is not particularly limited, and can be applied by the same method as the method for applying the lower antifouling paint composition (x) described above. The dirty paint composition (y) can form an upper antifouling coating film (Y) by drying. There are no particular restrictions on the drying conditions of the upper antifouling paint composition (y), but drying under conditions having a period exceeding 0 ° C. from the application of the upper antifouling paint composition (y) to its use is preferred. Further, drying under conditions having a period exceeding 10 ° C. is more preferable. Under such drying conditions, the laminated antifouling coating film can exhibit good appearance, physical properties, and antifouling properties.
The upper layer antifouling coating composition (y) is dried, for example, under conditions of an average temperature of 25 ° C., usually for 1 hour to 14 days, preferably about 1 to 7 days. You may go while doing it.

Prior to the application of the upper antifouling paint composition (y), the lower antifouling coating film (X) may be subjected to a pretreatment such as a roughening treatment with sandpaper or the like, or a surface washing with high-pressure water washing or the like. As long as the above requirements are satisfied, the upper antifouling coating (Y) of the laminated antifouling coating of the present invention is exhausted and exposed to the lower antifouling coating (X), and the antifouling purpose already in the sea On the antifouling coating film used for a certain period of time, an upper antifouling coating composition (y) may be further applied to form a laminated antifouling coating film.

The thickness of the upper antifouling coating film (Y) is arbitrarily selected according to the renewal speed of the upper antifouling coating film (Y), the period of use, etc., but is preferably about 40 to 1,500 μm. From the viewpoint of the antifouling property of the laminated antifouling coating film, the strength of the coating film, and the ease of forming the coating film, it is more preferably 60 to 800 μm, still more preferably 80 to 600 μm. As a method for producing a coating film of this thickness, the upper antifouling coating composition (y) is preferably 30 to 500 μm, more preferably 50 to 200 μm, once to multiple times per application. The method of apply | coating twice is mentioned.

The substrate with a laminated antifouling coating film of the present invention is produced by forming the laminated antifouling coating film on the substrate by the method as described above.
The laminated antifouling coating film of the present invention can be used for maintaining the antifouling property of a substrate over a long period of time in a wide range of industrial fields such as ships, fisheries, and marine structures. Examples of such base materials include ships (container ships, large steel ships such as tankers, fishing boats, FRP ships, wooden ships, yachts, etc. hull outer plates, new ships or repair ships, etc.), fishing materials (ropes, fishing nets, etc.) , Fishing gear, floats, buoys, etc.) and offshore structures such as mega floats. Among these, the base material is preferably selected from the group consisting of ships, underwater structures, and fishing gear, more preferably selected from the group consisting of ships and underwater structures, and is further a ship. preferable.

[Anti-fouling method, paint kit for forming laminated anti-fouling coating film, and upper anti-fouling paint composition]
The antifouling method of the present invention uses the above-mentioned laminated antifouling coating film, and is a method of preventing fouling by providing the laminated antifouling coating film of the present invention on various substrates.
The coating kit for forming a laminated antifouling coating film of the present invention includes at least the lower antifouling coating composition (x) and the upper antifouling coating composition (y) described above. The coating kit for forming a laminated antifouling coating film of the present invention combines a primer layer forming coating composition and the like in addition to the lower layer antifouling coating composition (x) and the upper layer antifouling coating composition (y). A kit comprising three or more coating compositions may be used.
Furthermore, the upper antifouling coating composition of the present invention is the above-described upper antifouling coating composition (y), which is formed on the lower antifouling coating film (X) formed by the lower antifouling coating composition (x). It is suitably used for forming an upper antifouling coating film (Y).

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. Hereinafter, unless otherwise specified, “part” means part by mass.
The “solid content” of each component used in the examples refers to a component excluding volatile components contained in each component as a solvent, and is obtained by drying each component in a hot air dryer at 125 ° C. for 1 hour. It is a thing.

[Production of hydrolyzable polymer (A)]
<Production Example 1: Production of hydrolyzable polymer solution (A-1)>
In a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen inlet tube, and heating / cooling jacket, 43 parts by mass of xylene, 10 parts by mass of triisopropylsilyl methacrylate, KF-2001 (manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass were charged and heated and stirred under a temperature of 80 ± 5 ° C. under a nitrogen stream. While maintaining the same temperature, 50 parts by mass of triisopropylsilyl methacrylate, 8 parts by mass of KF-2001 (manufactured by Shin-Etsu Chemical Co., Ltd.), 25 parts by mass of 2-methoxyethyl methacrylate, methyl methacrylate are added to the reaction vessel from the dropping device. A mixture consisting of 5 parts by mass and 2.0 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) was added dropwise over 2 hours. Thereafter, after stirring at the same temperature for 2 hours, 0.4 part by mass of AIBN was further added, the temperature was raised to 105 ° C. over 3 hours, 24 parts by mass of xylene was added, and colorless and transparent hydrolyzable A polymer solution (A-1) was obtained.
The composition of the monomer mixture used and the characteristic values of the hydrolyzable polymer solution (A-1) are shown in Table 1.

<Production Examples 2 to 4: Production of hydrolyzable polymer solutions (A-2) to (A-4)>
The hydrolyzable polymer solution was prepared in the same manner as in Production Example 1 except that the charge ratio of the monomer mixture used in Production Example 1, the type and amount of the polymerization initiator used at the time of dropping, and the charge order were appropriately adjusted. (A-2) to (A-4) were prepared.
Table 1 shows the composition of the monomer mixture used and the characteristic values of the hydrolyzable polymer solutions (A-2) to (A-4) and the polymers contained therein measured by the method described below.

Each component in Table 1 is as follows.
* 1 KF-2001: manufactured by Shin-Etsu Chemical Co., Ltd., side chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent = 1,900 g / mol
* 2 FM-0711 manufactured by JNC, one-end methacryloyloxyalkyl-modified organopolysiloxane, number average molecular weight Mn = 1,000

The viscosity of the obtained polymer solutions (A-1) to (A-4) and the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymers contained therein are measured 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 the weight average molecular weight (Mw) of the polymer were measured using GPC (gel permeation chromatography) under the following conditions.
GPC conditions Equipment: “HLC-8120GPC” (manufactured by Tosoh Corporation)
Column: “Super H2000 + H4000” (manufactured by 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 production example for dehydration, and the filtrate obtained by filtration through a membrane filter was used as a GPC measurement sample.

<Production Examples 5 to 8: Hydrolyzable polymer solutions (A-5) to (A-8)>
[Production Example M1: Production of metal ester group-containing monomer mixture (a12-1)]
A four-necked flask equipped with a cooler, thermometer, dropping funnel and stirrer was charged with 85.4 parts of PGM (propylene glycol monomethyl ether) and 40.7 parts of zinc oxide, and the temperature was raised to 75 ° C. while stirring. . Subsequently, a mixture consisting of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid and 5 parts of water was dropped from the dropping funnel at a constant rate over 3 hours. Further, after stirring for 2 hours, 36 parts of PGM was added to obtain a transparent metal ester group-containing monomer mixture (a12-1). The solid content was 44.8% by mass.

[Production Example M2: Production of metal ester group-containing monomer mixture (a12-2)]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 60 parts of xylene, 13 parts of PGM, and 40.7 parts of zinc oxide, and the temperature was raised to 75 ° C. while stirring. Subsequently, a mixture consisting of 32.3 parts of methacrylic acid, 27 parts of acrylic acid, 37.7 parts of oleic acid, 2.3 parts of acetic acid, and 5.8 parts of propionic acid was dropped from the dropping funnel at a constant rate over 3 hours. After further stirring for 2 hours, 77 parts of xylene and 46 parts of PGM were added to obtain a metal ester group-containing monomer mixture (a12-2). The solid content was 39.6%.

<Production Example 5: Production of hydrolyzable polymer solution (A-5)>
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of PGM, 65 parts of xylene, and 4 parts of ethyl acrylate, and heated to 100 ° C. while stirring. Subsequently, from the dropping funnel, 32.3 parts of methyl methacrylate, 13.9 parts of ethyl acrylate, 40 parts of FM-0711 (trade name, manufactured by JNC Corporation), a metal ester group-containing monomer mixture described in Production Example M1 ( a12-1) 21.7 parts, xylene 10 parts, chain transfer agent (manufactured by NOF Corporation, NOFMER MSD (trade name), α-methylstyrene dimer) 1.2 parts, AIBN 2.5 parts, 2, 2 A transparent mixture composed of 0.8 part of '-azobis (2-methylbutyronitrile) (AMBN) was added dropwise at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. A combined solution (A-5) was obtained.

<Production Example 6: Production of hydrolyzable polymer solution (A-6)>
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of PGM, 65 parts of xylene, and 4 parts of ethyl acrylate, and heated to 100 ° C. while stirring. Subsequently, from the dropping funnel, 32.3 parts of methyl methacrylate, 43.9 parts of ethyl acrylate, 10 parts of FM-0721 (trade name, manufactured by JNC Corporation), a metal ester group-containing monomer mixture described in Production Example M1 ( a12-1) 21.7 parts, xylene 10 parts, chain transfer agent (manufactured by NOF Corporation, NOFMER MSD (trade name), α-methylstyrene dimer) 1.2 parts, AIBN 2.5 parts, AMBN 3 parts The resulting clear mixture was added dropwise at a constant rate over 6 hours. After completion of the addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 10.1 parts of xylene was added to produce a pale yellow transparent hydrolyzable substance. A polymer solution (A-6) was obtained.

<Production Example 7: Production of hydrolyzable polymer solution (A-7)>
Into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction pipe, and a heating / cooling jacket, 10.0 parts of PGM, 63.0 parts of xylene, and 3.0 parts of ethyl acrylate were charged and stirred. The temperature was raised to 100 ± 5 ° C. While maintaining the same temperature, from the dropping device, 50.3 parts of the metal ester group-containing monomer mixture (a12-2) obtained in Preparation Example M2 in the reaction container, 9.0 parts of methyl methacrylate, 58 of ethyl acrylate 58 A mixture comprising 0.0 part, 5.0 parts of polymerization initiator AMBN and 10.0 parts of PGM was added dropwise over 4 hours. After completion of the dropping, 0.5 parts of a polymerization initiator t-butyl peroctoate and 7.0 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 12.0 parts of xylene was added, A pale yellow transparent hydrolyzable polymer solution (A-7) was prepared.

<Production Example 8: Production of hydrolyzable polymer solution (A-8)>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction tube, and a heating / cooling jacket was charged with 15.0 parts of PGM, 60.0 parts of xylene, and 4.0 parts of ethyl acrylate while stirring. The temperature was raised to 100 ± 5 ° C. While maintaining the same temperature, 40.2 parts of the metal ester group-containing monomer mixture (a12-1) obtained in Preparation Example M1, 45.0 parts of methyl methacrylate, 15.0 parts of methyl methacrylate, 0.0 part, n-butyl acrylate 15.0 parts, polymerization initiator AIBN 2.5 parts, polymerization initiator AMBN 6.5 parts, chain transfer agent “NOFMER MSD” 1.2 parts, and xylene 10.0 parts Was added dropwise over 6 hours. After completion of the dropwise addition, 0.5 parts of a polymerization initiator t-butyl peroctoate and 7.0 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, then 8.0 parts of xylene was added, A pale yellow transparent hydrolyzable polymer solution (A-8) was prepared.
Table 2 shows the constitution of the monomer components of the hydrolyzable polymer solutions (A-5) to (A-8) and the characteristic values of the hydrolyzable polymer solutions (A-5) to (A-8). Shown together. The viscosity, number average molecular weight, and weight average molecular weight were measured in the same manner as in the hydrolyzable polymer solution (A-1), and the zinc content (% by mass) was measured using an atomic absorption spectrophotometer (Shimadzu Corporation). Measured by AA6800 (trade name) manufactured by Seisakusho.

Each component in Table 2 is as follows.
* 2 FM-0711 manufactured by JNC, one-end methacryloyloxyalkyl-modified organopolysiloxane, number average molecular weight Mn = 1,000
* 3 FM-0721: JNC Co., Ltd., one-end methacryloyloxyalkyl-modified organopolysiloxane, number average molecular weight Mn = 5,000

[Production of Lower Antifouling Paint Composition (x), Upper Antifouling Paint Composition (y), and Laminated Antifouling Coating]
-Compounding component Each compounding component used for the lower layer antifouling paint composition (x) and the upper layer antifouling paint composition (y) is shown in Table 3.

The organic antifouling agent (C) used is soluble in xylene and propylene glycol monomethyl ether. The solubility of tralopyryl is 1 g / L or more for xylene, 100 g / L or more for propylene glycol monomethyl ether, DCOIT is 100 g / L or more for all, and PK is 1 g / L or more for all. Medetomidine is 1 g / L or more with respect to xylene, and 100 g / L or more with respect to propylene glycol monomethyl-ter.
Moreover, all the used polymers (B) are soluble in the organic solvent mixed liquid of the ratio described in the Example, The solubility is 100 g / L or more.

<Manufacture of lower layer antifouling paint composition (x) and upper layer antifouling paint composition (y)>
With the blending (parts by mass) listed in Tables 4 and 5, the blending components were mixed and stirred to obtain a lower layer antifouling paint composition (x) and an upper layer antifouling paint composition (y). In addition, the compounding quantity of each component described in Table 4 and Table 5 has shown the compounding quantity in solid. For example, in the top coat antifouling paint composition (y-1), the amount of fatty acid amide wax in the form (as a whole) is 2.0 parts by mass and the solid content is 20%, and therefore the effective The compounding quantity of the fatty acid amide wax which is a component is 0.4 mass part.
In addition, a silicone-based paint composition (trade name “CMP Bioclin HB”, manufactured by China Paint Co., Ltd., does not contain hydrolyzable polymer (A) and organic antifouling agent (B)) A coating composition obtained by mixing 3 parts by mass of tralopyril and 10 parts by mass of 2-heptanone with respect to 100 parts by mass of the composition (y-12) was obtained as a lower layer antifouling coating composition (x-20). It was.

[Examples 1 to 30 and Comparative Examples 1 to 19]
<Manufacture of laminated antifouling coating>
An epoxy resin rust preventive paint composition (trade name “Banno 500”, manufactured by China Paint Co., Ltd.) is applied to a sandblasted steel sheet (length 300 mm × width 100 mm × thickness 3.2 mm), and the dry film thickness is about 100 μm. It applied so that it might become. Subsequently, in the combinations shown in Table 6, Table 7 and Table 8, the lower layer antifouling paint composition (x) produced according to Table 4 was applied once so that the dry film thickness was about 100 μm, The upper antifouling paint composition (y) produced according to Table 5 was applied once so that the dry film thickness was about 200 μm, and then dried at 25 ° C. for 7 days to obtain a laminated antifouling agent. A test plate with a coating film was prepared. The above three coatings are performed once a day, that is, in the case of repeated coating, after coating the coating composition corresponding to the lower layer coating film, the coating composition is dried at 25 ° C. for at least 24 hours and applied on the coating film. A coating composition corresponding to the upper layer coating film was applied.

<Evaluation>
〔appearance〕
When the appearances of the laminated antifouling coating films obtained in Examples 1 to 30 and Comparative Examples 1 to 19 were evaluated visually, they were all good with no defects such as abnormal appearance.

[Barnacle immersion test]
The test plates of Examples 1 to 23 and Comparative Examples 1 to 13 prepared as described above were placed off the Miyajima island in Hiroshima Prefecture at a position of about 0.5 meters below the water surface and the test surface was horizontal to the water surface. There was soaking in the direction facing the sea floor. Immerse for 3 months and measure the area of the laminated antifouling coating that the barnacles occupy (barnacles occupying area). The antifouling property (barnacle resistance) of the film was evaluated. The results are shown in Tables 6 and 7.
(Anti-fouling evaluation criteria based on barnacle occupancy area)
5: Barnacle occupying area on the test surface is less than 1% of the whole 4: Same area as above 1% or more and less than 10% 3: Same as above area 10% or more and less than 30% of the whole 2: Same area as above 30% or more of the whole Less than 70% 1: Same area as above 70%

[Slime resistance promotion test]
The test plates of Examples 24 to 30 and Comparative Examples 14 to 19 produced as described above were speeds at which the surface of the test surface was about 15 knots at a position of about 0.5 meters below the water surface in Hiroshima Bay. It was attached to a rotating cylinder and immersed under sunlight exposure conditions. Six months after the start of immersion under this condition, the slime occupation area on the antifouling coating was measured, and the antifouling property of the laminated antifouling coating ( (Slime resistance) was evaluated. The results are shown in Table 8. Under these conditions, contamination by slime and plant marine organisms is particularly likely to occur due to the characteristics of the submerged sea area and conditions.
(Anti-fouling evaluation criteria based on slime occupation area)
5: The total area occupied by slime 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 as above 30% or more and less than 70% of the whole 1: Same area as above 70% or more of the whole

[Interlayer adhesion]
The test plate produced as described above was immersed in seawater at 50 ° C. for 1 month, and then a knife cut test was performed to evaluate interlayer adhesion according to the following criteria.
(Interlayer adhesion evaluation criteria)
5: No delamination is observed in the vicinity of the cut part 4: The range where the delamination occurs is less than 1 mm from the cut part 3: The range where the delamination occurs is 1 mm or more and less than 3 mm from the cut part 2: Delamination The range in which the delamination occurs is 3 mm or more and less than 10 mm from the cut portion. 1: The range in which delamination occurs is 10 mm or more from the cut portion. Tables 6 to 8 show the results.

As is clear from the results of Examples and Comparative Examples, according to the present invention, a laminated antifouling coating film having a good appearance and capable of exhibiting antifouling performance and interlayer adhesion, and this on a substrate. A substrate with a laminated antifouling coating film can be provided.

Claims

It is a laminated antifouling coating film in which a lower antifouling coating film (X) and an upper antifouling coating film (Y) are laminated,
The lower layer antifouling coating film (X) contains a polymer (B1) and an organic antifouling agent (C1),
The polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond,
The upper antifouling coating film (Y) contains a hydrolyzable polymer (A2).
The laminated antifouling coating film according to claim 1, wherein the lower antifouling coating film (X) further contains a hydrolyzable polymer (A1).
The laminated antifouling film according to claim 1 or 2, wherein the total amount of the polymer (B1) and the hydrolyzable polymer (A1) in the lower antifouling coating film (X) is 1 to 90% by mass. Paint film.
The hydrolyzable polymer (A1) and / or the hydrolyzable polymer (A2) has a structural unit derived from a silyl ester group-containing monomer (a11). The laminated antifouling coating film described.
The laminated antifouling coating film according to claim 4, wherein the silyl ester group-containing monomer (a11) is represented by the following formula (1-1).

(In formula (1-1), R 11 represents a hydrogen atom or a methyl group, and R 12 , R 13 and R 14 each independently represents a monovalent hydrocarbon group.)
The hydrolyzable polymer (A1) and / or the hydrolyzable polymer (A2) has a structural unit derived from a metal ester group-containing monomer (a12), according to any one of claims 1 to 5. The laminated antifouling coating film described.
The metal ester group-containing monomer (a12) is at least a monomer (a121) represented by the following formula (1-2) and a monomer (a122) represented by the following formula (1-3) The laminated antifouling coating film according to claim 6, comprising one.

(In formula (1-2), each R 21 independently represents a monovalent group containing a terminal ethylenically unsaturated group, and M represents a metal.)

(In the formula (1-3), R 31 represents a monovalent group containing a terminal ethylenically unsaturated group, and R 32 is a monovalent organic group having 1 to 30 carbon atoms which does not contain a terminal ethylenically unsaturated group. And M represents a metal.)
The lower antifouling coating film (X) is used as the organic antifouling agent (C1) as 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and 4 The laminated antifouling coating film according to any one of claims 1 to 7, which contains at least one selected from 1,5-dichloro-2-n-octyl-4-isothiazolin-3-one.
A substrate with a laminated antifouling coating film coated with the laminated antifouling coating film according to any one of claims 1 to 8.
The base material with a laminated antifouling coating film according to claim 9, wherein the base material is an underwater structure, a ship, or a fishing gear.
An antifouling method using the laminated antifouling coating film according to any one of claims 1 to 8.
Applying the lower layer antifouling coating composition (x) on the substrate to form the lower layer antifouling coating film (X), and the upper layer antifouling coating composition (X) applying y) and forming an upper antifouling coating film (Y),
The lower layer antifouling coating composition (x) contains a polymer (B1) and an organic antifouling agent (C1), and the polymer (B1) is derived from a monomer having an unsaturated double bond. A polymer having a structural unit
The manufacturing method of the base material with a lamination | stacking antifouling coating film in which the said upper layer antifouling paint composition (y) contains a hydrolysable polymer (A2) and an organic solvent (D2).
The laminated antifouling coating according to claim 12, wherein the organic solvent (D2) is soluble in the polymer (B1) and the organic antifouling agent (C1) contained in the lower layer antifouling coating composition (x). The manufacturing method of a base material with a film.
The antifouling laminate according to claim 12 or 13, wherein the organic solvent (D2) contains one or more selected from the group consisting of hydrocarbon solvents, alcohol solvents, ketone solvents, and ester solvents. The manufacturing method of a base material with a coating film.
The upper antifouling coating composition (y) contains an organic antifouling agent (C2), and the content (mass%) of the organic antifouling agent (C2) in the upper antifouling coating composition (y) is lower layer. The substrate with a laminated antifouling coating film according to any one of claims 12 to 14, which is lower than the content (% by mass) of the organic antifouling agent (C1) in the antifouling coating composition (x). Production method.
The method for producing a substrate with a laminated antifouling coating film according to any one of claims 12 to 15, wherein the upper antifouling coating composition (y) contains substantially no organic antifouling agent (C2). .
Lower layer antifouling paint composition (x) containing polymer (B1) and organic antifouling agent (C1), and upper antifouling paint containing hydrolyzable polymer (A2) and organic solvent (D2) A coating kit for forming a laminated antifouling coating film comprising the composition (y);
The polymer (B1) is a polymer having a structural unit derived from a monomer having an unsaturated double bond,
A coating kit for forming a laminated antifouling coating film, wherein the polymer (B1) and the organic antifouling agent (C1) contained in the lower antifouling coating composition (x) are soluble in the organic solvent (D2).
The upper layer antifouling coating composition is coated on the surface of the lower layer antifouling coating film (X) containing the polymer (B1) and the organic antifouling agent (C1). The polymer (B1) A polymer having a structural unit derived from a monomer having a heavy bond, wherein the upper antifouling coating composition contains a hydrolyzable polymer (A2) and an organic solvent (D2);
The organic solvent (D2) is soluble in the polymer (B1) and the organic antifouling agent (C1) contained in the lower antifouling coating film (X).