JP6689958B2 - Antifouling paint composition, antifouling coating film, antifouling base material and method for producing the same - Google Patents

Description

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

  Various kinds of aquatic organisms such as oysters, mussels and barnacles, plants such as Nori, and bacteria, and bacteria are easily attached to the surface of substrates such as ships, underwater structures and fish nets that are exposed to water for a long period of time. When these aquatic organisms propagate on the surface of the substrate, various problems occur. For example, when the base material is a ship, the surface roughness increases from the waterline of the ship to the bottom of the ship, resulting in a decrease in the speed of the ship and an increase in fuel consumption. Further, when the base material is a fish net such as an aquaculture net or a set net, the net may be blocked by aquatic organisms, which may cause serious problems such as oxygen deficiency of the aquaculture organisms and the caught organisms. Furthermore, if the base material is a seawater supply / drain pipe for a thermal power plant, a nuclear power plant, etc., the seawater (cooling water) supply / drain pipe will be blocked or the flow velocity will be reduced, which will interfere with the circulation system. Sometimes.

In order to prevent the adhesion of aquatic organisms to various base materials against such problems, research and development of antifouling paints (antifouling paint compositions) applied to the base materials are underway.
Patent Document 1 contains a copolymer obtained by reacting a methacrylic acid organosilicon ester monomer such as triisopropylsilyl methacrylate with a methacrylic acid alkoxyalkyl ester such as methoxyethyl methacrylate at a predetermined mass ratio. An antifouling coating composition is described.
Patent Document 2 describes A) one or more rosin-based compounds consisting of rosin, rosin derivatives or rosin metal salts, B) a specific organic silyl ester group-containing polymer, and C) an antifouling agent. A coating composition containing as an essential component is described.

Furthermore, Patent Document 3 relates to a coating composition for preventing organisms from adhering to the surface of an object in the sea, and is characterized by introducing a triorganosilyl group and an alkoxy group or an aryloxypolyethylene glycol group into a molecular side chain. A coating composition is described which comprises the copolymer (1) and an antifouling agent as essential components.
In Patent Document 4, in 100 parts by weight of the monomer component, 55 to 75 parts by weight of triisopropylsilyl (meth) acrylate (a), 2 to 20 parts by weight of methoxyethyl acrylate (b), and other polymerizable monomers (c ) 43 to 5 parts by weight, and a coating composition comprising the copolymer and an antifouling agent.

JP, 2005-82725, A JP, 10-30071, A JP, 7-102193, A JP 2001-226440 A

  It is an object of the present invention to provide an antifouling coating composition in which the resulting antifouling coating film has excellent antifouling properties and long-term durability, and also excellent long-term storage stability. A further object of the present invention is to provide an antifouling coating film obtained from the above antifouling coating composition, an antifouling substrate having the antifouling coating film, and a method for producing the same.

  The inventors of the present invention have made earnest studies in view of the above problems, and found that a silyl ester copolymer in which triisopropylsilyl methacrylate (TIPSMA) and 2-methoxyethyl acrylate (MEA) were copolymerized, copper pyrithione, and zinc oxide. The inventors have found that the above-mentioned problems can be solved by an antifouling coating composition containing a resin and a rosin compound, and completed the present invention.

The present invention relates to the following [1] to [7].
[1] 45 to 75 mass% of the structural unit (a1) derived from triisopropylsilyl methacrylate, 15 to 35 mass% of the structural unit (a2) derived from 2-methoxyethyl acrylate, and other ethylenically unsaturated monomers -Fouling paint containing a silylmethacrylate copolymer (A) containing 0 to 35% by mass of the structural unit (a3) derived from ## STR3 ##, copper pyrithione (B), zinc oxide (C), and rosin compound (D) Composition.
[2] Further, inorganic copper compound (E), color pigment (F), extender pigment (G), pigment dispersant (H), plasticizer (I), anti-sagging agent (J), anti-settling agent (K). The antifouling coating composition according to the above [1], which contains at least one component selected from the group consisting of: a dehydrating agent (L), and a solvent (M).
[3] A ternary copolymer of the silyl methacrylate-based copolymer (A) including a constitutional unit derived from triisopropylsilyl methacrylate, a constitutional unit derived from 2-methoxyethyl acrylate, and a constitutional unit derived from methyl methacrylate. The antifouling coating composition according to [1] or [2], which is a united body.
[4] An antifouling coating film formed from the antifouling coating composition according to any one of [1] to [3].
[5] An antifouling substrate having the antifouling coating film according to [4] formed on a substrate.
[6] The antifouling substrate according to [5], wherein the substrate is at least one selected from the group consisting of underwater structures, ships, and fishing gear.
[7] A step of applying the antifouling coating composition according to any one of [1] to [3] to a substrate, or the antifouling coating composition according to any of [1] to [3]. A method for producing an antifouling substrate, which comprises, in this order, a step of impregnating a substrate and a step of drying the antifouling coating composition to form an antifouling coating film on the substrate.

  According to the present invention, it is possible to provide an antifouling coating composition in which the obtained antifouling coating film is excellent in antifouling property and long-term durability, and further excellent in long-term storage stability. Further, according to the present invention, it is possible to provide an antifouling coating film obtained from the above antifouling coating composition, an antifouling substrate having the antifouling coating film and a method for producing the same.

Hereinafter, the antifouling coating composition, the antifouling coating film, the antifouling base material, and the method for producing the antifouling base material according to the present invention will be described in detail.
[Anti-fouling paint composition]
The antifouling coating composition of the present invention has a constitutional unit (a1) derived from triisopropylsilyl methacrylate of 45 to 75% by mass, a constitutional unit (a2) derived from 2-methoxyethyl acrylate of 15 to 35% by mass, and A silylmethacrylate copolymer (A) containing 0 to 35 mass% of a structural unit (a3) derived from another ethylenically unsaturated monomer, copper pyrithione (B), zinc oxide (C), and rosin compound (D). ) Is included.
According to the present invention, there is provided an antifouling coating composition in which the resulting antifouling coating film has excellent antifouling properties and long-term durability, and further has excellent long-term storage stability. Here, according to the antifouling coating composition of the present invention, an antifouling coating film having excellent antifouling property especially on a draft line or near the water can be obtained. That is, the antifouling property means that the adhesion of aquatic organisms is suppressed not only in the water but also in the draft line or at the water's edge even when it is immersed in seawater for a long time. Further, in the present invention, the long-term durability is excellent in internal hydrolysis resistance and appearance characteristics of the coating film when it is immersed in water, particularly seawater for a long time (the occurrence of cracks, cracks, etc. is suppressed for a long time). ) Is mentioned, and in particular, it can be evaluated by the crack resistance when it is immersed in seawater for a long period of time. In addition, long term storage stability means that viscosity increase with time is small.

As described in Patent Documents 1 to 4, a copolymer derived from triisopropylsilyl (meth) acrylate has hitherto been used as a hydrolyzable resin in many antifouling paint compositions for ships. ing. The present inventors have found that triisopropylsilyl methacrylate (TIPSMA) has particularly good water resistance, and further has long-term physical properties (crack resistance, adhesion, storage stability of coating film) of triisopropylsilyl acrylate (TIPSMA). It was found to be better than TIPSA).
However, a hydrolyzable resin composed of a copolymer derived from TIPSMA has high hydrophobicity because TIPSMA has a methyl group at the α-position, and thus is excellent in water resistance and long-term physical properties, but has a high water resistance. It has been found that since the antifouling agent is too high, the elution amount of the antifouling agent is small. Particularly, a remarkable difference is caused by the difference in antifouling property between the ship and the seawater on the draft line (at the waterside), and the antifouling paint containing the hydrolyzable resin composed of the copolymer derived from TIPSMA. The composition did not have sufficient antifouling property, especially in the draft line.
As a result of intensive investigations by the present inventors, a structural unit derived from triisopropylsilyl methacrylate (TIPSMA) excellent in long-term durability and a structural unit derived from 2-methoxyethyl acrylate (MEA), which is a hydrophilic monomer, Antifouling coating composition containing a silylmethacrylate copolymer having a desired mass ratio of other ethylenically unsaturated monomer-derived constitutional units, and copper pyrithione, zinc oxide, and a rosin compound, if necessary. By using, it is found that an antifouling coating film excellent in antifouling property and long-term durability can be obtained, and an antifouling coating composition excellent in long-term storage stability can be obtained, and the present invention is completed. Came to.

The detailed mechanism by which the above effects are obtained is unknown, but some of them are presumed as follows. That is, the hydrophobicity is enhanced by using triisopropylsilyl methacrylate, which has excellent water resistance, but by using 2-methoxyethyl acrylate, which is a hydrophilic monomer, the hydrophobicity of the resulting silyl methacrylate-based copolymer is improved. It is presumed that it was alleviated and, as a result, the antifouling property was improved. In addition, it is estimated that the use of triisopropylsilyl methacrylate improves storage stability and long-term durability as compared with the case of using triisopropylsilyl acrylate.
Further, although the detailed mechanism thereof is unknown, by using a specific silyl methacrylate-based copolymer in combination with copper pyrithione, zinc oxide and a rosin compound, excellent storage stability can be obtained, and the resulting antifouling coating can be obtained. It was discovered that an antifouling coating composition excellent in both antifouling property and long-term durability of the film can be obtained.

<1. Silyl Methacrylate Copolymer (A)>
The antifouling coating composition of the present invention contains a silyl methacrylate copolymer (A) for the purpose of improving the antifouling effect of a coating film, and the silyl methacrylate copolymer (A) is Structural unit (a1) derived from isopropylsilyl methacrylate (hereinafter also referred to as structural unit (a1)), structural unit (a2) derived from 2-methoxyethyl acrylate (hereinafter also referred to as structural unit (a2)), And a structural unit (a3) derived from another ethylenically unsaturated monomer (hereinafter, also referred to as a structural unit (a3)).
The "other ethylenically unsaturated monomer" means a polymerizable monomer having an ethylenically unsaturated bond except for triisopropylsilyl methacrylate and 2-methoxyethyl acrylate. Further, in the present invention, “(meth) acrylate” means “acrylate or methacrylate”.
Moreover, when X is a compound represented by the following formula (1), the “structural unit derived from X” is, for example, a constitutional unit represented by the following formula (2). Here, A ^{1 to} A ⁴ are arbitrary substituents.

  The term "containing component Z" in the antifouling coating composition of the present invention means that the antifouling coating composition of the present invention is prepared by blending component Z, for example, component Z Includes a case where the compound becomes a compound different from the compounded component Z by reacting with other components or forming a salt in the antifouling coating composition.

(Structural unit (a1) derived from triisopropylsilyl methacrylate)
The structural unit (a1) is a structural unit derived from triisopropylsilyl methacrylate (i).
From the viewpoint of obtaining an antifouling coating composition having good water resistance and various physical properties (crack resistance, adhesion, storage stability of coating film) over a long period of time, the silyl methacrylate copolymer (A) is a structural unit (A). a1) is contained in an amount of 45 to 75% by mass, preferably 50 to 70% by mass.
When the content of the structural unit (a1) is less than 45% by mass or exceeds 75% by mass, sufficient long-term durability and antifouling property cannot be obtained.
The content of the structural unit (a1) derived from triisopropylsilyl methacrylate should be approximated by the charging ratio (mass%) of triisopropylsilylmethacrylate in all the monomers constituting the silylmethacrylate copolymer (A). The same applies to other structural units.

(Structural unit (a2) derived from 2-methoxyethyl acrylate)
The structural unit (a2) is a structural unit derived from 2-methoxyethyl acrylate (ii).
From the viewpoint of obtaining an antifouling coating film having stable hydrolyzability, the silyl methacrylate copolymer (A) contains the structural unit (a2) derived from 2-methoxyethyl acrylate in an amount of 15 to 35% by mass, preferably Is contained in an amount of 20 to 30% by mass.

(Structural unit (a3) derived from other ethylenically unsaturated monomer)
The other ethylenically unsaturated monomer (iii) has an ethylenically unsaturated group. Examples of the group having an ethylenically unsaturated group include a vinyl group and a (meth) acryloyl group.
The other ethylenically unsaturated monomer is not particularly limited as long as it is an ethylenically unsaturated monomer excluding triisopropylsilyl methacrylate and 2-methoxyethyl acrylate, and an ester having an ethylenically unsaturated bond (unsaturated ester), And carboxylic acids having an ethylenically unsaturated bond (unsaturated carboxylic acids) are preferable. When the other ethylenic monomer is the above compound, good compatibility with triisopropylsilyl methacrylate and 2-methoxyethyl acrylate is obtained, and the reactivity is similar to that of triisopropylsilyl methacrylate and 2-methoxyethyl acrylate. Is preferable because it has

  Other ethylenically unsaturated monomers include (meth) acrylic acid esters, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and their half esters (monoesters) and diesters, vinyl esters; metal ester group-containing ( (Meth) acrylate; organosiloxane group-containing (meth) acrylate is exemplified. Moreover, styrenes are illustrated as a monomer other than unsaturated ester and unsaturated carboxylic acid.

  Specific examples of other ethylenically unsaturated monomers include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) Acrylic acid lauryl ester, (meth) acrylic acid tridecyl ester, (meth) acrylic acid stearyl ester, (meth) acrylic acid allyl ester, (meth) acrylic acid cyclohexyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic Acid isobornyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid hydroxyethyl ester, (meth) acrylic acid hydroxypropyl ester, (meth) acrylic acid hydroxy (Meth) acrylic acid esters such as butyl ester, (meth) acrylic acid methoxytriethylene glycol ester, (meth) acrylic acid ethoxydiethylene glycol ester, (meth) acrylic acid methoxydipropylene glycol ester; and (meth) acrylic acid Monocarboxylic acids; dicarboxylic acids such as itaconic acid, maleic acid, succinic acid and their half-esters (monoesters) and diesters; styrenes such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate And the like, and these may be used alone or in combination of two or more.

  The silyl methacrylate-based copolymer (A) contains 0 to 35% by mass, and preferably 5 to 30% by mass of the structural unit (a3) derived from another ethylenically unsaturated monomer.

  The silyl methacrylate copolymer (A) has a constitutional unit (a3) derived from another ethylenically unsaturated monomer, which has 4 or more carbon atoms, from the viewpoints of water resistance balance of the coating film and improvement of antifouling property against water for a long time. It is preferable not to have a linear alkyl group. From the same viewpoint, the silyl methacrylate copolymer (A) preferably contains a structural unit derived from an ethylenically unsaturated monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, and propyl methacrylate, It is more preferable to contain a structural unit derived from an ethylenically unsaturated monomer selected from the group consisting of methyl methacrylate and ethyl methacrylate, and it is more preferable to contain a structural unit derived from methyl methacrylate, and a structural unit (a3) Is more preferably only a structural unit derived from methyl methacrylate. That is, it is particularly preferable that the silyl methacrylate copolymer (A) is a ternary copolymer composed of triisopropylsilyl methacrylate, 2-methoxyethyl acrylate, and methyl methacrylate.

  The content of the silyl methacrylate-based copolymer (A) in the antifouling coating composition is the amount of non-volatile components of the antifouling coating composition from the viewpoint of ensuring antifouling property, long-term storage stability, and improving long-term durability. Is 100 mass%, preferably 5 to 50 mass%, more preferably 5 to 30 mass%.

The weight average molecular weight (Mw) of the silyl methacrylate-based copolymer (A) is preferably 5,000 to 100,000, more preferably 10,000 to 60,000. The antifouling coating film formed from the antifouling coating composition containing the silylmethacrylate-based copolymer (A) having a weight average molecular weight in the above range has good hydrolyzability and still standing antifouling property is further improved. In addition, it is possible to exhibit more excellent long-term durability.
The weight average molecular weight is a value measured by a gel permeation chromatography (GPC) method and obtained using a standard polystyrene calibration curve.

(Production Method of Silyl Methacrylate Copolymer (A))
The silyl methacrylate copolymer (A) is obtained by copolymerizing triisopropylsilyl methacrylate (i), 2-methoxyethyl acrylate (ii) and other ethylenically unsaturated monomer (iii) by a known polymerization method. Can be prepared. Examples of the polymerization method include solution polymerization, bulk polymerization, semi-batch polymerization, suspension polymerization, coordination polymerization, living polymerization, and radical or ionic polymerization in emulsion polymerization. Of these, considering that the silyl methacrylate-based copolymer (A) can be improved in productivity and workability and a silyl methacrylate-based copolymer (A) having a low viscosity can be prepared, toluene, xylene, methyl isobutyl ketone, It is preferable to carry out solution polymerization of the monomers (i) to (iii) using a commonly used organic solvent such as n-butyl acetate.

  As the catalyst used in the radical polymerization, known catalysts can be widely used. For example, 2,2′-azobis (2-methylbutyric acid) as described in JP-A-2001-151830, column [0099] and the like. Aronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis-isobutyronitrile (AIBN), benzoyl peroxide, t-butylperoxy-2- Peroxides such as ethyl hexanoate, t-butyl peroxybenzoate, t-butyl peroxy octoate are mentioned.

<2. Copper pyrithione (B)>
The antifouling coating composition of the present invention further improves the antifouling property of the antifouling coating film formed from the composition, and particularly, in order to effectively exhibit the antifouling performance against plant marine organisms, copper pyrithione is used. (B) is contained. From the viewpoint of exhibiting sufficient antifouling performance in the antifouling coating composition of the present invention, the content of the copper pyrithione (B) is preferably 0.1% with respect to 100 parts by mass of the silyl methacrylate copolymer (A). The amount is 01 to 500 parts by mass, more preferably 0.01 to 300 parts by mass. Further, when the nonvolatile content of the antifouling coating composition is 100% by mass, the content of copper pyrithione (B) is preferably 0.1 to 90% by mass, more preferably 0.5 to 80% by mass. is there.

<3. Zinc oxide (C)>
The antifouling coating composition of the present invention exerts appropriate strength, antifouling property (coating film consumable property), and renewal property on an antifouling coating film formed from the composition, and enables effective antifouling performance. In order to exhibit, zinc oxide (C) is contained. From the viewpoint of exhibiting sufficient strength and antifouling performance in the antifouling coating composition of the present invention, the content of zinc oxide (C) is preferably 100 parts by mass of the silyl methacrylate copolymer (A). The amount is 0.1 to 1000 parts by mass, more preferably 0.5 to 500 parts by mass. Further, when the nonvolatile content of the antifouling coating composition is 100% by mass, the content of zinc oxide (C) is preferably 0.1 to 80% by mass, more preferably 0.5 to 70% by mass. is there.

<4. Rosin compound (D)>
The antifouling coating composition of the present invention accelerates the elution of the antifouling agent from the antifouling coating film formed from the composition, and improves the antifouling property (particularly the antifouling property at the water's edge). , A rosin compound (D). Examples of the rosin compound here include rosin such as gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, and rosin derivatives such as disproportionated rosin.
Further, in the antifouling coating composition of the present invention, the silyl methacrylate copolymer content of (A) and (W _A), the content of the rosin compound _(D) (W D) ratio of (W _A / W _D) is preferably from 99.9 / 0.1 to 30/70 by weight, more preferably, 95 / 5-35 / 65, more preferably from 90 / 10-40 / 60. When the content ratio by weight is within such a range, it has an effect of enhancing the scouring property (coating film consumability) in the antifouling coating film formed from the antifouling coating composition, and the antifouling property (especially when it is near water) Antifouling property) can be improved.

  The antifouling coating composition of the present invention further comprises an inorganic copper compound (E), a coloring pigment (F), an extender pigment (G), a pigment dispersant (H), a plasticizer (I), an anti-sagging agent (J), It may contain at least one additive selected from the group consisting of an anti-settling agent (K), a dehydrating agent (L), and a solvent (M). Hereinafter, these (E) to (M) will be described in detail.

<5. Inorganic copper compound (E)>
The antifouling coating composition of the present invention may further contain an inorganic copper compound (E) in order to further improve the antifouling property of the antifouling coating film formed from the antifouling coating composition. Examples of the inorganic copper compound include powdery copper (copper powder), cuprous oxide, copper thiocyanate (also known as rhodan copper), cupronickel, and the like.
In the present invention, cuprous oxide is preferred as the inorganic copper compound (E). From the viewpoint of dispersibility in the antifouling coating composition, the average particle size of cuprous oxide is preferably less than 4.5 μm, more preferably 4 μm or less, still more preferably 3.5 μm or less. The average particle diameter is measured by a laser diffraction scattering method using SALD-2200 (manufactured by Shimadzu Corporation).
Specifically, a 0.2 mass% solution of HMPNa (sodium hexametaphosphate) and a few drops of a neutral detergent are added to a sample disperser of SALD-2200, ultrasonic waves are activated, and a pump speed is set to 7 and circulated. . Take about 100 mg of cuprous oxide in a mortar and add a few drops of neutral detergent to gently disperse to loosen secondary agglomeration. Water is added to the sample dispersed in the mortar so that no bubbles are formed, and the sample is poured into the sample disperser. After circulating and dispersing with a disperser for 10 minutes, the particle size distribution is measured. The refractive index at the time of particle size distribution calculation is "2.70-0.20i", and the median particle in the particle size distribution is the average particle size.

  In the antifouling coating composition of the present invention, the content of the inorganic copper compound (E) is preferably 0 based on 100 parts by mass of the silyl methacrylate copolymer (A) from the viewpoint of long-term antifouling property. 0.01 to 2,500 parts by mass, more preferably 0.1 to 1,000 parts by mass. When the nonvolatile content of the antifouling coating composition is 100% by mass, the content of the inorganic copper compound (E) is preferably 0.1 to 90% by mass, more preferably 0.5 to 80% by mass. Is.

<6. Color pigment (F)>
The antifouling coating composition of the present invention contains a coloring pigment (F) in order to adjust the color tone of an antifouling coating film formed from the antifouling coating composition or to impart an arbitrary color tone. Good.
Examples of the color pigment (F) include various known organic or inorganic color pigments. Examples of organic color pigments include carbon black, naphthol red, and phthalocyanine blue. Examples of inorganic color pigments include red iron oxide, barite powder, titanium white, and yellow iron oxide.

Further, the antifouling coating composition of the present invention may contain a colorant other than the color pigment (F), such as a dye, in addition to the color pigment (F) or in place of the color pigment (F). .
In the antifouling coating composition of the present invention, the content of the coloring pigment (F) is such that the antifouling coating film formed from the antifouling coating composition has coloring properties, hiding properties, exposure discoloration properties, antifouling properties, and coating properties. From the viewpoint of improving the membrane water resistance (mechanical properties), preferably 0.01 to 100 parts by mass, more preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the silyl methacrylate copolymer (A). It is a department. Further, when the nonvolatile content of the antifouling coating composition is 100% by mass, the content of the color pigment (F) is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass. is there.

<7. Extender pigment (G)>
The antifouling coating composition of the present invention contains an extender pigment (G) for the purpose of improving coating film properties such as crack resistance of the antifouling coating film formed from the antifouling coating composition. Good.
Examples of extender pigment (G) include talc, silica (diatomaceous earth, acid clay, etc.), mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, sulfuric acid. Examples include barium and zinc sulfide. Among these, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate and potassium feldspar are preferable.

  In the antifouling coating composition of the present invention, the content of the extender pigment (G) is such that the antifouling coating film formed from the antifouling coating composition has water resistance (mechanical properties), antifouling property, and coating film. From the viewpoint of improving the hydrolyzability (consumability), the amount is preferably 0.1 to 500 parts by mass, more preferably 50 to 300 parts by mass, relative to 100 parts by mass of the silyl methacrylate copolymer (A). . When the nonvolatile content of the antifouling coating composition is 100% by mass, the content of the extender pigment (G) is preferably 0.1 to 80% by mass, more preferably 0.5 to 70% by mass. is there.

<8. Pigment dispersant (H)>
When the antifouling coating composition of the present invention contains a color pigment (F) or an extender pigment (G), from the viewpoint of improving the dispersibility of the color pigment (F) or the extender pigment (G), a pigment dispersant (H ) May be contained.
Examples of the pigment dispersant (H) include various known organic or inorganic pigment dispersants. Examples of the pigment dispersant include aliphatic amines and organic acids (for example, "Duomin TDO" (manufactured by LION Co., Ltd.) and "Disperbyk 101" (manufactured by BYK Co., Ltd.)).

  In the antifouling coating composition of the present invention, the content of the pigment dispersant (H) is from the viewpoint of improving the effect of reducing the coating viscosity of the antifouling coating composition and the effect of preventing color separation of the antifouling coating film. The amount is preferably 0.01 to 100 parts by mass, and more preferably 0.01 to 50 parts by mass, relative to 100 parts by mass of the silyl methacrylate copolymer (A). When the nonvolatile content of the antifouling coating composition is 100% by mass, the content of the pigment dispersant (H) is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass. Is.

<9. Plasticizer (I)>
The antifouling coating composition of the present invention preferably contains a plasticizer (I) in order to improve the crack resistance of the obtained antifouling coating film.
Examples of the plasticizer (I) include chlorinated paraffin (chlorinated paraffin), petroleum resins, ketone resins, TCP (tricresyl phosphate), polyvinyl ethyl ether, dialkyl phthalate and the like. From the viewpoint of improving coating film water resistance (mechanical properties) and coating film hydrolyzability (consumability) of an antifouling coating film formed from an antifouling coating composition, these plasticizers (I) may be used as Of these, chlorinated paraffin (chlorinated paraffin), petroleum resins, and ketone resins are preferable. The plasticizer (I) may be used alone or in combination of two or more.

  Specific examples of the chlorinated paraffin include "Toyo Parax 150" and "Toyo Parax A-70" (both manufactured by Tosoh Corporation). Examples of petroleum resins include C5 series, C9 series, styrene series, dichloropentadiene series, and hydrogenated products thereof. Specific examples of petroleum resins include “Quinton 1500” and “Quinton 1700” (both manufactured by Nippon Zeon Co., Ltd.).

  In the antifouling coating composition of the present invention, the content of the plasticizer (I) is such that the antifouling coating film formed from the antifouling coating composition is hydrolyzable (consumable), antifouling, and coated. From the viewpoint of improving the membrane water resistance (mechanical properties), it is preferably 0.1 to 300 parts by mass, and more preferably 0.1 to 200 parts by mass, relative to 100 parts by mass of the silyl methacrylate copolymer (A). Parts, more preferably 0.1 to 150 parts by mass. Further, when the nonvolatile content of the antifouling coating composition is 100% by mass, the content of the plasticizer (I) is preferably 0.1 to 80% by mass, more preferably 0.5 to 70% by mass. is there.

<10. Anti-sagging agent (J)>
The antifouling coating composition of the present invention has an anti-sagging agent (J) (also referred to as an anti-flow agent) from the viewpoint that when the antifouling coating composition is applied to a substrate, generation of sagging due to the coating composition can be reduced. May be included).
Examples of the anti-sagging agent (J) include amide wax, hydrogenated castor oil wax, a mixture thereof, and synthetic fine powder silica (Aerosil (registered trademark)) and the like. Among them, the amide wax or the synthetic fine powder silica is used. Preferably there is. The use of amide wax or synthetic fine silica as the anti-sagging agent (J) improves the storage stability of the antifouling coating composition, and after forming the antifouling coating film, the same type of coating material is applied on the antifouling coating film. When a coating film (overcoating film) composed of a composition (antifouling coating composition) or a heterogeneous coating composition is formed, the adhesion between the antifouling coating film and the topcoating film (interlayer adhesion, recoating) It is possible to prevent a decrease in the property), which is preferable.

  Examples of commercially available anti-sagging agents (J) include "Disparlon A630-20X" (manufactured by Kusumoto Kasei Co., Ltd.) and "ASAT-250F" (manufactured by Ito Oil Co., Ltd.). In the antifouling coating composition of the present invention, the content of the anti-sagging agent (J) is preferably 0.1 to 100 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the silyl methacrylate copolymer (A). It is 0.1 to 50 parts by mass. Further, when the nonvolatile content of the antifouling coating composition is 100% by mass, the content of the anti-sagging agent (J) is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. Is.

<11. Anti-settling agent (K)>
The antifouling coating composition of the present invention may contain an anti-settling agent (K) from the viewpoint of preventing the generation of precipitates in the coating composition during storage and improving the stirring property.

  Examples of the anti-settling agent (K) include stearates of Al, Ca, or Zn, polyethylene wax, oxidized polyethylene wax, and the like, and oxidized polyethylene wax is preferable. Examples of commercially available polyethylene oxide waxes include "Disparlon 4200-20X" (manufactured by Kusumoto Kasei Co., Ltd.).

  In the antifouling coating composition of the present invention, the content of the anti-settling agent (K) is preferably 0.1 to 100 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the silyl methacrylate copolymer (A). It is 0.1 to 50 parts by mass. Further, when the nonvolatile content of the antifouling coating composition is 100% by mass, the content of the antisettling agent (K) is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. Is.

<12. Dehydrating agent (L)>
The antifouling coating composition of the present invention has excellent storage stability because it contains the silyl methacrylate copolymer (A) having good storage stability, but a dehydrating agent (L) may be added if necessary. It becomes possible to obtain more excellent long-term storage stability by adding Examples of the dehydrating agent (L) include an inorganic dehydrating agent and an organic dehydrating agent.

As the inorganic dehydrating agent, synthetic zeolite, anhydrous gypsum and hemihydrate gypsum are preferable. Examples of the organic dehydrating agent include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and trimethylethoxysilane, and polyalkoxy which is a condensate thereof. Silanes and alkyl orthoformate esters such as methyl orthoformate and ethyl orthoformate are preferred.
In the antifouling coating composition of the present invention, the content of the dehydrating agent (L) is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the silyl methacrylate copolymer (A). Further, when the nonvolatile content of the antifouling coating composition is 100% by mass, it is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass.

<13. Solvent (M)>
The antifouling coating composition of the present invention contains water or an organic solvent, if necessary, in order to improve the dispersibility of the silyl methacrylate-based copolymer (A) or the like and to adjust the viscosity of the composition. And the like (M) may be included. The solvent (M) may be the solvent used when preparing the silylmethacrylate-based copolymer (A), and when mixing the copolymer (A) with other components as necessary, It may be a solvent added separately.

Examples of the organic solvent include aromatic organic solvents such as xylene, toluene and ethylbenzene; ketones such as methylethylketone, methylisobutylketone and cyclohexanone; aliphatic compounds such as ethanol, isopropyl alcohol, n-butanol and isobutanol (having 1 to 1 carbon atoms). 10, preferably about 2 to 5) monohydric alcohols; ester solvents such as ethyl acetate and butyl acetate; and the like.
The content of the solvent (M) in the antifouling coating composition of the present invention is usually 5 to 80% by mass, preferably 10 to 70% by mass, when the total amount of the antifouling coating composition is 100% by mass. Further, it may be further added at the time of coating depending on workability.

<Method for producing antifouling coating composition>
The antifouling coating composition of the present invention can be produced by appropriately utilizing a known method. For example, the silylmethacrylate-based copolymer (A) and, if necessary, other components may be added at once or in any order to a stirring vessel, and mixed by a known stirring and mixing means to produce the mixture. it can.
After mixing the components, finally, an anti-sagging agent (J) (Amide wax (for example, Disparlon A630-20X)) is added (for example, by stirring the mixture for about 10 to 20 minutes). It is preferable to disperse and prepare an antifouling coating composition. This is because when the obtained antifouling coating composition is applied to a substrate, the occurrence of sagging can be reduced.

  Examples of stirring and mixing means include a high speed disperser, a sand grind mill, a basket mill, a ball mill, a triple roll, a Ross mixer, a planetary mixer, and a universal Shinagawa stirrer.

[Anti-fouling coating film and anti-fouling substrate]
The antifouling coating film of the present invention comprises the solid content of the antifouling coating composition of the present invention. The antifouling coating film of the present invention is formed from the antifouling coating composition of the present invention. For example, when the antifouling coating composition contains a solvent (M), the antifouling coating composition of the present invention is applied on a substrate. The dirty paint composition can be formed, for example, by natural drying or by using a drying means such as a heater (that is, by removing the solvent (M)).

  The antifouling substrate of the present invention comprises at least a substrate and the antifouling coating film of the present invention formed on the surface of the substrate. Target object, the object to be coated), for example, by using a coating means such as air spray, airless spray, brush, roller, or impregnated, the coating composition applied to the substrate or impregnated, For example, it can be produced by natural drying (a temperature of about room temperature) or by using a drying means such as a heater to form an antifouling coating film on the substrate.

  The antifouling substrate of the present invention forms an antifouling coating film on the surface of a temporary substrate with the antifouling coating composition of the present invention, and removes the antifouling coating film from the temporary substrate to prevent stains. It can also be manufactured by sticking to a base material. At this time, an antifouling coating film may be attached to the base material via the adhesive layer.

  The base material is not particularly limited, but is preferably a base material that comes into contact with seawater or fresh water, and specifically, water supply / drainage ports of various power plants (thermal power, nuclear power), coastal roads, undersea tunnels, harbors. Underwater structures such as sludge diffusion prevention membranes used for various marine or river civil engineering works such as facilities or canals or waterways, ship outer plates (particularly from the draft to the bottom of the ship), fishing materials (ropes, fishing nets such as fishing nets, etc.) , Floats or buoys).

  Examples of the material of the base material include steel, aluminum, wood, FRP and the like for ship outer plates, natural or synthetic fibers for fish nets and the like, and synthetic resin for floats, buoys and the like. The material is not particularly limited as long as it is a base material that is required to have antifouling property in water.

  On the surface of these base materials, especially when the base material is the bottom of a ship, etc., the surface of the base material made of steel is usually coated with a primer such as an anticorrosive paint on the surface of the primer-treated base material as described above. The antifouling paint composition of the present invention (antifouling paint) is applied once or several times by various methods, and the antifouling paint composition applied or impregnated (particularly when the substrate is a fish net etc.) is dried. When the antifouling coating film is formed by doing so, it has excellent properties (antifouling property, especially stationary antifouling property) that prevents adhesion of aquatic organisms such as Ulva, Barnacle, Aonori, Serpla, oyster, and leafworm The antifouling component contained in the antifouling coating film (eg, the copper pyrithione (B), the optional inorganic copper compound (E)) can be gradually released over a long period of time.

  In addition, when the base material is a ship outer plate (particularly the bottom of the ship), an underwater structure, etc. (usually, the surface of the base material may be treated with a primer or have a layer formed from various paints. .), The antifouling coating composition is applied to the surface of the base material a plurality of times (thick coating: dry film thickness of about 100 to 600 μm), and the resulting antifouling base material has excellent antifouling properties and a suitable level. Exhibits a good balance of flexibility and excellent crack resistance.

  In producing the antifouling base material, when the base material is a deteriorated antifouling coating-coated steel plate, fishnet, or the like, the antifouling coating composition of the present invention may be directly applied to or impregnated on the surface thereof. If the base material is steel sheet material, the base material such as a rust preventive or a primer is applied to the surface of the base material in advance to form the base layer, and then the base layer is formed. The antifouling coating composition of the present invention may be applied to the surface. Further, the antifouling coating film of the present invention may be further formed on the surface of the substrate on which the antifouling coating film of the present invention or the conventional antifouling coating film is formed for the purpose of repair.

  The thickness of the antifouling coating film of the present invention formed by one coating operation is not particularly limited, but when the base material is a ship or an underwater structure, it is, for example, about 30 to 250 µm. The underwater structure having the antifouling coating film of the present invention can maintain the function of the underwater structure for a long period of time because it can prevent the attachment of aquatic organisms for a long period of time. Further, the fish net having the antifouling coating film of the present invention is less likely to cause environmental pollution, and can prevent clogging of the net due to the prevention of adhesion of aquatic organisms.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
[Evaluation methods]
Evaluation of the copolymer, coating composition, coating film, etc. described later was performed as follows.
(1) Content of solid content in the copolymer solution 1.0 g (X ₁ (g)) of the copolymer solution was volatilized in a thermostat under the condition of 1 atm and 108 ° C. for 3 hours. The solid was removed to obtain a solid content (nonvolatile content). Then, the amount (X ₂ (g)) of the remaining solid content (nonvolatile content) was measured, and the content rate (%) of the solid content contained in the copolymer solution was calculated based on the following formula.
Solid content (%) = X ₂ / X ₁ × 100

(2) Average molecular weight of copolymer The weight average molecular weight (Mw) of the copolymer was measured using GPC (gel permeation chromatography) under the following conditions.
GPC conditions Device: "HLC-8220GPC" (manufactured by Tosoh Corporation)
Column: “TSKgel SuperH2000 + TSKgel SuperH4000” (manufactured by Tosoh Corporation, 6 mm (inner diameter) × 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: THF was added to the copolymer solution prepared in each production example to dilute it, and the filtered product obtained by filtering with a membrane filter was used as a GPC measurement sample.

(3) Viscosity of copolymer solution The viscosity (unit: mPa · s) of the copolymer solution at a liquid temperature of 25 ° C was measured using an E-type viscometer (TV-25 manufactured by Toki Sangyo Co., Ltd.).

(4) Storage stability test The viscosity at 25 ° C. (initial viscosity (poise)) of each coating composition immediately after the preparation (within 1 day) prepared in Examples and Comparative Examples was measured in accordance with JIS Z 8803 to form B. The viscosity was measured using a viscometer (VISCOMETER TVB-10M, SPINDLE No. M4, CORD No. 23 (manufactured by Toki Sangyo Co., Ltd.)) at a liquid temperature of 25 ° C. and a rotation speed of 60 rpm.
Further, each coating composition was stored in a thermostat at 60 ° C., and the viscosity at 25 ° C. (viscosity after storage (poise)) of each coating composition was measured every other week based on JIS Z 8803 B-type viscosity. The measurement was performed at a rotation speed of 60 rpm using a meter. The measurement was performed until 2 weeks later. Next, the degree of increase in viscosity was calculated based on the following formula (1).
Viscosity increase degree = viscosity after storage (poise) -initial viscosity (poise) (1)
In addition, "-" in Table 8 indicates that the storage stability was extremely poor and the measurement could not be performed.

(5) Coating accelerated deterioration test (evaluation of coating appearance)
Using an applicator on a sandblast plate (150 mm x 70 mm x 1.6 mm), use an epoxy-based paint (epoxy AC paint, trade name "Banno 500", made by China Paint Co., Ltd.) so that the dry film thickness is 150 μm. And then cured to form a cured coating film, and then using a applicator, a vinyl binder coating (trade name "Silvacs SQ-K", manufactured by China Paint Co., Ltd.) is applied onto the cured coating film. A test plate was prepared by coating so as to have a dry film thickness of 40 μm.

Then, each coating composition of the above Examples and Comparative Examples was applied onto a test plate (on the surface of a dry coating film formed from a vinyl binder coating material) using an applicator so that the dry film thickness would be 150 μm. Then, it is dried at 23 ° C. for 1 day to form an antifouling coating film, and the coating composition is applied to the surface of the antifouling coating film so that the dry film thickness is 150 μm. An antifouling coating film was formed by drying for a day to prepare a test plate with an antifouling coating film.
This test plate with antifouling coating film was immersed in artificial seawater at 50 ° C., and the appearance of the coating film was examined one month after the start of immersion based on the following evaluation criteria.

Appearance evaluation The degree of cracking on the surface of the antifouling coating film of the test plate with an antifouling coating film was visually observed, and the amount of cracking was evaluated by the grade according to JIS K5600-8-4 as shown in the table below. It was From the appearance evaluation, the long-term durability of the antifouling coating film and the antifouling substrate can be evaluated.

(6) Static antifouling test A sandblast plate (300 mm x 100 mm x 3.2 mm) was used with an applicator to use an epoxy-based paint (epoxy AC paint, trade name "Bannow 500", manufactured by China Paint Co., Ltd.). To a dry film thickness of 150 μm and cured to form a cured coating film, and then a vinyl binder coating (trade name “Silvax SQ-K”, Chinese coating (stock) )) Was applied to give a dry film thickness of 40 μm, and dried in a room for 1 day to prepare a test plate.

  Next day, on the next day (on the surface of the cured coating film formed from the vinyl binder coating), each antifouling coating composition of the following Examples and Comparative Examples was dried with an applicator to a dry film thickness of 150 μm. And then dried at 23 ° C. for 1 day to form an antifouling coating film, and further, the antifouling coating composition is applied on the surface of the antifouling coating film so that the dry film thickness is 150 μm. The sample was dried at 23 ° C. for 7 days to form an antifouling coating film, and a test plate with an antifouling coating film was prepared.

This test plate with antifouling coating film is exposed in seawater in Nagasaki Bay, Nagasaki Prefecture, 100 mm from the water surface as an exposed part, and 200 mm below the water surface is always submerged as a submerged part to be immersed in a semi-submerged state. It was in a soaked state imitating. When the total area of the antifouling coating film in the seawater always submerged portion of the test plate is set to 100% every one month from the start of immersion, the area of the part to which aquatic organisms are attached on the antifouling coating film (hereinafter "Attached area") (%), the aquatic organism attached area was measured at the seawater submerged part and the water edge of 50 mm at all times, and the static stain resistance was evaluated based on the following evaluation criteria.
[Evaluation criteria]
0: The adhered area is 0%.
0.5: The adhered area is more than 0% and less than 10%.
1: The adhesion area is 10% or more and less than 20%.
2: The adhesion area is 20% or more and less than 30%.
3: The adhesion area is 30% or more and less than 40%.
4: The adhesion area is 40% or more and less than 50%.
5: The adhesion area is 50% or more and 100% or less.

[Resin Production Example A1]
The reaction was carried out under normal pressure and nitrogen atmosphere. A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introducing tube and a dropping funnel was charged with 538 g of xylene, and heated while stirring with a stirrer until the temperature of xylene reached 80 ° C. While maintaining the temperature of xylene in the reaction vessel at 80 ± 5 ° C., 500 g of triisopropylsilyl methacrylate (TIPSMA), 200 g of 2-methoxyethyl acrylate (MEA) and 300 g of methyl methacrylate (MMA) and 2,2′-azobis. A monomer mixture consisting of 8.5 g of isobutyronitrile (AIBN) was added dropwise to the reaction vessel over 2 hours using a dropping funnel. Then, after stirring at the same temperature for 1 hour, 1 g of AIBN was added 4 times every 30 minutes, and the liquid temperature was raised to 110 ° C. at a temperature rising rate of 10 ° C./h to complete the polymerization reaction. Next, 128.6 g of xylene was added to the reaction vessel, and the mixture was stirred until the solution became uniform to obtain a copolymer solution A1.
Table 2 shows the heating residue, viscosity, and Mw of the copolymer solution A1.

[Resin Production Examples A2 to A8 and Comparative Resin Production Examples B1 to B4]
A silylmethacrylate copolymer was prepared in the same manner as in Production Example A1 except that a monomer mixture having a composition shown in Table 2 or 3 was used instead of the monomer mixture used in Resin Production Example A1. Then, various physical properties were measured. The results are shown in Tables 2 and 3.
The abbreviations of the monomers used in Tables 2 and 3 are as follows.
TIPSMA: triisopropylsilyl methacrylate TIPSA: triisopropylsilyl acrylate MEA: 2-methoxyethyl acrylate MEMA: 2-methoxyethyl methacrylate MMA: methyl methacrylate BA: n-butyl acrylate

[Example 1]
<Preparation of antifouling coating composition>
13.2 parts by mass of xylene as a solvent, Solvesso No. 2.5 parts by mass of 100 (aromatic hydrocarbon solvent, manufactured by ExxonMobil), 4.8 parts by mass of gum rosin, 1 part by mass of ethyl silicate 28, and 16 parts by mass of copolymer solution A1 were added to each component. Were mixed using a paint shaker until the was uniformly dispersed or dissolved. Then, in a plastic container, 5 parts by mass of talc FC-1, 5 parts by mass of zinc oxide (Zinc Hua No. 3), 45 parts by mass of cuprous oxide NC301, 0.5 parts by mass of Novo Palm Red F5RK, titanium white R-5N. 2 parts by mass, 1 part by mass of copper omazine (copper pyrithione) and 2 parts by mass of Disparlon 4200-20X were added, and these components were dispersed by stirring for 1 hour using a paint shaker.

  After dispersion, 2.5 parts by mass of Disparlon A630-20X was further added, and the mixture was stirred for 20 minutes using a paint shaker. Then, the mixture was filtered through a filter net (opening: 80 mesh) to remove the residue, and the filtrate was obtained. (Coating composition AA1) was obtained. Table 4 shows the manufacturers of the above various additives. Various properties of the obtained coating composition AA1 were evaluated. The results are shown in Table 7.

[Examples 2 to 15 and Comparative Examples 1 to 9]
A coating composition was prepared and various properties were evaluated in the same manner as in Example 1 except that the types and amounts of the compounding ingredients were changed as shown in Tables 5-6. The results are shown in Tables 7-8. The coating compositions AA2 to AA15 and the coating compositions BB1 to BB9 shown in Tables 5 to 8 represent the coating compositions obtained in Examples 2 to 15 and Comparative Examples 1 to 9, respectively.

In Examples 1 to 15, it was revealed that a coating film having excellent long-term storage stability and excellent antifouling property and long-term durability was formed with any of the coating compositions.
On the other hand, in Comparative Example 1 in which the copolymer solution B1 containing a copolymer using 2-methoxyethyl methacrylate was used instead of 2-methoxyethyl acrylate, copper pyrithione, zinc oxide, and a rosin compound were used. Even if it is, sufficient antifouling property is not obtained (aquatic organisms always adhere to the submerged part and the water side after 3 months of immersion, and the adhered area is 20% or more and less than 30%, soaking for 6 months). At this time, aquatic organisms always adhered to the submerged part and at the water's edge, and the adhered area was 40% or more and less than 50%. Also, sufficient long-term durability was not obtained (evaluation of the amount of cracks after 3 months). The score is 1 and 5 months later and the evaluation score is 2).
In Comparative Example 2 in which the copolymer solution B2 containing a copolymer using triisopropylsilyl acrylate instead of triisopropylsilyl methacrylate was used, copper pyrithione, zinc oxide, and a rosin compound were used. However, the storage stability was inferior, the viscosity increased (10 poise) after 1 week, and the viscosity increased by 30 poise after 2 weeks. In addition, sufficient long-term durability was not obtained (the evaluation point of the amount of cracks was 1 after 2 months, and the evaluation point was 3 after 4 months). In addition, it was also inferior in antifouling property (aquatic organisms always adhered to the submerged part and the water after immersion for 3 months, and the adhered area was 10% or more and less than 20%. The area of attachment of aquatic organisms in the water portion was 30% or more and less than 40%.).

In the comparative example 3 in which the copolymer solution B3 containing the copolymer whose content of triisopropylsilylmethacrylate is 40% by mass, which is less than the range (45 to 75% by mass) of the present application, was used, copper pyrithione ( Even when B), zinc oxide (C), and rosin compound (D) are used, the antifouling property is particularly inferior (aquatic organisms are always attached to the submerged part and the water by immersion for 2 months, The area was 10% or more and less than 20%, and the area where aquatic organisms adhered was 40% or more and less than 50% at the submerged part and the waterside at the time of immersion for 6 months.) In addition, sufficient long-term durability was also obtained. It was not possible (the evaluation of the amount of cracks was 1 after 3 months, and the evaluation was 2 after 4 months).
In the comparative example 4 in which the copolymer solution B4 containing the copolymer whose content of triisopropylsilyl methacrylate exceeds the range (45 to 75% by mass) of the present application and is 80% by mass, copper pyrithione (B ), Zinc oxide (C), and rosin compound (D) are also inferior in antifouling property (always aquatic organisms adhere to the submerged part and the water by immersion for 2 months, and the adhesion area is It is 10% or more and less than 20%, and the area where the aquatic organisms are attached is 40% or more and less than 50% at the submerged part and the water at all times after immersion for 6 months.) Moreover, sufficient long-term durability cannot be obtained. (The evaluation point of the amount of cracks was 1 after 2 months, and the evaluation point was 3 after 5 months).

It contains a silyl methacrylate copolymer (A) containing 45 to 75% by mass of the structural unit (a1), 15 to 35% by mass of the structural unit (a2), and 0 to 35% by mass of the structural unit (a3). Even in the case, in Comparative Example 5 containing no copper pyrithione (B), the antifouling property is particularly poor (aquatic organisms are always attached to the submerged part and the water by immersion for 2 months, and the attached area is 10% or more. It was less than 20%, the aquatic organism adhesion area at the water's edge was 50% or more and 100% or less after immersion for 6 months, and sufficient long-term durability was not obtained (amount of cracks after 4 months). The evaluation score of 1 is 1, 5 months later. In Comparative Example 9 containing zinc pyrithione instead of copper pyrithione (B), the storage stability was extremely poor and the viscosity could not be measured after 1 week. In addition, it was particularly inferior in long-term durability (a rating of the amount of cracks after 1 month was 1 and a rating after 3 months was 3), and sufficient antifouling property was not obtained (soaking for 2 months). , The aquatic organisms were always attached to the submerged part and the water's edge, and the attachment area was 10% or more and less than 20%, and the aquatic organism's attachment area was 30% or more and less than 40% at the water's edge after 6 months of immersion.) .
It contains a silyl methacrylate copolymer (A) containing 45 to 75% by mass of the structural unit (a1), 15 to 35% by mass of the structural unit (a2), and 0 to 35% by mass of the structural unit (a3). Even in the case, in Comparative Example 6 containing no zinc oxide (C), sufficient antifouling property was not obtained (aquatic organisms adhered to the water by immersion for 2 months, and the adhered area was 10% or more and 20% or more). The amount of aquatic organisms adhering to the submerged part was always 20% or more and less than 30% and the amount of aquatic organisms adhering to the water was 30% or more and less than 40% after immersion for 6 months.) No long-term durability was also obtained (the evaluation score of the amount of cracks was 1 after 3 months, and the evaluation score was 2 after 4 months).
It contains a silyl methacrylate copolymer (A) containing 45 to 75% by mass of the structural unit (a1), 15 to 35% by mass of the structural unit (a2), and 0 to 35% by mass of the structural unit (a3). Even in the case, in Comparative Example 7 containing no rosin compound (D), the antifouling property was particularly poor (aquatic organisms always adhered to the submerged part and the waterside by immersion for 1 month, and the adhesion area was 10% or more. It was less than 20%, the aquatic organism adhesion area in the submerged part and at the waterside was always 50% or more and 100% or less after immersion for 6 months. Moreover, sufficient long-term durability was not obtained (4 The number of cracks was 1, 2 months later, and 2 months later. In Comparative Example 8 containing a versatic acid as an elution aid instead of the rosin compound (D), sufficient antifouling property was not obtained (aquatic organisms were always attached to the submerged part and the water at the immersion for 3 months). , The adhesion area was 20% or more and less than 30%, and the adhesion area of aquatic organisms at the submerged part and the waterside was always 30% or more and less than 40% after immersion for 6 months.), And sufficient long-term durability Was not obtained (the evaluation score of the amount of cracks was 2 after 3 months, and the evaluation score was 3 after 4 months).
Thus, as in the present invention, silyl methacrylate containing 45 to 75 mass% of the structural unit (a1), 15 to 35 mass% of the structural unit (a2), and 0 to 35 mass% of the structural unit (a3). When the system copolymer (A), copper pyrithione (B), zinc oxide (C), and rosin compound (D) are contained, the resulting coating film has excellent specificity and excellent storage stability. It was found that an antifouling coating composition having excellent properties and long-term durability can be obtained.

Claims (9)

45-75 mass% of the structural unit (a1) derived from triisopropylsilyl methacrylate, 15-35 mass% of the structural unit (a2) derived from 2-methoxyethyl acrylate, and a structural unit (a3) derived from methyl methacrylate. silyl methacrylate terpolymer containing from 5 to 35 wt% (a), copper pyrithione (B), zinc oxide (C), and an antifouling paint composition containing a rosin compound (D).   Further, inorganic copper compound (E), color pigment (F), extender pigment (G), pigment dispersant (H), plasticizer (I), anti-sagging agent (J), anti-settling agent (K), dehydrating agent The antifouling coating composition according to claim 1, containing at least one component selected from the group consisting of (L) and a solvent (M).   The silyl methacrylate-based terpolymer (A) has a structural unit (a1) derived from triisopropyl methacrylate of 50 to 70% by mass, a structural unit (a2) derived from 2-methoxyethyl acrylate of 20 to 30% by mass, The antifouling coating composition according to claim 1 or 2, which is a silyl methacrylate terpolymer (A) containing 5 to 30 mass% of a structural unit (a3) derived from methyl methacrylate.   The antifouling coating composition according to any one of claims 1 to 3, further comprising a dehydrating agent (L).   Further, the antifouling coating composition according to any one of claims 1 to 4, further comprising an inorganic copper compound (E). Antifouling coating film formed from the antifouling paint composition according to any one of claims 1-5. An antifouling substrate, wherein the antifouling coating film according to claim 6 is formed on a substrate. The antifouling substrate according to claim 7 , wherein the substrate is at least one selected from the group consisting of underwater structures, ships, and fishing gear. The step of applying an antifouling coating composition according to the substrate to any one of claims 1 to 5, or a step of impregnating a base material antifouling coating composition according to any one of claims 1 to 5 And a method for producing an antifouling substrate, which comprises a step of drying the antifouling coating composition and forming an antifouling coating film on the substrate in this order.