JPWO2009123263A1 - Antifouling paint composition for freshwater bodies, coating film thereof, and antifouling method - Google Patents

Abstract

The antifouling paint composition for fresh water according to the present invention comprises (A) formula (I): CH2 = C (R1) -COO-MO-CO-C (R1) = CH2 [in formula (I), M is magnesium, zinc or copper, and R1 is independently a hydrogen atom or a methyl group. And a metal salt bond-containing polymer containing the component unit (a1) derived from the (meth) acrylic acid metal salt monomer (a1) represented by the formula (B) and an ester group, a hydroxyl group and a carboxyl group. And an alicyclic hydrocarbon resin having at least one group. When the antifouling paint composition for fresh water according to the present invention is used, it is excellent in strength even after being immersed in fresh water, and the adhesion after the immersion in fresh water when the coating interval is open is maintained. After that, it is possible to form an antifouling coating film that is not excessively consumed in seawater and that has an appropriate antifouling property while maintaining appropriate coating wearability in seawater.

Description

  The present invention relates to an antifouling paint composition for freshwater bodies, a coating film thereof, and an antifouling method, and more specifically, a ship constructed in a large river (freshwater) such as China and Vietnam as well as the ocean (saltwater). Anti-fouling paint composition applicable to fresh water bodies, anti-fouling paint film applicable to fresh water areas, base material with anti-fouling paint film applicable to fresh water areas, and anti-fouling anti-fouling coating material on substrate surface The present invention relates to a method for forming an antifouling coating film and an antifouling method for a substrate.

  In recent years, in China and other continents, along with economic development, not only port areas facing the ocean such as the Pacific Ocean, but also large river basins such as the Yellow River and the Yangtze River, the industry has become increasingly popular, and construction of large ocean-going vessels Has become popular.

  However, when an antifouling paint exclusively for marine vessels, such as a conventionally known cuprous oxide-containing hydrolyzable antifouling paint, is directly applied to ships used mainly in fresh water, such as large rivers, the coating is applied. The film has a problem that the resistance to fresh water is not sufficient, and when a ship with such a coating is built at a shipyard in the river water area, the coating is noticeably softened, and in some cases In some cases, defects such as blistering, cracks, and peeling occurred.

  In JP-A-2006-70104 (Patent Document 1), as an antifouling coating composition for solving such a problem, a sub-surface treated with a specific metal salt copolymer [A] and a higher fatty acid is disclosed. A fresh water region antifouling paint composition comprising copper oxide [B] is disclosed.

  On the other hand, JP 2005-15531 A (Patent Document 2) and JP 2006-152205 A (Patent Document 3) describe a hydrolyzable resin and an alicyclic hydrocarbon resin having a functional group such as an ester group. An antifouling paint containing is disclosed, and as a hydrolyzable resin, an acrylic resin side chain,

(Where X is

, K is 0 or 1, Y is a hydrocarbon, M is a divalent metal, and A is an organic acid residue of a monobasic acid. )
A group represented by

(Wherein, R ^1, R ² and R ³ are the same or different and each represents a hydrocarbon residue having 1 to 20 carbon atoms.)
An acrylic resin having a group represented by:

  These antifouling paints are intended for antifouling of underwater structures (such as ships and fishing nets) used in seawater, and are not supposed to be used for antifouling of underwater structures used in freshwater bodies.

JP 2006-70104 A JP 2005-15531 A JP 2006-152205 A

  However, further improvements are required for the freshwater region antifouling paint composition described in Patent Document 1. Further, it was found that the water resistance of the coating film formed from the antifouling paint described in each of Patent Documents 2 and 3 is drastically insufficient when used in fresh water.

  The present invention has been made in view of such problems in the prior art, and is excellent in strength even after being immersed in fresh water, and even after being immersed in fresh water even when the coating interval is widened. Adhesion (adhesion between antifouling paints) is maintained, and after being immersed in fresh water, the wear level does not become excessive in seawater, and practical film consumption in seawater is maintained and prevented. An object of the present invention is to provide an antifouling coating composition capable of forming an antifouling coating film having excellent soiling properties, an antifouling coating film exhibiting such an effect, and a substrate provided with such an antifouling coating film It is said.

  Moreover, this invention aims at providing the formation method of the antifouling coating film which exhibits the above effects.

  A further object of the present invention is to provide a substrate antifouling method capable of exhibiting the effects described above.

  As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by using a specific metal salt bond-containing polymer and an alicyclic hydrocarbon resin as essential components, thereby completing the present invention. It was.

The antifouling paint composition for freshwater bodies of the present invention,
(A) formula _{(I): CH 2 = C} (R 1) -COO-M-O-CO-C (R 1) = CH 2
[In formula (I), M is magnesium, zinc or copper, and R ¹ is independently a hydrogen atom or a methyl group. ]
A metal salt bond-containing polymer containing a component unit (a1) derived from a (meth) acrylic acid metal salt monomer (a1) represented by:
(B) It contains the alicyclic hydrocarbon resin which has at least 1 group chosen from an ester group, a hydroxyl group, and a carboxyl group.

  The metal salt bond-containing polymer (A) further contains a component unit (a2) derived from another unsaturated monomer (a2) that can be copolymerized with the monomer (a1). In general, the content of the component unit (a1) is 5 to 100% by weight, and the content of the component unit (a2) is 0 to 95% by weight.

  The antifouling paint composition for freshwater bodies contains the alicyclic hydrocarbon resin (B), preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the metal salt bond-containing polymer (A). To do.

  The fresh water-corresponding antifouling paint composition may further contain an extender pigment, and zinc oxide is preferred as the extender pigment.

  The fresh water region antifouling coating composition may further contain an inorganic antifouling agent, and cuprous oxide is preferred as the inorganic antifouling agent.

  The fresh water region antifouling paint composition may further contain an organic antifouling agent. Examples of the organic antifouling agent include pyrithione compounds, triorganoboron and amine complexes thereof, and 4,5-dichloro-2. At least one compound selected from the group consisting of -n-octyl-4-isothiazolin-3-one is preferred.

  The antifouling paint composition for freshwater bodies is another solid resin (that is, a resin solid at room temperature other than the metal salt bond-containing polymer (A) and the alicyclic hydrocarbon resin (B)). The other solid resin preferably contains a rosin and / or a terpene phenol resin.

  The freshwater region-compatible antifouling coating film of the present invention is formed from the freshwater region-compatible antifouling coating composition.

  The substrate with antifouling coating for fresh water according to the present invention is characterized in that the surface of the substrate is coated with the antifouling coating for fresh water.

  As this base material, an underwater structure and a ship outer plate are preferable.

  The method for forming an antifouling coating film for a fresh water region on the surface of the substrate according to the present invention is applied by applying or impregnating the antifouling coating composition for a fresh water region onto the surface of the substrate, and then curing. It is characterized by forming a film.

  The antifouling method for a base material according to the present invention is characterized in that the antifouling coating film is formed by applying or impregnating the antifouling paint composition for fresh water bodies onto the surface of the base material, and then curing. Yes.

  According to the present invention, after being immersed in fresh water, the strength is excellent, and the adhesion (adhesion to the base material) after the immersion in fresh water when the coating interval is maintained is maintained. An antifouling paint composition capable of forming an antifouling coating film that does not become excessively depleted in seawater and that has an appropriate antifouling property while maintaining adequate film wear in seawater. And a base material provided with such an antifouling coating film are provided.

  Moreover, according to this invention, the formation method of the antifouling coating film corresponding to a fresh water area to the base-material surface which can exhibit the above effects is provided.

  Furthermore, according to this invention, the antifouling method of a base material which can exhibit the above effects is provided.

  Hereinafter, the antifouling paint composition for fresh water according to the present invention, the antifouling coating for fresh water, the substrate with the antifouling coating for fresh water, the antifouling coating for fresh water on the substrate surface The forming method and the antifouling method of the substrate will be described in more detail.

[Anti-fouling antifouling paint composition]
The antifouling paint composition for fresh water according to the present invention (hereinafter also simply referred to as “antifouling paint composition”) includes a metal salt bond-containing polymer (A) as described below, and an alicyclic hydrocarbon. Resin (B) is contained.

<(A) Metal salt bond-containing polymer>
The metal salt bond-containing polymer (hydrolyzable metal crosslinked polymer) (A) (hereinafter also simply referred to as “polymer (A)”)
Formula _{(I): CH 2 = C} (R 1) -COO-M-O-CO-C (R 1) = CH 2
[In formula (I), M is magnesium, zinc or copper, and R ¹ is independently a hydrogen atom or a methyl group. ]
The component unit (a1) derived from the (meth) acrylic acid metal salt monomer (a1) represented by the formula (hereinafter also simply referred to as “monomer (a1)”) is contained.

  The structure of the component unit (a1) is mainly composed of

It is considered that the structure is represented by

  The monomer (a1) may be contained in the obtained polymer without necessarily using the (meth) acrylic acid metal salt monomer (a1) as a monomer during the production of the metal salt bond-containing polymer (A). As long as the derived component unit (component unit (a1)) is present, the production method of the polymer (A) is not particularly limited.

As the (meth) acrylic acid metal salt monomer (a1), (CH ₂ ═CHCOO) ₂ Mg, (CH ₂ ═C (CH ₃ ) COO) ₂ Mg, (CH ₂ ═CHCOO) (CH ₂ ═C (CH ₃₎ COO), such as Mg (meth) magnesium _{acrylate, (CH 2 = CHCOO) 2} Zn, (CH 2 = C (CH 3) COO) 2 Zn, (CH 2 = CHCOO) (CH 2 = C (CH ₃₎ COO), such as Zn (meth) zinc _{acrylate, (CH 2 = CHCOO) 2} Cu, (CH 2 = C (CH 3) COO) 2 Cu, (CH 2 = CHCOO) (CH 2 = C (CH ₃₎ COO) (meth) acrylic acid copper such as Cu and the like.

  The component unit (a1) may be included singly or in combination of two or more. For example, the component unit (a1) may include a component unit derived from zinc (meth) acrylate and a component unit derived from copper (meth) acrylate.

  In addition to the component unit (a1) derived from the monomer (a1), the metal salt bond-containing polymer (A) can be copolymerized with this monomer (a1). Having the component unit (a2) derived from the “mer (a2)” is desirable in terms of adjusting the elution rate of the resin.

  Examples of the “other unsaturated monomer (a2)” include the following monobasic acid metal (meth) acrylate (a21) and other unsaturated monomer (a22).

  Therefore, this metal salt bond-containing polymer (A) is derived from the following monobasic acid metal (meth) acrylate (a21) in addition to the component unit (a1) derived from the monomer (a1). The component unit (a21) may be present, or the component unit (a22) derived from another unsaturated monomer (a22) may be present. These component unit (a21) and component unit ( Both of a22) may exist.

  The monobasic metal (meth) acrylate (a21) is represented by the following formula (II).

^{_{CH 2 = C (R 3)}} -COO-M-O-COR 2 ··· (II)
[In the formula (II), M is magnesium, zinc or copper, R ² is a non-polymerizable monovalent organic group, and R ³ is a hydrogen atom or a methyl group. ]
The organic group R ² is a monovalent saturated aliphatic group having 2 to 30 carbon atoms, preferably 9 to 20 carbon atoms; a monovalent unsaturated aliphatic group having 2 to 30 carbon atoms, preferably 9 to 20 carbon atoms. A hydrocarbon group such as a saturated or unsaturated monovalent alicyclic group having 3 to 20 carbon atoms, preferably 9 to 20 carbon atoms, a monovalent aromatic group having 6 to 30 carbon atoms, or a substituent thereof. The organic acid residue of the monobasic acid which consists of, etc. are mentioned.

  Among these, a monobasic acid comprising a monovalent saturated or unsaturated aliphatic group having 9 to 20 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 9 to 20 carbon atoms, or a substituent thereof. These organic acid residues are preferred from the viewpoint of resin viscosity, elution of the resin in the coating film, and storage stability of the paint.

The organic group R ² is represented by Versatic acid (R ^a R ^b R ^c C—COOH (R ^a , R ^b and R ^c are each independently an alkyl group)), and has 9 to 11 carbon atoms. (Mainly a mixture of carboxylic acids of 10), palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, An organic acid residue (R ² ) formed from a monobasic acid (R ¹ COOH) such as naphthenic acid is an antifouling coating composition obtained from the viewpoint of ease of synthesis of the metal salt bond-containing polymer (A). The metal salt-bonded polymer (A) can be gradually hydrolyzed from the coating film formed from the above to exhibit antifouling properties, and the environmental load when hydrolyzed is small, and the durability of the antifouling effect High point, table Good renewability, preferably the like of excellent recoatability on such repair painting.

Specifically, as CH ₂ ═C (R ³ ) —COO—MO—CO— in the monobasic metal (meth) acrylate (a21), specifically, zinc versatate (meth) acrylate (CH ₂ ═ ^{C (R 23) -COO-Zn} -O-CO- ( versatic acid residue)), zinc isostearate (meth) acrylate ^{_{(CH 2 = C (R 23}} ) -COO-Zn-O-CO- ( isostearic acid Residue)), copper (meth) acrylate of versatic acid (CH ₂ ═C (R ²³ ) —COO—Cu—O—CO— (residue of versatic acid)), copper (meth) acrylate of isostearate (CH ₂ ═C (R ²³ ) —COO—Cu—O—CO— (isostearic acid residue)) and the like. These monobasic acid metal (meth) acrylates (a21) are used singly or in combination of two or more.

  In addition, the monobasic acid metal (meth) acrylate (a21) is not necessarily used as a monomer when the metal salt bond-containing polymer (A) having the component unit (a21) derived from the monomer (a21) is produced. In any case, as long as the component unit (a21) is present in the obtained polymer, the production method of the polymer (A) is not particularly limited.

  Examples of the “other unsaturated monomer (a22)” include unsaturated compounds such as alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, and hydroxyalkyl (meth) acrylates. 1 to 20 alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates having 1 to 20 carbon atoms in the alkoxy group and 1 to 20 carbon atoms in the alkylene group, hydroxyalkyl having 1 to 20 carbon atoms in the hydroxyalkyl group (Meth) acrylate is preferred.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate,
Examples of the alkoxyalkyl (meth) acrylate include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxymethyl (meth) acrylate, and 3-methoxy. Butyl (meth) acrylate, 3-methyl-3-methoxybutyl (meth) acrylate, etc.
Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate.

  Among these, as other unsaturated monomer (a22), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate are coating film properties. From the viewpoint of sustaining elution of the resin from the coating film.

  These “other unsaturated monomers (a22)” may be used singly or in combination of two or more.

  In the metal salt bond-containing polymer (A), the component unit (a1) is usually 5 to 100% by weight (the total component unit amount in the polymer (A) is 100% by weight. The same shall apply hereinafter. ), Preferably 5 to 99.9% by weight, more preferably 20 to 99.9% by weight, and the component unit (a2) is usually 0 to 95% by weight, preferably 0.1 to 95% by weight. %, More preferably in an amount of 0.1 to 80% by weight, from the viewpoint of easy adjustment of the elution rate of the resin in the coating film.

  Further, in 100% by weight of the component unit (a2), the component unit (a21) derived from the monobasic metal (meth) acrylate (a21) is, for example, 0 to 90% by weight, and other unsaturated components. The said component unit (a22) derived from a monomer (a22) is contained in the quantity used as 100 to 10 weight%, for example.

  The number average molecular weight Mn of the metal salt bond-containing polymer (A) (polystyrene equivalent value; the same applies hereinafter. Measured by GPC. Measurement conditions: column; Super H2000 + H4000) is usually 1,000 to 100,000 (100,000). ), Preferably 1,000 to 10,000 (10,000) in view of the resin viscosity and the elution rate of the resin in the coating film.

  The total content of magnesium (Mg), zinc (Zn) and copper (Cu) in the metal salt bond-containing polymer (A) is usually 0.5 to 20% by weight, preferably 5 to 20% by weight. % (The amount of the metal salt bond-containing polymer (A) is 100% by weight) is desirable in that the resin viscosity, the storage stability of the paint, and the elution of the resin in the coating film are good.

The metal salt bond-containing polymer (A) can be produced by a conventionally known method. As a specific production method,
(Method 1): A method for producing the metal salt bond-containing polymer (A) by polymerizing the monomer (a1) together with the monomer (a2) as necessary;
(Method 2): Copolymerizable monomer capable of deriving divalent metal di (meth) acrylate (alkyl (meth) acrylate such as methyl methacrylate (MMA), acrylic acid, methacrylic acid, etc.) and divalent metal oxide (ZnO, MgO, CuO, etc.) and water are contacted (reacted) in a solvent (PGM, n-BuOH, xylene, etc.), and then the resulting reaction mixture (metal-containing reactant) Copolymer (a22) and, if necessary, the monomer (a21) in the presence of an initiator (AIBN, AMBN, t-butyl peroctoate, etc.), a chain transfer agent, etc. The method etc. which manufacture a metal salt bond containing polymer (A) by are mentioned.

<(B) Alicyclic hydrocarbon resin>
The antifouling coating composition of the present invention has an alicyclic hydrocarbon resin (B) having at least one functional group selected from the group consisting of an ester group, a hydroxyl group and a carboxyl group.

  Examples of the ester group include an RCOO- group and an ROCO- group (R is an alkyl group). Examples of the alkyl group R include an alkyl group having 1 to 10 carbon atoms.

  The said alicyclic hydrocarbon resin (B) may have only 1 type in an ester group, a hydroxyl group, and a carboxyl group, and may have 2 or more types.

  The alicyclic hydrocarbon resin (B) has the following formula (b1):

(M is an integer of 1-20.)
It may have a structural unit having a norbornene skeleton represented by:

  As the alicyclic hydrocarbon resin (B), for example, alicyclic hydrocarbon resins described in JP-A-2006-152205, [0029] to [0043] can be used. The hydrogen resin (B) can be obtained, for example, by copolymerizing a cyclopentadiene oligomer and a vinyl compound having a desired functional group under normal reaction conditions.

  As the cyclopentadiene oligomer, the following formula (b2):

(N is an integer of 0 to 20)
And, for example, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, pentacyclopentadiene, hexacyclopentadiene, and the like. These may be used alone or in combination of two or more. May be used in combination. The cyclopentadiene oligomer can be obtained by heat treatment of dicyclopentadiene (conditions: for example, 0.1 to 60 hours, 125 to 250 ° C.).

  Examples of vinyl compounds having an ester group include vinyl alcohol esters such as vinyl acetate and vinyl propionate, and (meth) acrylate esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. Examples of the vinyl compound having a hydroxyl group include allyl alcohol and a hydroxyl group-containing vinyl compound such as hydroxyethyl (meth) acrylate; the vinyl compound having a carboxylic acid group includes (meth) acrylic acid, maleic anhydride, Examples thereof include vinyl carboxylic acids such as maleic acid. These vinyl compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Further, the cycloaliphatic hydrocarbon resin (B) can be obtained by further reacting a vinyl compound with a cyclopentadiene oligomer into which a functional group has been introduced. If the resin (B) has an ester group, an acid can be obtained. The said alicyclic hydrocarbon resin (B) can also be obtained by half esterification of an anhydride.

  The number average molecular weight (value in terms of polystyrene by GPC (gel permeation chromatography)) of the alicyclic hydrocarbon resin (B) is preferably 150 to 2000, more preferably 200 to 1000. If it is smaller than the above range, it may not contribute to improving the strength of the resulting coating film, and if it is larger than the above range, the leveling property at the time of forming the coating film may be lowered.

  The softening point (JIS K 2207 ring and ball type) of the alicyclic hydrocarbon resin (B) is preferably 60 to 150 ° C, more preferably 75 to 150 ° C. If it is smaller than the above range, it may not contribute to the improvement of the strength of the resulting coating film, and if it is larger than the above range, the leveling property and flexibility when forming the coating film may be lowered.

  When the alicyclic hydrocarbon resin (B) has an ester group, the saponification value (JIS K 0070) is preferably 100 to 300 mgKOH / g, more preferably 150 to 200 mgKOH / g. If it is smaller than the above range, the compatibility with the paint components may be poor, and if it is larger than the above range, it may be difficult to adjust the fine solubility in seawater that is not strongly hydrophilic due to the ester group. .

  When the alicyclic hydrocarbon resin (B) has a hydroxyl group, the hydroxyl value (JIS K 0070) is preferably 50 to 300 mgKOH / g, more preferably 200 to 250 mgKOH / g. If it is smaller than the above range, it may be difficult to ensure the fine solubility in seawater, and if it is larger than the above range, the compatibility with the paint component may be inferior.

  When the said alicyclic hydrocarbon resin (B) has a carboxyl group, the acid value becomes like this. Preferably it is 30-250 mgKOH / g, More preferably, it is 50-200 mgKOH / g. When it is smaller than the above range, it may be difficult to ensure fine solubility in seawater. When it is larger than the above range, the alicyclic hydrocarbon resin (B) becomes too hard and fragile. There is.

  As a commercial item of the said alicyclic hydrocarbon resin (B) containing an ester group, quinton 1500, quinton 1525L (brand name, the product made from Nippon Zeon) etc. can be mentioned, The said alicyclic containing a hydroxyl group. As a commercial item of hydrocarbon resin (B), Quinton 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.) and the like can be given.

  The said alicyclic hydrocarbon resin (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the alicyclic hydrocarbon resin (B) in the antifouling coating composition of the present invention is such that the metal salt bonding is performed from the viewpoints of reducing swelling of the coating film, preventing the occurrence of swelling, and maintaining the wear of the coating film. Preferably it is 0.1-100 weight part with respect to 100 weight part of containing polymer (A) (solid content), More preferably, it is 0.1-50 weight part, More preferably, it is 0.1-25 weight part. .

  In addition to the metal salt bond-containing polymer (A) and the alicyclic hydrocarbon resin (B), which are essential components, the freshwater body antifouling paint composition of the present invention further contains the following components: You may do it.

<Inorganic antifouling agent>
The antifouling coating composition of the present invention may contain an inorganic antifouling agent. When the antifouling coating composition of the present invention contains an inorganic antifouling agent, it is desirable in that the obtained coating film is excellent in antifouling property, and is excellent in physical properties of the coating film, particularly in crack resistance.

  Examples of the inorganic antifouling agent include copper and / or an inorganic copper compound. The copper and / or inorganic copper compound is not particularly limited in its average particle size and particle size distribution. For example, when the copper and / or inorganic copper compound has an average particle size of 6 to 50 μm, for example, There is a tendency that an antifouling coating film excellent in long-term antifouling property can be obtained because of excellent persistence of decomposition, continuous coating film consumption (constant coating film consumption) for a long period of time.

  The inorganic copper compound may be any of inorganic copper compounds, for example, cuprous oxide, copper thiocyanide (cuprous thiocyanate, rhodan copper), basic copper sulfate, basic copper acetate, base Copper carbonate, cupric hydroxide, and the like, and such a copper compound can be used alone or in combination of two or more in place of copper.

  As the copper and / or inorganic copper compound, cuprous oxide is desirable in that the obtained coating film is excellent in antifouling property, the physical properties of the coating film, particularly in crack resistance, and the like.

  The content of the inorganic antifouling agent is usually 0.1 to 500 parts by weight, preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the polymer (A) (solid content). If it exists, it is desirable at the point that the coating film obtained is excellent in antifouling property, the coating film physical property surface, especially crack resistance. On the other hand, if it is less than this range, the coating film tends not to exhibit a sufficient antifouling effect, and the renewability of the coating film surface tends to be inhibited. There is a tendency for cracks to occur.

<Organic antifouling agent>
The antifouling coating composition of the present invention may contain an organic antifouling agent. When the antifouling paint composition of the present invention contains an organic antifouling agent, the resulting coating film exhibits antifouling ability particularly in highly fouled sea areas where the fouling is severe, durability of the antifouling effect, surface renewal It is preferable at the point that it is excellent in property.

In the present invention, the organic antifouling agent is a metal-pyrithione represented by the following formula [III] and its derivative (pyrithione compound) [in the formula [III], R ^{1 to} R ⁴ are each independently a hydrogen atom, An alkyl group, an alkoxy group or a halogenated alkyl group, M represents a metal such as Cu, Na, Mg, Zn, Ca, Ba, Pb, Fe, Al, etc. Then, as M, Cu and Zn are preferable. n represents a valence. ]:

And at least one organic antifouling agent selected from the group consisting of triorganoboron and its amine complex, and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. This is particularly preferred from the viewpoint of excellent antifouling properties of the film and storage stability of the paint.

  In the present invention, the organic antifouling agent is copper pyrithione, zinc pyrithione, triphenylboron pyridine complex, 4-isopropylpyridine-diphenylmethylborane complex and 4,5-dichloro-2-n-octyl-4-isothiazoline- It is particularly preferable that at least one selected from the group consisting of 3-ones is excellent in terms of a good balance between the storage stability of the paint, the wear of the coating film, and the durability of the antifouling property.

  The content of the organic antifouling agent is usually 0.1 to 200 parts by weight, preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the polymer (A) (solid content). The antifouling property of the resulting antifouling coating film, in particular, the durability thereof is good (that is, the degree of coating film consumption is low), the load on the environment is low, and the coating film water resistance is excellent. Desirable in terms.

<External pigment>
The extender pigment has a low refractive index and is transparent and does not hide the coated surface when kneaded with oil or varnish. Examples of such extender pigments include zinc oxide (zinc white), talc, silica, mica, Examples include clay, diatomaceous earth, calcium carbonate, kaolin, alumina white, which is also used as an anti-settling agent, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, which are also used as a matting agent. Among these, zinc oxide (zinc white) is preferable because it improves the strength of the coating film, and an extender pigment selected from the group consisting of talc, clay, diatomaceous earth, and silica is preferable because it reduces the internal stress of the coating film. .

  These extender pigments may be used alone or in combination of two or more. Moreover, the wear degree of a coating film can be adjusted with the kind of extender.

  The content of the extender pigment is usually 0.1 to 400 parts by weight, preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the metal salt bond-containing polymer (A). Thus, it is possible to achieve both the cost reduction and increase effect of the obtained coating material and the transparency, fleshiness and crack resistance of the obtained coating film.

<Coloring pigment>
As the coloring pigment, conventionally known various organic and inorganic pigments can be used.

  Examples of organic pigments include carbon black, naphthol red, and phthalocyanine blue.

  Examples of inorganic pigments include bengara, barite powder, titanium white, and yellow iron oxide. Various colorants such as dyes may also be included.

  In the present invention, as the color pigment, as the inorganic color pigment, any of petals, titanium white, and yellow iron oxide is particularly preferable in terms of coloring power, and the organic pigment also has a particularly vivid color coating film. It is preferable in that it can be provided and has less discoloration.

  The content of the color pigment is usually about 0.1 to 200 parts by weight, preferably about 0.1 to 100 parts by weight with respect to 100 parts by weight of the metal salt bond-containing polymer (A).

<Anti-sagging / Anti-settling agent (fading agent)>
The antifouling coating composition of the present invention may further contain a sagging prevention / antisettling agent (fading agent).

  Examples of the anti-sagging and anti-settling agent (fading agent) include Al, Ca, Zn amine salts, stearate salts, lecithin salts, alkyl sulfonate salts, etc .; polyethylene wax, amide wax, hydrogenated castor oil wax Organic waxes such as polyamide wax and oxidized polyethylene wax; synthetic fine silica and the like are commercially available products such as “DISPARON 305”, “DISPARON 4200-20”, “DISPARON” manufactured by Enomoto Kasei Co., Ltd. A630-20X ".

  The content of the anti-sagging / precipitating agent (fading agent) is usually 0.1 to 100 parts by weight, preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the metal salt bond-containing polymer (A). About a part.

<Other solid resins>
In the antifouling coating composition of the present invention, a solid resin other than the polymer (A) (also referred to as “other solid resin” in the present invention) as a coating film forming component is contrary to the object of the present invention. Such “other solid resins” include difficult or water-insoluble resins and water-soluble resins, and terpene phenol resins can be used as long as they are difficult or water-insoluble resins. , Acrylic resin, acrylic silicone resin, unsaturated polyester resin, fluororesin, polybutene resin, silicone rubber, urethane resin (rubber), epoxy resin, polyamide resin, vinyl chloride copolymer resin, chlorinated rubber (resin), chlorinated olefin Resin, styrene / butadiene copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, alkyd resin, coumarone resin, petroleum resin, etc. It is. The terpene phenol resin is insoluble in water but has little adverse effect on the wear of the coating film. Examples of commercially available terpene phenol resins include terpene phenol YP90L (trade name, manufactured by Yasuhara Chemical Co., Ltd.).

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

  Other solid resins are preferably rosin and terpene phenol resins from the viewpoint of maintaining the coating film wearability.

  The content of the other solid resin is usually 0.1 to 100 parts by weight, preferably about 0.1 to 50 parts by weight with respect to 100 parts by weight of the metal salt bond-containing polymer (A).

<Other ingredients>
In addition to the above components, the antifouling coating composition of the present invention includes a thixotropic agent, an inorganic dehydrating agent (stabilizer), an antifungal agent, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, a heat A conductivity improver, an adhesion-imparting agent, and the like may be further included.

<Solvent>
In the antifouling coating composition of the present invention, the above-described components are usually dissolved or dispersed in a solvent. As this solvent, for example, various solvents such as aliphatic, aromatic, ketone, ester, and ether that are usually blended in antifouling paints can be used. Examples of the aromatic solvent include xylene and toluene. Examples of the ketone solvent include methyl isobutyl ketone (MIBK). Examples of the ether solvent include propylene glycol monomethyl ether, Examples include propylene glycol monomethyl ether acetate (PMAC).

[Production of antifouling paint composition]
The antifouling coating composition of the present invention comprises the above-mentioned polymer (A) and alicyclic hydrocarbon resin (B), which are essential components, and other components described above as raw materials, if necessary. These raw materials can be blended at once or in any order, and can be produced by stirring and mixing, etc., using a conventionally known method as appropriate.

  For the stirring / mixing of each component, a conventionally known mixing / stirring apparatus such as a loss mixer, a planetary mixer, or a universal Shinagawa stirrer can be used.

[Anti-fouling anti-fouling coating, etc.]
The freshwater region-compatible antifouling coating film of the present invention is formed from the freshwater region-compatible antifouling coating composition.

  The substrate with antifouling coating for fresh water according to the present invention is characterized in that the surface of the substrate is coated with the antifouling coating for fresh water.

  As this base material, an underwater structure and a ship outer plate are preferable.

  In addition, as an aspect (form which coat | covers the base material surface with the fresh water region antifouling coating film of this invention) as an aspect (form which coat | covers the base material surface with the fresh water region antifouling coating film of this invention) on the base material surface, it is directly on the base material surface. The aspect which forms the said antifouling coating film corresponding to a fresh water area, and the aspect which forms the said antifouling coating film corresponding to a fresh water area further on the coating film already formed in the base-material surface are mentioned.

  The method for forming an antifouling coating film for a fresh water region on the surface of the substrate according to the present invention is applied by applying or impregnating the antifouling coating composition for a fresh water region onto the surface of the substrate, and then curing. It is characterized by forming a film.

  The base material antifouling method of the present invention is characterized in that the antifouling coating film is formed by applying or impregnating the antifouling paint composition for fresh water bodies onto the surface of the base material, and then curing. .

  A coating film formed by applying and curing the antifouling paint composition for fresh water according to the present invention on the surface of a base material such as a hull or an underwater structure is water (ie, in seawater or freshwater), for example, river water in China or the like. During the construction period of the ship at the shipyard in the area, even if the paint film is temporarily immersed in the river water, peeling and blistering are not likely to occur, so it can be applied not only to seawater but also to freshwater. It is suitable as a "corresponding type" coating film.

  The antifouling paint composition for fresh water according to the present invention is a variety of organisms that live in seawater or freshwater, for example, shellfish such as barnacles, mussels and oysters that live in seawater, and coelenterates such as cell plastics. New shipbuilding in seawater (saltwater) and freshwater (freshwater) areas, and hulls operated and operated in these seawater and freshwater areas. It can also be used for antifouling treatment for underwater structures.

  Antifouling treatment of ship hulls, particularly ship outer plates that come into contact with fresh water, and antifouling treatment of the surface of underwater structures, particularly underwater structures, are carried out on the surface of a hull or freshwater underwater structure constructed in fresh water. It is performed by applying the antifouling paint composition corresponding to freshwater bodies and forming an antifouling coating film.

  By applying such antifouling coating film forming method or antifouling method to ships or underwater structures constructed in freshwater areas, the surface of the ship skin or freshwater underwater structures in contact with freshwater A ship or underwater structure coated with the antifouling coating film formed from the antifouling paint composition for fresh water bodies is obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited at all by this Example.

  In the following Examples, Comparative Examples, etc., “parts” means parts by weight unless it is contrary to the purpose.

  The details of the raw material for the antifouling coating composition are as follows.

  Moreover, the measuring method of various physical properties in the following examples etc. is as follows.

<Gardner viscosity measurement conditions>
The Gardner viscosity was measured at 25 ° C. at a resin concentration of 35% by weight according to JIS K7233 4.3 as described in JP-A-2003-55890.

<Solid content>
The solid content refers to the heating residue when the solvent, etc. is volatilized by heating and drying the reaction mixture containing the polymer, solvent, etc., paint, uncured coating film, etc., usually resin content and pigment It becomes a coating film forming component. In addition, the monomer etc. (Example: Table 2) which are contained in the paint etc. and can react and form resin (solid content) are also included in the solid content and calculated.

<Measurement of number average molecular weight Mn, weight average molecular weight Mw>
The weight average molecular weight Mw of a resin such as a metal-containing resin was eluted with DLC (dimethylformamide) to which 20 mM LiBr was added using two TSK-gel α-type separation columns (α-M) using HLC-8120GPC. It was used as a liquid and measured. The weight average molecular weight (Mw) was calculated | required as polystyrene conversion.

  Moreover, the number average molecular weight Mn of resin was calculated | required as polystyrene conversion by GPC same as the above.

[Production Example 1]
(Production of metal-containing monomer A-1)
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 85.4 parts of propylene glycol methyl ether (PGM) and 40.7 parts of zinc oxide and heated to 75 ° C. while stirring. Subsequently, a mixture consisting of 50.0 parts of methyl methacrylate (MMA), 36.1 parts of acrylic acid (AA), and 5 parts of water was dropped from the dropping funnel at a constant rate over 3 hours. After completion of the dropwise addition, the reaction solution became transparent from the milky white state. After further stirring for 2 hours, 36 parts of propylene glycol methyl ether (PGM) was added to obtain a transparent mixture solution A containing the metal-containing monomer A-1.

  The solid content (metal-containing monomer A-1) in the obtained mixture solution A was 44.8% by weight. The composition and the like are shown in Table 2.

[Production Example 2]
(Production of metal-containing monomer A-2)
A transparent mixture solution E containing the metal-containing monomer A-2 was obtained in the same manner as in Production Example 1 except that 20.2 parts of magnesium oxide was used instead of 40.7 parts of zinc oxide.

  The solid content (metal-containing monomer A-2) in the obtained mixture solution E was 44.6% by weight. The composition and the like are shown in Table 2.

[Production Example 3]
(Production of metal salt bond-containing polymer (A1))
A four-necked flask equipped with a cooler, thermometer, dropping funnel and stirrer was charged with 15 parts of propylene glycol methyl ether, 57 parts of xylene and 4 parts of ethyl acrylate, and the temperature was raised to 100 ° C. while stirring.

  Subsequently, 1 part of methyl methacrylate (MMA), 70.2 parts of ethyl acrylate (EA), 5.4 parts of 2-methoxyethyl acrylate (2-MEA), and the mixture solution A obtained in Production Example 1 were added from the dropping funnel. 52 parts, 10 parts of xylene, 1 part of chain transfer agent (manufactured by NOF Corporation, “NOFMER MSD”), 2.5 parts of azobisisobutyronitrile (AIBN, Nippon Hydrazine Industry Co., Ltd.), azobismethylbutyro A transparent mixture composed of 7 parts of nitrile (AMBN, Nippon Hydrazine Kogyo Co., Ltd.) was dropped at a constant rate over 6 hours (Drip process I).

  After completion of dropping, 0.5 part of t-butyl peroctoate (TBPO) and 7 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 4.4 parts of xylene was added to contain a metal salt bond. A resin composition containing the polymer (A1), free from insolubles, and pale yellow and transparent was obtained. Table 3 shows the molecular weight (Mn) of the obtained metal salt bond-containing polymer (A1) and the physical properties (Gardner viscosity, solid content (% by weight)) of the reaction mixture containing the polymer (A1).

[Production Example 4]
(Production of metal salt bond-containing polymer (A2))
A metal salt bond-containing polymer (A2) was produced in the same manner as in Production Example 3 except that the dropping components in the dropping step I were changed as shown in Table 3. The physical properties of the metal salt bond-containing polymer (A2) and the reaction mixture containing the polymer (A2) were evaluated in the same manner as in Production Example 3 (Production Example of Polymer (A1)). The results are shown in Table 3.

[Example 1]
<Preparation of antifouling paint composition>
A plastic container having a capacity of 1000 ml was charged with xylene (88 g) and Solvesso 150 (32 g) as a solvent, and then the metal salt bond-containing polymer (A1) (280 g) and alicyclic hydrocarbon resin obtained in Production Example 4 (Quinton 1500, 4 g) was added and dispersed using a paint shaker until uniform.

  Next, talc FC-1 (136 g), zinc oxide (144 g), Nova Palm Red F5RK (4 g), RED IRON OXIDE BB (12 g), PK boron (56 g), Zinc Omadine (16 g), Disparlon 4200-20X (8 g) And 200 g of glass beads were added, and these were dispersed for 1 hour using a paint shaker.

  Further, Disparlon A630-20X (16 g) was added, and the mixture obtained by dispersing for 10 minutes with a paint shaker was filtered through an 80 mesh filter screen to prepare an antifouling paint composition.

<State of paint film after immersion in fresh water>
The antifouling coating composition obtained in Example 1 was applied directly to a hard vinyl chloride resin plate (50 mm × 50 mm × thickness 1.5 mm) that had not been primed so that the dry film thickness would be 300 μm. And then dried. The obtained test plate with a coating film was immersed in fresh water at 35 ° C. for 1 month, and then the appearance of the coating film was visually observed and evaluated according to the following criteria. The results are shown in Table 4.

    ○: There was no change in appearance (swelling, cracks, swelling, etc.).

    X: The coating film was significantly swollen.

<Degree of wear of antifouling paint film after immersion in fresh water in sea water>
The antifouling paint composition obtained in Example 1 was applied directly to a hard vinyl chloride resin plate (50 mm × 50 mm × thickness 1.5 mm) that had not been primed so that the dry film thickness would be 150 μm. And then dried. The obtained test plate with a coating film was immersed in fresh water at 35 ° C. for one month, and then attached to a rotating drum installed in seawater in Nagasaki Bay, Nagasaki Prefecture, and rotated at a peripheral speed of 15 knots. Consumable film thickness (total amount μm of coating film consumption immediately after installation, coating film consumption level) was measured for 4 months. The results are shown in Table 4.

<Interfacial accelerated exposure adhesion / fresh water immersion>
An epoxy primer (epoxy AC paint, trade name “Banno 500”, manufactured by China Paint Co., Ltd.) is applied to a sandblasted steel plate (70 mm × 150 mm × thickness 1.6 mm) so that the dry film thickness becomes 150 μm. Then, an epoxy binder (epoxy binder paint trade name “Banno 500N”, manufactured by China Paint Co., Ltd.) was applied so that the dry film thickness was 100 μm, and further obtained in Example 1. A test plate was prepared by applying the antifouling coating composition so that the dry film thickness was 100 μm. The coating interval of each coating film was 1 day. The test plate was set on a sunshine / weather meter device, irradiated with a sunshine carbon arc light source for 78 hours, and the antifouling coating composition obtained in Example 1 was again applied onto the coating film so that the dry film thickness was 100 μm. Painted and dried. The obtained test plate with a coating film was immersed in fresh water at 40 ° C., and adhesion after 30 days (knife test) was confirmed. The results are shown in Table 4.

<Degree of paint wear in seawater>
The antifouling paint composition obtained in Example 1 was applied directly to a hard vinyl chloride resin plate (50 mm × 50 mm × thickness 1.5 mm) that had not been primed so that the dry film thickness would be 150 μm. The test plates with coatings obtained were attached to a rotating drum installed in seawater (in Nagasaki Bay, Nagasaki Prefecture), rotated at a peripheral speed of 15 knots, and a consumable film thickness (installed every month) The total amount [mu] m of coating film consumption immediately afterwards, and the degree of coating film consumption) was measured for 4 months. The results are shown in Table 4.

<Standing antifouling property of antifouling coating film>
Sand blasted steel plate (length 300mm x width 100mm x thickness 3.2mm) and epoxy anticorrosive paint (epoxy AC paint, trade name "Banno 500", manufactured by China Paint Co., Ltd.) have a dry film thickness of 150µm Then, an epoxy binder paint (trade name “Banno 500N”, manufactured by China Paint Co., Ltd.) was applied so that the dry film thickness was 100 μm.

  Subsequently, the antifouling paint composition obtained in Example 1 was applied once so as to have a dry film thickness of 150 μm and dried to prepare a test plate with a coating film. The coating interval was set to 1 day / 1 coat between any paint (eg, “Banno 500”) and the paint (eg, “Banno 500N”) coated on the surface thereof.

  After the test plate was dried at room temperature for 7 days, it was immersed in Nagasaki Bay, Nagasaki Prefecture for 6 months, and the adhesion area (%) of attached organisms was examined every month during that period. The results are shown in Table 4.

  The evaluation criteria for static antifouling properties (evaluation criteria for aquatic organisms attached area) are as follows.

0: No attachment of aquatic organisms 0.5 ... Attachment area of aquatic organisms is about 10% 1 ... Attachment area of aquatic organisms is about 20% 3 ... The adhesion area of aquatic organisms is about 40% 4 ... The adhesion area of aquatic organisms is about 50% 5 ... The adhesion area of aquatic organisms is about 100%.

[Examples 2-14, Comparative Examples 1-4]
An antifouling paint composition was produced in the same manner as in Example 1 except that the blending composition was changed as shown in Table 2, and each antifouling paint composition was evaluated in the same manner as in Example 1. The results are shown in Table 4.

Claims (16)

(A) Formula (I):
^{_{CH 2 = C (R 1)}} -COO-M-O-CO-C (R 1) = CH 2
[In formula (I), M is magnesium, zinc or copper, and R ¹ is independently a hydrogen atom or a methyl group. ]
A metal salt bond-containing polymer containing a component unit (a1) derived from a (meth) acrylic acid metal salt monomer (a1) represented by:
(B) An antifouling paint composition for fresh water bodies, comprising an alicyclic hydrocarbon resin having at least one group selected from an ester group, a hydroxyl group and a carboxyl group.   The copolymer wherein the metal salt bond-containing polymer (A) further contains a component unit (a2) derived from another unsaturated monomer (a2) that can be copolymerized with the monomer (a1). The fresh water according to claim 1, wherein the content of the component unit (a1) is 5 to 100% by weight and the content of the component unit (a2) is 0 to 95% by weight. Anti-fouling paint composition for areas.   The alicyclic hydrocarbon resin (B) is contained in an amount of 0.1 to 100 parts by weight with respect to 100 parts by weight of the metal salt bond-containing polymer (A). Antifouling paint composition for freshwater bodies.   The fresh anti-fouling paint composition according to any one of claims 1 to 3, further comprising an extender pigment.   The antifouling paint composition for freshwater bodies according to claim 4, wherein the extender pigment is zinc oxide.   The inorganic antifouling agent is further contained, The antifouling paint composition for fresh water bodies according to any one of claims 1 to 5.   The antifouling paint composition for fresh water bodies according to claim 6, wherein the inorganic antifouling agent is cuprous oxide.   The organic antifouling agent is further contained, The antifouling paint composition for fresh water bodies according to any one of claims 1 to 7.   The organic antifouling agent is at least one compound selected from the group consisting of pyrithione compounds, triorganoboron and its amine complexes, and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. The antifouling paint composition for fresh water bodies according to claim 8, wherein   The fresh water region antifouling paint composition according to any one of claims 1 to 9, further comprising another solid resin.   The said other solid resin is a rosin and / or a terpene phenol resin, The antifouling paint composition corresponding to fresh water bodies according to claim 10.   A fresh water area-compatible antifouling coating film, which is formed from the fresh water area-type antifouling paint composition according to any one of claims 1 to 11.   A base material with a freshwater region-compatible antifouling coating film, wherein the surface of the substrate is coated with the freshwater region-compatible antifouling coating film according to claim 12.   The base material with an antifouling coating film for fresh water according to claim 13, wherein the base material is an underwater structure or a ship outer plate.   A surface of a substrate, wherein the surface of the substrate is coated or impregnated with the antifouling paint composition for freshwater bodies according to any one of claims 1 to 11, and then cured to form a coating film. A method for forming an antifouling coating film for freshwater bodies.   A base for forming an antifouling coating film by applying or impregnating the antifouling paint composition for freshwater bodies according to any one of claims 1 to 11 onto a surface of a substrate and then curing Antifouling method for wood.