JP2011026357A - Contamination-proof coating composition, manufacturing method for the composition, contamination-proof coating film formed using the composition, coated article having the coating film on surface, and contamination-proofing treatment method for forming the coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a contamination-proof coating composition capable of exhibiting stable solubility and contamination-proof effect in sea water from an initial stage and forming a coating film excellent in water-resistance and capable of effectively exhibiting contamination-proof effect over a long period of time, and further having a small amount of volatile organic compounds (VOCs) scattered into the atmosphere and high environmental safety. <P>SOLUTION: The contamination-proof coating composition includes (A) a polymer having a number average molecular weight of 1,000-20,000 obtained by polymerizing a polymerizable unsaturated carboxylic acid tri-organo silyl and (B) at least one zinc salt selected from a rosin zinc salt and a zinc salt of a rosin derivative. In the contamination-proof coating composition, (1) the weight ratio ((A)/(B)) of the content of the polymer (A) and the content of the zinc salt (B) is 45/55-10/90, (2) the content of non-volatile compound is 75 wt.% or higher, and (3) a rosin and a rosin derivative having a free carboxyl group are not substantially contained. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antifouling coating composition, a method for producing the composition, an antifouling coating film formed using the composition, a coated article having the coating film on the surface, and an antifouling forming the coating film. It relates to the processing method.

  Aquatic fouling organisms such as barnacles, cell plastics, blue mussels, scallops, sea squirts, blue sea breams, blue sea breams, slime, etc., become submarine structures such as ships (especially ship bottoms), fishing nets, fishing net accessories, etc. Adhering causes problems such as damage to the functions of the ship and the like, and the appearance.

  Conventionally, an antifouling paint containing an organic tin-containing copolymer has been applied to the surface of ships, fishing equipment, and underwater structures to prevent the attachment of water fouling organisms. For example, a coating film formed by applying an antifouling paint containing a polymer having a tributyltin group gradually dissolves in the seawater and the coating surface is constantly renewed. It is possible to prevent the adhesion of water fouling organisms to the membrane. Moreover, antifouling performance can be exhibited continuously by overcoating the coating after dissolution. However, the use of the antifouling paint has been stopped due to the problem of marine pollution.

In recent years, triorganosilyl ester group-containing copolymers having triorganosilyl groups that are less toxic and less burdensome on the environment than organotin groups have been developed as hydrolyzable copolymers instead of organotin-containing copolymers. Has been used. (References 1-12)
However, the coating film containing a triorganosilyl ester-containing copolymer uses a copolymer obtained by copolymerizing a triorganosilyl ester-containing monomer having a linear alkyl group such as a tri-n-butylsilyl group. Because the coating film has a high hydrolysis rate, the dissolution rate of the coating film gradually increases, and after a long period of time, the dissolution rate of the coating film becomes too large, and the water resistance is poor, causing swelling and cracks. There is a problem that long-term use is difficult.

  Therefore, triorganosilyl ester-containing copolymers in which all organo groups have branched alkyl groups have been studied (Patent Documents 6 to 12). However, the triorganosilyl ester-containing copolymer having only a branched alkyl group is improved in water resistance, but because the coating film has a low hydrolysis rate, it takes time until the coating film starts to dissolve. The antifouling effect was poor, and there was a problem that the aquatic fouling organisms adhered in the initial stage in the sea area where fouling organisms were active or in the low seawater temperature sea area.

  In order to solve these problems, attempts have been made to adjust the coating film dissolution rate by using a triorganosilyl ester-containing copolymer in combination with rosin (or a rosin derivative) (Patent Documents 2 to 10). ).

  However, when rosin (or a rosin derivative) is used, a part of it reacts with a metal compound contained in the coating composition at the time of coating production to form a metal salt, but its reactivity is not sufficient, so that free carboxylic acid is used. Rosin with acid (or rosin derivative) remains in the coating composition. In particular, when a large amount of rosin is used, there is a tendency that the ratio of the rosin (or rosin derivative) remaining in the coating composition increases. Since the rosin (or rosin derivative) has high hydrophilicity, the water resistance of the coating film is lowered, and as a result, the coating film tends to have abnormalities such as blisters and cracks.

  Therefore, a method of premixing an excess metal compound and rosin has also been proposed (Patent Documents 9 and 10). However, in such a method, even if an excessive amount of the metal compound is used, the metal compound and the rosin do not sufficiently react, so it is difficult to completely eliminate rosin (or rosin derivative) having a free carboxylic acid. is there.

  In recent years, due to environmental problems, solvent-based paints have been regulated worldwide because many organic solvents are volatilized in the air, and attempts have been made to reduce the content of organic solvents (patents). Documents 11 and 12) show that it is difficult to obtain an antifouling paint having good coating film properties and antifouling performance by these methods.

In the case of a new ship, in order to use the dock efficiently, the hull is built in the dock, the bottom of the hull is painted, the hull is floated on the sea outside the dock, the interior of the hull is then installed, etc. In some cases, re-entry and finish painting. However, since it takes about three months to float the ship on the sea and perform interior decoration, organisms adhere to the surface of the coating during this period, or even if the organism can be prevented from adhering, slime will adhere. There is. This organism and slime cannot be removed sufficiently even by washing with water. When finish coating is performed with organisms and slime attached, cracks, peeling, etc. may occur in the coating film during navigation, which has been a problem.
Japanese Patent Laid-Open No. 10-30071 JP 11-116857 A JP-A-11-116858 JP 2000-248228 A JP 2000-265107 A JP 2000-265107 A JP 2002-53796 A JP 2002-53797 A JP 2002-97406 A JP 2003-261816 A WO 2005/005516 A1 Japanese Patent Application Laid-Open No. 2005-082725

  In the seawater, the present invention can form a coating film that exhibits stable solubility and good antifouling effect from the beginning, has excellent water resistance, and can effectively exhibit the antifouling effect over a long period of time. It is an object of the present invention to provide an antifouling paint composition having a small amount of volatile organic compounds (VOC) scattered therein and having a high environmental safety.

  As a result of intensive studies to solve the above problems, the present inventor has found that a composition having a specific configuration can solve the above problems, and has completed the present invention.

That is, the present invention provides the following antifouling paint composition, a method for producing the composition, an antifouling coating film formed using the composition, a coated article having the coating film on the surface, and the coating film. It relates to the antifouling treatment method to be formed.
1. (A) a polymer having a number average molecular weight of 1,000 to 20,000, obtained by polymerizing a polymerizable unsaturated carboxylic acid triorganosilyl;
(B) An antifouling paint composition containing at least one zinc salt selected from rosin zinc salts and zinc salts of rosin derivatives,
(1) The weight ratio ((A) / (B)) between the content of the polymer (A) and the content of the zinc salt (B) is 45/55 to 10/90,
(2) The non-volatile content is 75% by weight or more,
(3) substantially free of rosin and rosin derivatives having a free carboxyl group,
Antifouling paint composition.
2. Item 2. The antifouling coating composition according to Item 1, wherein the polymer (A) has a number average molecular weight of 2,000 to 15,000 and a molecular weight dispersity of less than 2.5.
3. Item 3. The antifouling coating composition according to Item 1 or 2, wherein the polymer (A) has a glass transition temperature of 20 to 70 ° C.
4). Item 4. The antifouling coating composition according to any one of Items 1 to 3, wherein the polymer (A) is a triisopropylsilyl (meth) acrylate copolymer.
5. The triisopropylsilyl (meth) acrylate copolymer comprises (a) 30 to 60% by weight of triisopropylsilyl (meth) acrylate, (b) 10 to 50% by weight of methyl methacrylate, and (c) (a). The antifouling paint composition according to any one of Items 1 to 4, which is obtained by copolymerizing 0 to 60% by weight of (meth) acrylic acid ester other than (b).
6). The rosin zinc salt is at least one zinc salt selected from the group consisting of gum rosin zinc salt, wood rosin zinc salt and tall oil rosin zinc salt, and the zinc salt of the rosin derivative is a hydrogenated rosin zinc salt and a disproportionated rosin. Item 6. The antifouling coating composition according to Item 1 to 5, which is at least one zinc salt selected from the group consisting of zinc salts.
7). Item 7. The antifouling paint composition according to Item 1-6, wherein the content of nonvolatile components is 80% by weight or more, and the viscosity at 25 ° C. measured using a Stormer viscometer is 80 to 100 KU.
8). Item 8. The antifouling coating composition according to any one of Items 1 to 7, wherein the content of the volatile organic compound is less than 400 g / L.
9. The antifouling coating composition according to any one of Items 1 to 8, further comprising 10 to 100 parts by weight of zinc oxide with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B). .
10. Furthermore, the antifouling paint composition of the said claim | item 1-9 containing 100-400 weight part of cuprous oxide with respect to 100 weight part of total amounts of the said polymer (A) and the said zinc salt (B).
11. Item 11. The antifouling coating composition according to Item 10, wherein the cuprous oxide is cuprous oxide having an average particle size of 8 to 20 µm.
12 The antifouling coating composition according to any one of Items 1 to 11, further comprising 1 to 100 parts by weight of an organic antifouling agent relative to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B). .
13. Furthermore, the antifouling paint composition of the said item | term 1-12 containing 1-50 weight part of plasticizers with respect to 100 weight part of total amounts of the said polymer (A) and the said zinc salt (B).
14 Item 14. The antifouling coating composition according to Item 13, wherein the plasticizer is an epoxidized oil.
15. The antifouling coating composition according to any one of Items 1 to 14, further comprising a dehydrating agent in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B).
16. Item 16. The antifouling coating composition according to Item 15, wherein the dehydrating agent is at least one water binder selected from alkoxysilanes and alkyl orthoformate.
17. Furthermore, the antifouling paint composition of said claim | item 1-16 containing 1-50 weight part of fatty acid amide type dispersing agents with respect to 100 weight part of total amounts of the said polymer (A) and the said zinc salt (B). .
18. The antifouling processing method which forms an antifouling coating film on the surface of a to-be-coated-film formation object using the antifouling coating material composition of the said items 1-17.
19. The antifouling coating film formed using the antifouling paint composition of the said items 1-17.
20. Item 20. A coated article having the antifouling coating film according to Item 19 on the surface.
21. A method for producing an antifouling paint composition, comprising:
(A) a polymer having a number average molecular weight of 1,000 to 20,000, which is obtained by polymerizing a polymerizable unsaturated carboxylic acid triorganosilyl;
(B) mixing at least one zinc salt selected from rosin zinc salts and zinc salts of rosin derivatives;
(1) The weight ratio ((A) / (B)) between the content of the polymer (A) and the content of the zinc salt (B) is 45/55 to 10/90,
(2) The non-volatile content is 75% by weight or more,
(3) substantially free of rosin and rosin derivatives having a free carboxyl group,
A method for producing an antifouling paint composition.
22. In addition to the polymer (A) and the zinc salt (B), after further mixing a cuprous oxide having an average particle diameter of 3 to 10 μm, the obtained mixture is mixed and dispersed using a disperser. The manufacturing method of the antifouling coating composition of 21.
23. A mixture obtained by mixing the polymer (A) and the zinc salt (B) is mixed and dispersed using a disperser, and then cuprous oxide having an average particle size of 10 to 20 μm is added and mixed. Item 22. A method for producing an antifouling paint composition according to Item 21 above.

Antifouling paint composition The antifouling paint composition of the present invention comprises:
(A) a polymer (polymer (A)) having a number average molecular weight of 1,000 to 20,000 obtained by polymerizing a polymerizable unsaturated carboxylic acid triorganosilyl;
(B) At least one zinc salt selected from rosin zinc salt and zinc salt of rosin derivative (zinc salt (B))
An antifouling paint composition comprising:
(1) The weight ratio ((A) / (B)) between the content of the polymer (A) and the content of the zinc salt (B) is 45/55 to 10/90,
(2) The non-volatile content is 75% by weight or more,
(3) It is substantially free of rosin and rosin derivatives having a free carboxyl group.

<Polymer (A)>
The antifouling coating composition of the present invention is a polymer obtained by polymerizing a polymerizable unsaturated carboxylic acid triorganosilyl (polymerized unsaturated carboxylic acid triorganosilyl unit-containing polymer), and has a number average molecular weight (Mn ) Contains a polymer of 1,000 to 20,000, preferably 2,000 to 15,000.

    By containing the said polymer (A), the antifouling performance can be exhibited effectively and the coating film which can prevent suitably the adhesion of a chickenpox fouling organism can be formed.

  When the Mn of the polymer (A) is 1,000 to 20,000, the coating film to be formed has good coating film physical properties (hardness and toughness of the coating film), so that cracks and peeling are unlikely to occur. As a result, the antifouling effect can be maintained for a long time. When Mn is less than 1,000, the amount of coating film dissolved becomes large, but the coating film becomes brittle and easily cracks. When Mn exceeds 20,000, the antifouling effect by a coating film cannot be maintained for a long time. Specifically, when Mn exceeds 20,000, the coating film becomes tough, but the solubility of the coating film becomes worse and the antifouling effect may be gradually lowered. Moreover, when Mn exceeds 20,000, since the viscosity of the said polymer (A) is high, the viscosity of coating composition itself containing the said polymer (A) will become high too much. When such a coating composition is used as a coating, a large amount of organic solvent (thinner) is required, which causes environmental problems and is not economical.

  Examples of the method for measuring Mn include gel permeation chromatography (GPC). When Mn is measured by GPC, Mn is displayed as a value (polystyrene equivalent value) obtained by creating and measuring a calibration curve using polystyrene as a standard substance.

  The dispersion degree of the molecular weight of the polymer (A) is preferably less than 3.0. When the degree of dispersion of the molecular weight is less than 3.0, the viscosity of the coating composition can be suitably reduced, and the amount of solvent used when used as a coating can be effectively reduced. Further, it is possible to obtain an antifouling paint having good coating film properties and capable of effectively exhibiting the antifouling effect for a long period.

  In particular, the polymer (A) is preferably a polymer having Mn of 2,000 to 15,000 and a molecular weight dispersity of less than 2.5, and Mn of 5,000 to 10,000. A polymer having a molecular weight dispersity of 2.0 to 1.0 is more preferred.

  20-70 degreeC is preferable and, as for the glass transition temperature (Tg) of the said polymer (A), 30-60 degreeC is more preferable. When Tg is 20 to 70 ° C., moderate hardness and toughness can be maintained for a long period of time without being significantly affected by the water temperature and temperature. When Tg is less than 20 ° C., a soft coating film is obtained. Therefore, as the water temperature and temperature rise, the coating film becomes too soft, and abnormalities such as cold flow tend to occur. When Tg exceeds 60 ° C., the coating film is too hard, so that the coating film tends to cause cracks or peeling.

  The polymer (A) is obtained by (co) polymerizing at least a triorganosilyl group-containing monomer represented by the following general formula (I).

In general formula (I), R ¹ is not particularly limited as long as it is a hydrocarbon group having a polymerizable unsaturated double bond,

Are preferable, and CH ₂ ═C (CH ₃ ) — or CH ₂ ═CH— is more preferable.

Examples of R ⁵ include a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, an unsaturated alkyl group, and an aralkyl group.

  Examples of the linear or branched alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, 2 -Methylbutyl group, 2-ethylbutyl group, pentyl group, 3-methylpentyl group, hexyl group, heptyl group, octyl group and the like can be mentioned.

  Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.

  Examples of the unsaturated alkyl group include 2-propenyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group and the like.

  Examples of the aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group.

  The alkyl group, cycloalkyl group, unsaturated alkyl group, aralkyl group and the like may have a substituent. Examples of the substituent include an alkoxy group and an acyl group. The number of substituents and the substitution position are not particularly limited as long as the effects of the present invention are not hindered.

R ^{6 to} R ⁸ are the same or different and represent a branched alkyl group having 3 to 8 carbon atoms or a phenyl group. Examples of the branched alkyl group having 3 to 8 carbon atoms include isopropyl group, isobutyl group, s-butyl group, t-butyl group, 2-methylbutyl group, isopentyl group, 2-ethylbutyl group, and 3-methylpentyl group. Can be mentioned. In particular, R ^{6 to} R ⁸ are preferably an isopropyl group, an s-butyl group, a t-butyl group, and a phenyl group, and more preferably an isopropyl group.

In general formula (I), it is preferable that R < ² > -R < ⁴ > is the same or different, respectively, and is a C3-C8 branched alkyl group or a phenyl group. The branched alkyl group having 3 to 8 carbon atoms is the same as the alkyl group exemplified for R ^{6 to} R ⁸ . In particular, R ^{2 to} R ⁴ are preferably an isopropyl group, a s-butyl group, a t-butyl group, and a phenyl group, and more preferably an isopropyl group.

Examples of the triorganosilyl group-containing monomer represented by the general formula (I) include a triisopropylsilyl group-containing monomer, a triisobutylsilyl group-containing monomer, a tris-butylsilyl group-containing monomer, Triisopentylsilyl group-containing monomer, triphenylsilyl group-containing monomer, diisopropylisobutylsilyl group-containing monomer, diisopropyl s-butylsilyl group-containing monomer, diisopropylisopentylsilyl group-containing monomer, diisopropylphenyl Silyl group-containing monomer, isopropyl diisobutylsilyl group-containing monomer, isopropyl dis-butylsilyl group-containing monomer, t-butyldiisobutylsilyl group-containing monomer, t-butyldiisopentylsilyl group-containing monomer , T-butyldiphenylsilyl group-containing monomers, and the like. These triorganosilyl group-containing monomers can be used alone or in combination of two or more. Among these, a triisopropylsilyl group-containing monomer, a tris-butylsilyl group-containing monomer, and a t-butyldiphenylsilyl group-containing monomer are particularly preferable, and a triisopropylsilyl group-containing monomer is more preferable. In particular, from the viewpoint of production process, production cost, raw material availability, and environmental safety, the triorganosilyl group-containing monomer is a triisopropylsilyl group-containing monomer in which all of R ^{2 to} R ⁴ are isopropyl groups. Is preferred.

  Specific examples of the triisopropylsilyl group-containing monomer include triisopropylsilyl (meth) acrylate, triisopropylsilyl 4-pentenoate, bis (triisopropylsilyl) maleate, methyltriisopropylsilyl maleate, malein Ethyl triisopropylsilylate, n-butyltriisopropylsilyl maleate, isobutyltriisopropylsilyl maleate, t-butyltriisopropylsilyl maleate, n-pentyltriisopropylsilyl maleate, isopentyltriisopropylsilyl maleate, maleic acid 2-ethylhexyltriisopropylsilyl, cyclohexyltriisopropylsilyl maleate, bis (triisopropylsilyl) fumarate, methyltriisopropylsilyl fumarate, fumarate Ethyltriisopropylsilyl, n-butyltriisopropylsilyl fumarate, isobutyltriisopropylsilyl fumarate, n-pentyltriisopropylsilyl fumarate, isopentyltriisopropylsilyl fumarate, 2-ethylhexyltriisopropylsilyl fumarate, cyclohexyl fumarate And triisopropylsilyl. These can be used alone or in combination of two or more. In particular, the triisopropylsilyl group-containing monomer is preferably triisopropylsilyl (meth) acrylate.

    In addition, (meth) acrylic acid triisopropylsilyl means triisopropylsilyl acrylate or triisopropylsilyl methacrylate.

    As said polymer (A), (meth) acrylic-acid triisopropylsilyl copolymer (copolymer (A)) is preferable. In particular, as the copolymer (A), (a) triisopropylsilyl (meth) acrylate 30 to 60% by weight, preferably 30 to 50% by weight, (b) methyl methacrylate 10 to 50% by weight, preferably Is preferably obtained by copolymerizing 10 to 40% by weight, and (c) (meth) acrylic acid esters other than (a) and (b) 0 to 60% by weight, preferably 0 to 50% by weight.

    The “wt%” indicates the use ratio of each monomer when the total amount of monomers to be copolymerized is 100 wt%.

  When the usage ratio of the monomer (a) is 30 to 60% by weight, the formed coating film can effectively exhibit a desired antifouling effect. Moreover, the hydrolysis rate of a coating film can be suppressed suitably and the antifouling effect can be exhibited for a long period of time. Furthermore, the water resistance and toughness of the coating film can be improved.

  When the proportion of the monomer (a) used is less than 30% by weight, it is difficult for the coating film to exhibit an antifouling effect for a long time because the coating film solubility is poor. When the proportion of the monomer (a) used exceeds 60% by weight, the coating film solubility becomes too high, and the coating film design becomes difficult. Further, sufficient water resistance and toughness cannot be imparted to the coating film.

  When the proportion of the monomer (b) used is 10 to 50% by weight, the resulting coating film can maintain appropriate hardness and toughness for a long period of time. When the proportion of the monomer (b) used is less than 10% by weight, the coating film becomes soft and abnormalities such as cold flow tend to occur. When the proportion of the monomer (b) used exceeds 50% by weight, the toughness of the coating film is improved, but it becomes too hard and cracks and peeling may occur.

The “other (meth) acrylic acid ester” of the monomer (c) means an acrylic acid ester or a methacrylic acid ester other than methyl methacrylate. For example, methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) alkyl (meth) acrylates such as lauryl acrylate; 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, (meth) acrylic acid 2-ethoxy phenoxyethyl, etc. (meth) acrylic acid alkoxyalkyl such; (meth) acrylic acid ethylene glycol monomethyl, (meth) (meth) acrylic acid alkylene glycol monomethyl ethers, such as acrylic acid propylene glycol monomethyl, (meth) acrylic acid 2-Hydroxyethyl, 2-hydroxyprop (meth) acrylic acid (Meth) acrylic acid hydroxyalkyls such as (meth) acrylic acid dimethylaminoethyl, (meth) acrylic acid diethylaminoethyl and other (meth) acrylic acid dialkylaminoethyls; (meth) acrylic acid tri-n-butylsilyl, ( (Meth) acrylic acid triisobutylsilyl, (meth) acrylic acid tris-butylsilyl, (meth) acrylic acid triphenylsilyl, (meth) acrylic acid t-butyldiphenylsilyl (meth) other than the above monomer (a) ) Triorganosilyl acrylates and the like. Other examples include benzyl (meth) acrylate and phenyl (meth) acrylate. The exemplified monomer (c) can be used alone or in combination of two or more as the monomer component of the copolymer (1). In particular, monomers (c) include ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and (meth) acrylic. Acid 2-methoxypropyl and the like are more preferable.

  When the copolymer (A) is synthesized, a monomer other than the monomers (a), (b), and (c) is further used in combination so long as the amount is not particularly affected by water resistance and coating film solubility. You can also

  Examples of the monomer that can be used in combination include a vinyl compound having a functional group, an aromatic compound, acrylic acid, and methacrylic acid. Examples of the vinyl compound having a functional group include vinyl chloride, vinylidene chloride, (meth) acrylonitrile, vinyl acetate, butyl vinyl ether, lauryl vinyl ether, N-vinyl pyrrolidone and the like. Examples of the aromatic compound include styrene, vinyl toluene, α-methyl styrene and the like.

  Particularly, the copolymer (A) includes triisopropylsilyl (meth) acrylate (monomer (a)), methyl methacrylate (monomer (b)), ethyl (meth) acrylate, ( At least one monomer selected from the group consisting of n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 2-methoxypropyl (meth) acrylate A copolymer with (monomer (c)) is preferred.

    The polymer (A) may be any copolymer of a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer.

    The polymer (A) can be obtained, for example, by polymerizing the monomer (a), the monomer (b) and the monomer (c) in the presence of a polymerization initiator.

    Examples of the polymerization initiator used in the polymerization reaction include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2 ′. -Azo compounds such as azobisisobutyrate, and diacyl peroxide compounds such as dibenzoyl peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dilauryl peroxide, T-butyl peroxide compounds such as di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroctoate, t-amylperoxy-2-ethylhexano Ate, t-amyl peroxyacetate, t-amyl peroxy T-Amylperoxide compounds such as xyisononanoate, t-amylperoxybenzoate, t-amylperoxyacetate, di (t-amylperoxide), 1,1-di (t-amylperoxy) cyclohexane , And t-hexylperoxy-2-ethylhexanoate, t-hexylperoxybenzoate, t-hexylperoxy-isopropyl monocarbonate, t-hexylperoxypivalate, t-hexylperoxyneodecanoate, etc. And t-hexyl peroxide compounds. These polymerization initiators can be used alone or in combination of two or more. As the polymerization initiator, diacyl peroxide compounds, t-butyl peroxide compounds, t-amyl peroxide compounds and t-hexyl peroxide compounds are preferable, and t-amyl peroxide compounds and t-hexyl. Peroxide compounds are more preferred. By using t-amyl peroxide compounds and t-hexyl peroxide compounds as polymerization initiators, it is possible to obtain a polymer having a narrow molecular weight distribution and a lower viscosity than when other polymerization initiators are used. .

  The molecular weight of the polymer (A) can be adjusted by appropriately setting the amount of the polymerization initiator used.

  Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like. Among these, the solution polymerization is particularly preferable because the polymer (A) can be synthesized easily and accurately.

  In the polymerization reaction, an organic solvent may be used as necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; isopropyl Examples include alcohol solvents such as alcohol and butyl alcohol; ether solvents such as dioxane, diethyl ether, and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among these, an aromatic hydrocarbon solvent is particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.

  What is necessary is just to set the reaction temperature in a polymerization reaction suitably according to the kind etc. of a polymerization initiator, and it is 70-140 degreeC normally, Preferably it is 80-120 degreeC. What is necessary is just to set the reaction time in a polymerization reaction suitably according to reaction temperature etc., and is about 4 to 8 hours normally.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.

<Zinc salt (B)>
The antifouling coating composition of the present invention contains at least one zinc salt (zinc salt (B)) selected from a rosin zinc salt and a zinc salt of a rosin derivative. Since the zinc salt is highly compatible with the polymer (A), it can be stably present in the coating film. Therefore, the composition of this invention is excellent in long-term storage property.

  When using sodium salt other than the zinc salt, calcium salt, magnesium salt, etc. as the metal salt of rosin (or rosin derivative), it is not as much as rosin (or rosin derivative) having a free carboxyl group, Since hydrophilicity is too high, there exists a possibility that the water resistance of a coating film may fall.

  Examples of the rosin zinc salt include gum rosin zinc salt, wood rosin zinc salt, tall oil rosin zinc salt and the like. These can be used alone or in combination of two or more.

  Examples of zinc salts of rosin derivatives include maleated rosin zinc salts, formylated rosin zinc salts, polymerized rosin zinc salts, hydrogenated rosin zinc salts, and disproportionated rosin zinc salts. These can be used alone or in combination of two or more.

  In the present invention, the rosin zinc salt is at least one zinc salt selected from the group consisting of gum rosin zinc salt, wood rosin zinc salt and tall oil rosin zinc salt, and the zinc salt of the rosin derivative is a hydrogenated rosin zinc salt. And at least one zinc salt selected from the group consisting of disproportionated rosin zinc salts.

Commercially available products can be used as the rosin salt and rosin derivative salt. The rosin salt and rosin derivative salt can also be produced by a known method. For example, a zinc salt of rosin (or rosin derivative) can be synthesized by reacting rosin (or rosin derivative) having a free carboxyl group (COO ⁻ group) with zinc oxide while heating in a solution.

  The composition of the present invention is characterized by containing a relatively large amount of the zinc salt (B). The weight ratio ((A) / (B)) between the content of the polymer (A) and the content of the zinc salt (B) is preferably 45/55 to 10/90, and 40/60 to 20 / 80 is more preferable. When the weight ratio is 45/55 to 10/90, since the hardness and toughness of the coating film are good, the dissolution amount of the coating film can be suitably suppressed, and the coating film exhibits an antifouling effect for a long period of time. Can do.

  The rosin zinc salt and the zinc salt of the rosin derivative have a lower viscosity than other metal salts such as a copper salt and the polymer (A). Therefore, the viscosity of the coating composition can be lowered by using a large amount of the rosin zinc salt and the zinc salt of the rosin derivative so as to be in the above weight ratio range. In this case, since the viscosity of the resulting coating composition is low, the use of the solvent can be suppressed when the composition is used as a coating, and as a result, the nonvolatile content is high, that is, a volatile organic compound (VOC). An antifouling paint (low VOC antifouling paint) having a small content of

  The composition of the present invention is substantially free of rosin and rosin derivatives having a free carboxyl group. Specifically, the content of the rosin and rosin derivative in the composition of the present invention is preferably 1% by weight or less, and more preferably 0 to 0.1% by weight. Rosin and rosin derivatives having a free carboxyl group are highly hydrophilic. Therefore, when the said coating film contains the said rosin and a rosin derivative, since the water resistance of a coating film falls, there exists a possibility that abnormality, such as a blister and a crack, may arise in a coating film.

<Copper oxide>
It is preferable that the antifouling coating composition of the present invention further contains cuprous oxide. The cuprous oxide can serve as an antifouling agent. By containing cuprous oxide, the formed coating film can effectively exhibit the antifouling effect.

  The shape of the cuprous oxide is not particularly limited as long as it does not hinder the effects of the present invention. For example, a particulate thing can be used as cuprous oxide.

  3-20 micrometers is preferable and, as for the average particle diameter of a particulate cuprous oxide, 8-20 micrometers is more preferable. When the average particle diameter of cuprous oxide is 3 to 20 μm, the dissolution rate of the coating film can be suitably suppressed, and as a result, the antifouling effect can be exhibited for a long time. Moreover, when the average particle diameter of a cuprous oxide is 8-20 micrometers, the viscosity of the coating composition of this invention can further be lowered | hung and the low VOC antifouling coating material can be obtained suitably as a result.

  As said cuprous oxide, what coated the periphery with the coating agent is preferable. For example, when using a particulate thing as said cuprous oxide, it is preferable to coat the surface of each particle | grain with a coating agent. By coating with a coating agent, oxidation of the cuprous oxide can be suitably prevented.

  Examples of the coating agent include stearic acid, lauric acid, glycerin, sucrose, and lecithin. About these coating agents, 1 type can be used individually or in mixture of 2 or more types.

  The composition of the present invention preferably contains 100 to 400 parts by weight of the cuprous oxide based on 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), and 200 to 300 parts by weight. More preferably. When the content of the cuprous oxide is 100 to 400 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt, the coating film can suitably exhibit an antifouling effect.

  The cuprous oxide in the composition is preferably covered with the polymer (A), the zinc salt (B), an organic solvent described later, and the like. When the cuprous oxide is not sufficiently covered with the polymer (A) or the like, the cuprous oxide may not be sufficiently dispersed in the composition and may aggregate. When the cuprous oxide aggregates, cracks and peeling are likely to occur in the formed coating film.

  The composition of the present invention may further contain an inorganic antifouling agent other than the cuprous oxide as long as it does not inhibit the antifouling effect. Examples of the inorganic antifouling agent include copper thiocyanate (generic name: rhodan copper), cupronickel, copper powder, and the like. These can be used alone or in combination of two or more.

<Pigment>
The antifouling coating composition of the present invention may contain various pigments. By containing the pigment, the strength, weather resistance and water resistance of the coating film, and the solubility of the coating film can be improved.

  In particular, the composition of the present invention preferably further contains zinc oxide. By containing zinc oxide, dissolution of the formed coating film in seawater is promoted, and the antifouling effect can be effectively exhibited. The shape of zinc oxide is not particularly limited. For example, a particulate thing can be used as zinc oxide.

  In the case of using particulate zinc oxide, the particle diameter is not particularly limited as long as it does not interfere with the effects of the present invention.

  The content of the zinc oxide in the composition of the present invention is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), and 20 to 50 parts by weight. Is more preferable. When content of the said zinc oxide is 10-100 weight part with respect to 100 weight part of total amounts of the said polymer (A) and the said zinc salt (B), the dissolution rate of a coating film can be adjusted suitably. When the content of the zinc oxide is less than 10 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), it sufficiently promotes dissolution of the coating film in seawater. I can't. When the content of the zinc oxide exceeds 100 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), the coating film solubility becomes too high, It becomes difficult to adjust the dissolution rate.

  Besides the zinc oxide, known water-soluble pigments and water-insoluble pigments may be added as pigments.

  Examples of water-soluble pigments include cuprous oxide, copper oxide, copper thiocyanate, zinc carbonate, zinc sulfide, calcium hydrogen phosphate, calcium phosphate, calcium silicate, iron carbonate, iron carbonyl, magnesium hydroxide, and magnesium carbonate. It is done. These can be used individually by 1 type or in combination of 2 or more types. In particular, it is preferable to use at least one water-soluble pigment selected from cuprous oxide and copper thiocyanate as the water-soluble pigment.

  The cuprous oxide exemplified as the water-soluble pigment may be the same as or different from the cuprous oxide described in the section <copper oxide>.

  Examples of the water-insoluble pigment include titanium oxide, iron oxide, talc, calcium carbonate, silica, kaolin, pearlite, mica, barium sulfate, graphite, and carbon black. These can be used individually by 1 type or in combination of 2 or more types. In particular, at least one water-insoluble pigment selected from the group consisting of titanium oxide, iron oxide, talc, calcium carbonate, silica, kaolin and barium sulfate is preferably used as the water-insoluble pigment.

  The water-soluble pigment has an effect of improving the solubility of the coating film in seawater. The zinc oxide is a compound belonging to a water-soluble pigment. The water-insoluble pigment has an effect of suppressing the solubility of the coating film in seawater. Therefore, the physical properties of the coating film and the solubility of the coating film can be suitably adjusted by appropriately setting the types of the water-soluble pigment and the water-insoluble pigment and the amount of these pigments used.

  The pigment content in the composition of the present invention is not particularly limited, but is adjusted so that the pigment volume concentration (PVC) in the formed coating film is 20 to 50%, preferably 25 to 45%. It is desirable.

  A coating film having a PVC of less than 20% is soft and insufficient in strength. A coating film with PVC exceeding 50% is brittle and easily cracks.

  The PVC can be calculated by the following formula.

PVC (%) = total amount of pigment (including pigment not dissolved in solvent) (ml) ÷ total amount of solid content (ml) × 100
In the above formula, “volume of the total solid content” means the total volume of the pigment, the polymer (A), the zinc salt (B) and the like. When the composition of the present invention contains cuprous oxide described in the above section <cuprous oxide>, an organic antifouling agent, a plasticizer, a dehydrating agent, a dispersing agent, etc. described later, these volumes are also referred to as “all Included in “volume of solids”.

  The pigment in the composition is preferably covered with the polymer (A) or the like, like the cuprous oxide. When the pigment is sufficiently covered with the polymer (A) or the like, it is possible to effectively prevent the occurrence of cracks and peeling in the formed coating film.

<Organic antifouling agent>
The antifouling coating composition of the present invention may further contain an organic antifouling agent.

  The organic antifouling agent is not particularly limited as long as the organic antifouling agent is a substance having a killing or repelling action against marine fouling organisms. For example, organic copper compounds such as 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate (generic name: Dinebu ), Bis (dimethyldithiocarbamate) zinc (generic name: diram), bis (dimethyldithiocarbamate), ethylenebis (dithiocarbamate) dizinc (generic name: polycarbamate), and other organic zinc compounds; pyridine, triphenylborane, 4 Organic boron compounds such as isopropylpyridyl-diphenylmethylborane, 4-phenylpyridyl-diphenylborane, triphenylboron-n-octadecylamine, triphenyl [3- (2-ethylhexyloxy) propylamine] boron; 6- Maleimide compounds such as lichloromaleimide and N- (2,6diethylphenyl) 2,3-dichloromaleimide; other, 4,5-dichloro-2-n-octyl-3-isothiazolone (generic name: Cineine 211), 3,4-dichlorophenyl-N-N-dimethylurea (generic name: diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (generic name: Irgarol 1051), 2,4 , 5,6-tetrachloroisophthalonitrile (generic name: chlorothalonil), N-dichlorofluoromethylthio-N ′, N′-dimethyl-Np-tolylsulfamide (generic name: trifluanide), N-dichloromethylthio -N ', N'-dimethyl-N-phenylsulfamide (generic name: dichlorofluanide), 2- (4 Thiazolyl) benzimidazole (generic name: thiabendazole), 3- (benzo [b] thien-2-yl) -5,6-dihydro-1,4,2-oxathiazine-4-oxide (generic name: betoxazine) 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econia 028), and the like. Among these, zinc pyrithione, copper pyrithione, pyridine triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, betoxazine, dineb, cineine 211 and irgarol 1051 are preferable, and copper pyrithione, zinc pyrithione, pyridine triphenylborane and betoxazine are more preferable. preferable. These organic antifouling agents can be used alone or in combination of two or more.

  The content of the organic antifouling agent in the composition of the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B). 30 parts by weight is more preferable. When the content of the organic antifouling agent is less than 1 part by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), the antifouling effect by the organic antifouling agent is obtained. Cannot fully demonstrate. When the content of the organic antifouling agent exceeds 50 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), the content of the organic antifouling agent is increased. The improvement of the antifouling effect is not seen, and it is economically wasteful.

<Plasticizer>
The antifouling coating composition of the present invention may further contain a plasticizer. By containing a plasticizer, the plasticity of the composition can be improved, and as a result, a tough coating film can be suitably formed. Moreover, the adhesiveness of the coating film with respect to the coating film-formed product can be improved.

  Examples of the plasticizer include phosphate esters such as tricresyl phosphate, trioctyl phosphate, and triphenyl phosphate; phthalate esters such as dibutyl phthalate and dioctyl phthalate; adipic acid such as dibutyl adipate and dioctyl adipate Esters; sebacic acid esters such as dibutyl sebacate and dioctyl sebacate; epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil; alkyl vinyl ether polymers such as methyl vinyl ether polymer and ethyl vinyl ether polymer; polyethylene Polyalkylene glycols such as glycol and polypropylene glycol; t-nonyl pentasulfide, petrolatum, polybutene, trimellitic acid tris (2-ethylhexyl), silicone Le, liquid paraffin, chlorinated paraffin, Tg can be cited such as -20 ° C. or less of the ethylenically unsaturated carboxylic acid ester polymers. These can be used alone or in combination of two or more.

  In the present invention, the plasticizer is at least one plasticizer selected from the group consisting of phosphoric acid esters, epoxidized oils and fats, and an ethylenically unsaturated carboxylic acid ester polymer having a Tg of −20 ° C. or lower. It is preferable that epoxidized oils and fats are more preferable.

  The content of the plasticizer in the composition of the present invention depends on the content of the zinc salt of the rosin zinc salt and / or rosin derivative in the composition, but the polymer (A) and the zinc salt 1 to 50 parts by weight is preferable and 5 to 30 parts by weight is more preferable with respect to 100 parts by weight of the total amount of (B). When the content of the plasticizer is less than 1 part by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), the effect of improving physical properties (toughness, adhesiveness, etc.) is obtained. Not fully expressed. When the content of the plasticizer exceeds 50 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), the problem is that the formed coating film is so soft that it cannot withstand practical use. Is likely to occur.

<Water removal agent>
It is preferable that the antifouling coating composition of the present invention further contains a dehydrating agent. The dehydrating agent is a drug for removing water in the composition. Examples of the water removing agent include a water binder and a dehydrating agent. About a water binder and a dehydrating agent, you may use individually, respectively, and may use both together.

  The water binder is a compound having a property of removing water in the coating composition by reacting with water. For example, orthoformate alkyl esters such as methyl orthoformate and ethyl orthoformate; tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrakis (2-ethoxybutoxy) silane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldi Examples include alkoxysilanes such as ethoxysilane, trimethylethoxysilane, and diphenyldiethoxysilane; and acid anhydrides such as maleic anhydride and phthalic anhydride.

The dehydrating agent is a compound having a property of removing water in the composition by incorporating water as crystal water. Examples thereof include anhydrous gypsum, molecular sieve, magnesium sulfate, sodium sulfate and the like.
As the dehydrating agent, a water binder is particularly preferable, at least one water binder selected from the group consisting of alkoxysilanes and alkyl orthoformates is more preferable, and tetraethoxysilane is most preferable.

  The content of the dehydrating agent in the composition of the present invention is not particularly limited, but is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B). 2 to 30 parts by weight is more preferable. When the content of the dehydrating agent is less than 1 part by weight relative to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), sufficient storage stability may not be obtained. When the content of the dehydrating agent exceeds 50 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), the coating film may become brittle. In particular, the water binder is liable to volatilize in the air. Therefore, from the viewpoint of environmental problems, when using a water binder as a dehydrating agent, the amount used is 30 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B). The following is preferable.

<Dispersant>
It is preferable that the composition of the present invention further contains a dispersant (an anti-settling agent). By containing a dispersing agent, the components (for example, pigment, cuprous oxide, zinc oxide, titanium oxide, petal, talc, etc.) in the composition are precipitated during storage of the composition of the present invention and hard cake ( Can be effectively prevented. Moreover, when forming a coating film on the surface of a to-be-coated-formed object using the composition of this invention, the problem that the said composition (paint) droops can be solved effectively.

  Examples of the dispersant include polyethylene oxide dispersants, fatty acid amide dispersants, fatty acid ester dispersants, hydrogenated castor oil dispersants, vegetable polymer oil dispersants, polyether ester type surfactants, sulfate esters. Type anionic surfactant, polycarboxylic acid amine salt dispersant, polycarboxylic acid dispersant, polymer polyether dispersant, acrylic polymer dispersant, special silicon dispersant, talc dispersant, bentonite Examples thereof include a system dispersant, a kaolinite-based dispersant, and a silica gel-based dispersant. These dispersants can be used alone or in combination of two or more. The composition of the present invention preferably contains a fatty acid amide dispersant as the dispersant. The composition of the present invention is produced, for example, by preparing a mixed solution containing the polymer (A) and the like and then mixing and dispersing the mixed solution. When the said liquid mixture contains the said fatty acid amide type dispersing agent, the storage stability of this liquid mixture can be improved, and the composition of this invention can be obtained more simply and reliably.

  A commercially available thing can be used for the said dispersing agent. For example, as the fatty acid amide-based dispersant, for example, Disparon A603-10X (or 20X), Disparon 6900-10X (or 20X), Disparon 6810-10X (or 20X) (all manufactured by Enomoto Kasei Co., Ltd.), Talen 7500 -20, Flownon SP-1000 (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be used.

The dispersant may be used by being dispersed in an organic solvent such as xylene.
The content of the dispersant in the composition of the present invention is not particularly limited, but is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B). 2-30 weight part is more preferable. When the content of the dispersant is less than 1 part by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), the effect of using the dispersant (that is, suppressing the formation of hard cake) (Effect) may not be fully exhibited. That is, the storage stability of the composition of the present invention may be insufficient. When the content of the dispersant exceeds 50 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), the viscosity of the composition becomes too high, and the coating is performed. May be difficult. Moreover, the improvement of the effect which suppresses the hard cake production | generation by increasing content of the said dispersing agent is not seen, but it is wasteful also economically.

<Other additives>
The composition of the present invention may further contain a dye, a color separation inhibitor, an antifoaming agent and the like.

  The composition of the present invention is usually dissolved or dispersed in an organic solvent. Thereby, it can use suitably as a coating material. Examples of the organic solvent include xylene, toluene, mineral spirit, MIBK, butyl acetate and the like. Among these, xylene or MIBK is particularly preferable. These organic solvents can be used alone or in admixture of two or more.

  In particular, when the composition of the present invention is used, the use of the organic solvent can be suppressed. This is because the composition of the present invention has a low viscosity. A paint using such a composition may be referred to as a “high solid paint” in the art.

  That is, the composition of the present invention can be used as a low VOC antifouling coating composition. Since the coating material using the composition of the present invention has less scattering of volatile organic compounds to the atmosphere, the burden on the environment can be reduced.

  The VOC content of the composition of the present invention is preferably less than 400 g / L, more preferably 300 to 350 g / L.

  The nonvolatile component content of the composition of the present invention is 75% by weight or more, preferably 80% by weight or more, and more preferably 85% by weight or more.

  The composition of the present invention preferably has a viscosity at 25 ° C. of 70 to 100 KU, more preferably 80 to 100 KU, measured using a Stormer viscometer. When the viscosity at 25 ° C. measured using a Stormer viscometer is 70 to 100 KU, a thick coating film can be easily formed using the coating composition of the present invention even if the amount of solvent used is small. Moreover, it can preserve | save for a long period of time, preventing effectively the component (For example, a pigment, cuprous oxide, a zinc oxide, a titanium oxide, a petal, a talc etc.) in the composition of this invention.

  The viscosity can be measured in accordance with JIS-5400 (or ASTM D562-01). A commercially available Stormer viscometer may be used.

  The composition of the present invention is excellent in storage stability and hardly gels or solidifies even when stored for a long period of time.

Method for producing antifouling paint composition The method for producing the antifouling paint composition of the present invention comprises:
(A) a polymer (polymer (A)) having a number average molecular weight of 1,000 to 20,000 obtained by polymerizing a polymerizable unsaturated carboxylic acid triorganosilyl;
(B) At least one zinc salt selected from rosin zinc salt and zinc salt of rosin derivative (zinc salt (B))
Mixing with,
(1) The weight ratio ((A) / (B)) between the content of the polymer (A) and the content of the zinc salt (B) is 45/55 to 10/90,
(2) The non-volatile content is 75% by weight or more,
(3) substantially free of rosin and rosin derivatives having a free carboxyl group,
This is a method for producing an antifouling paint composition.

  According to the production method of the present invention, the antifouling coating composition of the present invention can be suitably produced.

  As the polymer (A) and the zinc salt (B), the polymer (A) and the zinc salt (B) described in the above <Polymer (A)> and <Zinc salt (B)> are used. That's fine. Moreover, you may mix various additives, such as the said pigment, the said cuprous oxide, the said organic antifouling agent, the said dehydrating agent, the said dispersing agent, as needed.

  About the usage-amount of the said polymer (A), the said zinc salt (B), etc. so that it may become content of the said polymer (A), the said zinc salt (B), etc. in the said antifouling coating composition, respectively. What is necessary is just to adjust suitably.

  When mixing, it is preferable to dissolve or disperse various materials such as the polymer (A) in a solvent. For example, the polymer (A) and the zinc salt (B) may be mixed with other materials (such as the organic antifouling agent) in a state of being dissolved or dispersed in a solvent. Examples of the solvent include xylene, toluene, mineral spirit, MIBK, butyl acetate and the like. Of these, xylene is particularly preferable. These solvents can be used alone or in admixture of two or more.

  When using cuprous oxide when manufacturing the antifouling paint composition of the present invention, it is preferable to employ the following manufacturing method 1 and manufacturing method 2 according to the average particle size of the cuprous oxide.

  Specifically, when cuprous oxide having an average particle diameter of 3 to 10 μm, preferably 3 to 8 μm is used as the cuprous oxide, it is preferable to employ the following production method 1.

<Manufacturing method 1>
In addition to the polymer (A) and the zinc salt (B), a cuprous oxide having an average particle size of 3 to 10 μm, preferably 3 to 8 μm, was mixed, and the resulting mixture was then dispersed using a disperser. Mix and disperse.

  Cuprous oxide having an average particle size of 3 to 10 μm tends to cause secondary aggregation. For this reason, simply mixing each material containing cuprous oxide may cause lumps in the resulting composition, resulting in cracks and the like in the formed coating film. According to the production method 1, a mixture containing cuprous oxide having an average particle diameter of 3 to 10 μm is mixed using a disperser, and the cuprous oxide and the like in the mixture are dispersed to cause secondary aggregation. An antifouling coating composition in which the cuprous oxide is suitably dispersed while destroying the cuprous oxide can be obtained.

According to the production method 1, the antifouling agent is obtained by mixing and dispersing the polymer (A), the zinc salt (B), and the mixture containing cuprous oxide having an average particle diameter of 3 μm to 10 μm using a disperser. A coating composition can be produced.
You may make the said mixture contain various additives, such as the said pigment, the said organic antifouling agent, the said dehydrating agent, the said dispersing agent, as needed.

  The contents of the polymer (A), the zinc salt (B), the cuprous oxide and the like in the mixture are respectively the polymer (A) and the zinc salt (B) in the antifouling coating composition. The content of the cuprous oxide and the like may be adjusted as appropriate.

  The mixture is preferably prepared by dissolving or dispersing various materials such as the polymer (A) in a solvent. For example, when preparing the mixture, the polymer (A) and the zinc salt (B) are mixed with other materials (such as the organic antifouling agent) while being dissolved or dispersed in a solvent. Also good. As the solvent, the same solvents as described above can be used.

  As the disperser, for example, one that can be used as a fine pulverizer can be suitably used. For example, a mill or a dissolver can be used.

  As the mill, for example, a mill generally used for mixing and dispersing paints such as a ball mill, a sand mill, a bead mill, a pearl mill, a dyno mill, a cowless mill, a basket mill, and an attritor can be used.

  The dissolver is a disperser provided with a rotary blade type grinder, and the mixed liquid can be mixed and dispersed by rotating the grinder. When a dissolver is used as the disperser, it is preferable to rotate the grinder of the dissolver at a high speed. By rotating the grinder at a high speed, the secondary agglomerated cuprous oxide can be suitably broken.

  The dissolver is sometimes called a disper.

  When cuprous oxide having an average particle diameter of 10 to 20 μm, preferably 13 to 20 μm is used as the cuprous oxide, it is preferable to employ the following production method 2.

<Manufacturing method 2>
After mixing and dispersing the mixture obtained by mixing the polymer (A) and the zinc salt (B) using a disperser, the sub-oxidation has an average particle size of 10 to 20 μm, preferably 13 to 20 μm. Add and mix copper.

Cuprous oxide having an average particle size of 10 to 20 μm is relatively unlikely to aggregate secondary. Therefore, after the mixture containing the polymer (A) and the zinc salt (B) is mixed and dispersed using a disperser, the cuprous oxide is added to the obtained mixed dispersion, and cuprous oxide particles are added. The composition of the present invention can be produced by mixing using a mixing device so as not to grind as much as possible. According to this method, since the cuprous oxide is hardly pulverized, the surface area of the cuprous oxide in the obtained composition can be kept in a relatively small range. For example, the surface area of the cuprous oxide can be 1.3 × 10 ⁻³ mm ² or less, preferably 3.0 × 10 ^{−4 to} 1.3 × 10 ⁻³ mm ² .

  As described above, it is desirable that the cuprous oxide in the composition is sufficiently covered with the polymer (A) or the like.

  When the surface area of the cuprous oxide is small, it is possible to reduce the amount of the polymer (A), the zinc salt (B), the organic solvent and the like necessary for covering the surface of the cuprous oxide, A low VOC antifouling paint can be suitably obtained.

  Also, in the antifouling coating film, when the surface area of the cuprous oxide is small, the seawater temperature is high, specifically, even when the seawater temperature is 30 ° C. or higher, the dissolution rate of the coating film Can be effectively suppressed. Moreover, according to the said manufacturing method 2, the processing time by the said disperser can be shortened and the manufacturing cost of the composition of this invention can be held down.

  The said mixture is the same as the mixture of the said manufacturing method 1 except not containing the said cuprous oxide.

  What is necessary is just to adjust suitably the addition amount of the said cuprous oxide so that it may become content of the cuprous oxide in the said antifouling coating composition.

  As the disperser, the same disperser used in the production method 1 can be used.

  The mixing device is not particularly limited, and a known mixing device can be used. For example, the above dissolver can be used. When using the dissolver, the grinder is preferably rotated at a medium speed or a low speed. By rotating at a medium or low speed, pulverization of the cuprous oxide can be effectively prevented.

Antifouling treatment method, antifouling coating film , and coated article The antifouling treatment method of the present invention is characterized in that an antifouling coating film is formed on the surface of a film-forming article using the antifouling coating composition. To do. According to the antifouling treatment method of the present invention, the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing the adhesion of chickenpox fouling organisms. Moreover, after dissolving a coating film, the antifouling effect can be exhibited continuously by overcoating the said composition.

  Examples of the coating film formation include ships (particularly ship bottoms), fishing equipment, underwater structures, and the like. Examples of the fishery tools include aquaculture or stationary fishing nets, fishing net accessories such as floats and ropes used in the fishing nets, and the like. Examples of the underwater structure include a power plant conduit, a bridge, a port facility, and the like.

  The antifouling coating film of the present invention can be formed by applying the above antifouling coating composition to the surface (entirely or partly) of the coating film forming product.

  Examples of the coating method include brush coating, spraying, dipping, flow coating, and spin coating. These may be used alone or in combination of two or more.

After application, dry. The drying temperature may be room temperature. What is necessary is just to set drying time suitably according to the thickness etc. of a coating film.
What is necessary is just to set the thickness of the said antifouling coating film suitably according to the kind of coating film formation thing, the navigation speed of a ship, seawater temperature, etc. For example, when the coating film formation is the bottom of a ship, the thickness of the antifouling coating is usually 50 to 500 μm, preferably 100 to 400 μm.

  The antifouling coating film of the present invention is 1) The coating film dissolves stably in seawater for a long period of time, and the surface of the coating film is constantly renewed. Marine organisms do not adhere to the surface. 2) The water resistance of the paint film is good, and even if the paint film is in the sea for a long time, it does not cause any paint film abnormalities such as blisters, swelling, cracks, etc. on the paint film surface. It has the advantage that coating film abnormality such as cold flow is unlikely to occur, and 4) the adhesiveness to the coating film formation is high and the construction is easy.

  The coated article of the present invention has the antifouling coating film on the surface. The coated product of the present invention may have the antifouling coating film on the entire surface or a part thereof.

  Since the coated article of the present invention is provided with the antifouling coating film having the advantages 1) to 4), it can be suitably used as the ship (especially ship bottom), fishing equipment, underwater structure and the like.

  For example, when the antifouling coating film is formed on the ship bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, and the coating film surface is constantly renewed, thereby preventing adhesion of waterpox fouling organisms. it can.

  In addition, the antifouling coating film is suitably suppressed in hydrolysis rate in seawater. Therefore, the ship can maintain antifouling performance for a long period of time. For example, even in a stationary state such as during berthing or during outfitting, there is little adhesion and accumulation of Minamata fouling organisms, and the antifouling effect can be exhibited for a long period of time.

  In addition, even after a long period of time, the antifouling coating on the surface is basically free from cracks or peeling. Therefore, it is not necessary to perform another operation such as forming a coating film after the coating film is completely removed. Therefore, an antifouling coating film can be suitably formed by directly overcoating the antifouling coating film composition. Thereby, it is possible to easily and continuously maintain the antifouling performance at low cost.

  According to the antifouling paint composition of the present invention, since the content of volatile organic compounds (organic solvents, etc.) in the paint can be suppressed, in forming an antifouling coating film having a required film thickness, There are few organic compounds scattered in the environment, and the burden on the environment is small.

  Moreover, the composition of this invention is excellent in long-term storage stability. That is, the composition of the present invention hardly thickens or gels and solidifies even when stored for a long period of time. Furthermore, the antifouling paint composition of the present invention has high environmental safety, and even when dissolved in seawater, there is almost no problem of marine pollution.

  The antifouling coating film formed using the antifouling coating composition of the present invention has a good antifouling effect because 1) the coating film dissolves stably in seawater for a long period of time and the coating film surface is constantly renewed. Even if it is in the sea for a long time, marine organisms do not adhere to the coating surface. 2) The water resistance of the paint film is good, and even if the paint film is in the sea for a long time, it does not cause any paint film abnormalities such as blisters, swelling, cracks, etc. on the paint film surface. It has the advantage that coating film abnormality such as cold flow is unlikely to occur, and 4) the adhesiveness to the coating film formation is high and the construction is easy.

  Since the coated article of the present invention is provided with the antifouling coating film having the advantages 1) to 4), it can be suitably used as the ship (especially ship bottom), fishing equipment, underwater structure and the like. For example, when the antifouling coating film is formed on the ship bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, and the coating film surface is constantly renewed, thereby preventing adhesion of waterpox fouling organisms. it can.

  And the said antifouling coating film has moderate solubility. Therefore, even when the ship is in a stationary state such as when it is anchored or during the outfitting period, there is little adhesion and accumulation of Minamata fouling organisms, and the antifouling effect can be exhibited for a long period of time. As a result, the frictional resistance of the ship is reduced, and fuel can be saved during navigation.

  In addition, the antifouling coating film on the surface is basically free from coating film defects even after a long period of time. Therefore, an antifouling coating film can be suitably formed by directly overcoating the antifouling coating composition after using the coated product for a certain period of time. Thereby, it is possible to easily and continuously maintain the antifouling performance at low cost.

  Examples and the like will be described below to further clarify the features of the present invention. However, the present invention is not limited to the examples.

  In each production example, comparative production example, example and comparative example,% indicates% by weight.

  The viscosity of the copolymer (A) solution is a measured value at 25 ° C., and is a value determined by a B-type viscometer.

  The heating residue is a value obtained by heating at 125 ° C. for 1 hour in accordance with JIS K5601-1-2 (or ISO3251).

  The number average molecular weight (Mn) is a value (polystyrene conversion value) measured by GPC.

The conditions of GPC are as follows.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-M 2 Flow rate: 0.35 mL / min
Detector: RI
Column bath temperature: 40 ° C
Free liquid: THF
The molecular weight dispersity is a value obtained by dividing the weight average molecular weight (Mw) obtained by GPC by Mn.

  The glass transition temperature (Tg) of the copolymer is a value measured using a differential scanning calorimeter of Seiko Instruments SSC / 5200 in accordance with JIS K 7121.

The viscosity of the coating composition is a value measured at 25 ° C. using a Stormer viscometer in accordance with JISK 5400. The measurement conditions are as follows.
Stormer viscometer: Stormer viscometer NO. 453
Measurement temperature: 25 ± 0.5 ° C
Sample volume: 500ml (put up to the marked line of 500ml sample can)
Weight: 75-1000g
Measurement method: Measure the time until the rotor blades rotate 100 times. Measured by changing the weight, select the value closest to 30 seconds in the range of 27 to 33 seconds until 100 rotations, and convert to KU from the number of seconds until 100 rotations and the weight of the weight used The KU value was determined using the table.

  Moreover, the unit of the compounding quantity of each component in Table 1 is g.

Production Example 1 (Production of copolymer (A) solution)
After charging 330 g of xylene in a 1000 ml flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel, 150 g of triisopropylsilyl acrylate was added to the flask while stirring at 115 to 120 ° C. in a nitrogen atmosphere. Then, 150 g of methyl methacrylate, 50 g of n-butyl acrylate, 150 g of 2-methoxyethyl methacrylate and 5 g of t-butyl peroctoate were added dropwise over 3 hours. After the dropping, a polymerization reaction was performed at 115 to 120 ° C. for 2 hours. Next, 2 g (addition) of t-butyl peroctoate was added to the obtained reaction solution, and a polymerization reaction was further performed at 115 to 120 ° C. for 2 hours to obtain a copolymer (A) solution S-1. Table 1 shows the viscosity, heating residue, number average molecular weight (Mn), molecular weight dispersity (Mw / Mn), and glass transition temperature (Tg) of S-1.

Production Examples 2 to 6 (Production of copolymer (A) solution)
Copolymer (A) solutions S-2 to S-6 were obtained by performing a polymerization reaction in the same manner as in Production Example 1 using the solvents, monomers, and polymerization initiators shown in Table 1. Table 1 shows the viscosity, heating residue, number average molecular weight (Mn), molecular weight dispersity (Mw / Mn), and glass transition temperature (Tg) of each copolymer solution obtained.

Comparative Production Example 1 (Production of copolymer solution H-1)
A copolymer solution H-1 was obtained by performing a polymerization reaction in the same manner as in Production Example 1 using the organic solvent, monomer, polymerization initiator, and reaction temperature shown in Table 1. Table 1 shows the viscosity, heating residue, number average molecular weight (Mn), molecular weight dispersity (Mw / Mn), and glass transition temperature (Tg) of each copolymer solution obtained.

Comparative Production Example 2 (Production of copolymer solution H-2)
After charging 330 g of xylene into a 1000 ml flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel, 150 g of triisopropylsilyl methacrylate was added to the flask while stirring at 90-100 ° C. in a nitrogen atmosphere. Then, 150 g of methyl methacrylate, 50 g of n-butyl acrylate, 100 g of n-butyl methacrylate, 50 g of 2-methoxyethyl methacrylate and 1 g of t-butyl peroctoate were added dropwise over 2 hours. After the dropping, a polymerization reaction was performed at 90 to 100 ° C. for 2 hours. Subsequently, 2 g (addition) of t-butyl peroctoate was added to the obtained reaction solution, and a polymerization reaction was further performed at 90 to 100 ° C. for 2 hours to obtain a copolymer solution H-2. Table 1 shows the viscosity, heating residue, number average molecular weight (Mn), molecular weight dispersity (Mw / Mn), and glass transition temperature (Tg) of H-2.

Examples 1-2 and Comparative Examples 1-5 (Manufacture of coating composition)
Copolymer (A) solutions S-1 to S-6 (solid content of about 60%) obtained in Production Examples 1 to 6 as copolymers or copolymer solution H-1 obtained in Comparative Production Examples 1 to 2 ~ H-2 (solid content about 60%) as rosin zinc salt, gum rosin zinc salt xylene solution (solid content about 60%) or hydrogenated rosin zinc salt xylene solution (solid content about 60%) as rosin A xylene solution of gum rosin (solid content of about 60%) or xylene solution of hydrogenated rosin (about 60%), cuprous oxide, cuprous oxide having an average particle size of 3 μm or 6 μm, Organic antifouling chemicals, pigments, additives, and solvents are blended in the proportions (% by weight) shown in Table 2 and mixed in a small bench-top sand mill for experiments (using glass beads with a diameter of 1.5 to 2.5 mm). A coating composition was produced by dispersing. Table 2 shows the nonvolatile content, VOC content, PVC and coating viscosity of the coating composition obtained.

Examples 3 to 8 (Production of coating composition)
The co-child combination (1) solution S-3 to S-6 obtained in Production Examples 3 to 6 as a copolymer is used as a rosin zinc salt, a gum rosin zinc salt xylene solution (solid content of about 60%) or hydrogenated rosin zinc. A salt xylene solution (solid content of about 60%) and further antifouling chemicals, pigments, additives, and solvents listed in Table 2 were blended in the proportions (% by weight) shown in Table 2, and a small desktop for experiments. The mixture was dispersed by a sand mill (using glass beads having a diameter of 1.5 to 2.5 mm), and the resulting mixture was taken out. Next, a coating composition was prepared by adding cuprous oxide having an average particle size of 13 μm or 19 μm to the mixture and stirring slowly with a stirring blade. Table 2 shows the nonvolatile content, VOC content, PVC and coating viscosity of the coating composition obtained.

Test example 1 (spray paintability)
The coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were spray-coated on a blasted tin plate (75 × 150 mm) so that the thickness as a dry coating film was about 100 μm. The case where spray coating was possible was evaluated as ◎, and the case where it was impossible was evaluated as ×.

Test Example 2 (Paint stability test)
The coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were sealed in a 100 ml wide-mouth tin can and stored in a thermostat at 40 ° C. for 1 month, and then the viscosity of the coating composition was changed to B Measured with a viscometer.

  When the viscosity change of the paint is less than 500 mPa · s / 25 ° C. (the paint state hardly changed), the viscosity change of the paint is 500 to 5000 mPa · s / 25 ° C. (slightly thickened) ), ◯ for paint viscosity change of 5000-100000 mPa · s / 25 ° C (largely thickened), △ for paint viscosity changed to unmeasurable (gelled or solidified) ) Was marked with x.

  The results are shown in Table 3.

  From Table 3, it can be seen that the composition (Comparative Examples 2 and 3) containing rosin (or rosin derivative) having a free carboxyl group lacks long-term stability.

Test Example 3 (Coating film hardness)
The antifouling paint compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied on a transparent glass plate (75 × 150 × 1 mm) so that the thickness as a dry coating film was about 100 μm. Dried for 1 day at ° C. The coating film hardness of the obtained dried coating film was measured at 25 ° C. using a pendulum type hardness meter (pendulum hardness meter). The results (count number) are shown in Table 3. A count number of 20 to 50 is practically preferable.

Table 3 shows that the coating film formed using the coating composition (Examples 1-8) of this invention has moderate hardness.

Test Example 4 (Coating adhesion test)
The adhesion test of the coating film was performed in accordance with JIS K-5600-5-6. Specifically, the test was conducted according to the following method. First, the fiber reinforced plastic board (FRP board) (75 * 150 * 2 mm) and tin plate (75 * 150 * 2 mm) which carried out the blasting finish for the coating composition obtained in Examples 1-8 and Comparative Examples 1-5. ) Was applied so that the thickness as a dry coating film was about 100 μm. Next, a dried coating film having a thickness of about 100 μm was produced by drying at 40 ° C. for 1 day. An adhesion test was performed on the dried coating film (2 mm × 2 mm, number of cells = 100).

  The case where the number of the non-peeled bombs is 70 to 100, ◎, the case where the number of the non-peeled moths is 40 to 69, ◯, the number of the non-peeled galores is 20 to The case of 39 was shown as Δ, and the case where the number of gouges that did not peel was 0-19 was shown as x.

  The results are shown in Table 3.

  From Table 3, the coating film formed using the coating composition of the present invention (Examples 1 to 8) can be firmly bonded regardless of whether it is formed on either the FRP plate or the tin plate. Recognize.

Test Example 5 (Coating Flexibility Test)
The coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied to a blasted tin plate (75 × 150 mm) so that the thickness as a dry coating film was about 100 μm. Subsequently, the obtained coated material was dried at 40 ° C. for 1 day to prepare a dry coating film having a thickness of about 100 μm. The tinplate on which the dried coating film was formed was bent at 90 degrees, and the state of the coating film was confirmed by visual observation.

  The case where almost no crack was generated was rated as ◎, the case where a fine crack was generated as ○, the case where a large crack was generated as Δ, and the case where a part of the coating film was easily peeled as X.

  The results are shown in Table 3.

  Table 3 shows that the coating film formed using the coating-film composition (Examples 1-8) of this invention is a tough coating film which is not weak.

Test Example 6 (Water resistance test of coating film)
On a frosted glass plate (75 × 150 × 1 mm), a rust preventive paint (vinyl A / C) was applied so that the thickness after drying was about 50 μm, and dried to form a rust preventive coating. Thereafter, the coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied on the rust-proof coating film so that the film thickness as a dry coating film was about 100 μm. The obtained coated material was dried at 40 ° C. for 1 day to prepare a test piece having a dry coating film having a thickness of about 100 μm. After immersing the test piece in natural seawater at 35 ° C. for 3 months, the state of the coating film was confirmed by visual observation.

  The case where there was no change in the coating film was evaluated as ◎, the case where the color changed slightly, ○, the case where slight blistering occurred, and the case where abnormalities such as cracks, swelling and peeling were confirmed.

  The results are shown in Table 3.

  From Table 3, it turns out that the coating film formed using the coating-film composition (Examples 1-8) of this invention is excellent in water resistance.

Test Example 7 (Coating film solubility test (rotary test))
A rotating drum having a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and an automatic pH controller for keeping the pH of the seawater constant were attached.

  Two test plates were prepared according to the following method.

  First, a rust-preventing coating film was formed by applying and drying a rust-preventive paint (vinyl A / C) on a hard PVC plate (75 × 150 × 1 mm) so that the thickness after drying was about 50 μm. Thereafter, the antifouling coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied on the anticorrosive coating film so that the thickness after drying was about 300 μm. The obtained coated material was dried at 40 ° C. for 3 days to prepare a test plate having a dry coating film having a thickness of about 300 μm.

  One of the produced test plates was fixed to the rotating drum of the rotating device of the apparatus so as to contact seawater, and the rotating drum was rotated at a speed of 20 knots. Meanwhile, the temperature of the seawater was maintained at 25 ° C. and the pH at 8.0 to 8.2, and the seawater was replaced every week.

  The initial film thickness of each test plate and the remaining film thickness after 1 month, 3 months and 6 months are measured with a laser focus displacement meter, and the dissolved film thickness is calculated from the difference between the initial 6 months. The amount of coating film dissolved was determined.

  About the coating-film dissolution amount, it represented with the total dissolution amount (micrometer) of the coating film in the period. The results are shown in Table 4.

  From Table 4, it can be seen that the coating films formed using the coating compositions of the present invention (Examples 1 to 8) have a sufficiently large dissolution of the coating film from the beginning and have a good initial antifouling effect.

  It turns out that the coating film formed using the coating composition of Comparative Examples 1-5 is hard to melt | dissolve in seawater at the initial stage, and cannot exhibit an antifouling effect effectively. Since the coating films formed using the coating compositions of Comparative Examples 2 and 3 had low water resistance, cracks and peeling occurred in the middle.

Test Example 8 (Slime adhesion test)
The coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied to both sides of a hard PVC plate (100 × 200 × 2 mm) so that the thickness after drying was about 100 μm. The obtained coated material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 100 μm. The test plate was immersed in 1.5 m below the sea level in Kushimoto City, Wakayama Prefecture, and the state of slime adhesion to the test plate after 1 month, 2 months and 3 months after immersion was confirmed by visual observation.

  The results are shown in Table 5.

  The numbers in the table represent the degree of slime adhesion. 0 for slime that can hardly be confirmed, 1 for slightly attached slime, 2 for thickly attached slime but easy to remove by brush, 2 for thickly adhered slime, and removed by brush Difficult thing was set to 3.

  From Table 5, compared with the coating film formed using the coating composition of Comparative Examples 1-5, in the coating film formed using the coating composition (Examples 1-8) of this invention, it is almost. It turns out that slime does not adhere. This is because the coating film formed using the coating composition of the present invention has a necessary and sufficient coating film dissolution from the beginning.

Test Example 9 (Topcoat test)
The test plate subjected to the slime property test of Test Example 8 was washed with ion-exchanged water and dried at room temperature (25 ° C.) for 1 day. Thereafter, the coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied to one side of each test plate so that the thickness as a dry coating film was about 100 μm. The obtained coated material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate in which a new coating film having a thickness of about 100 μm was overcoated on the old coating film. With respect to these test plates, an adhesion test of the coating film was performed according to JIS K-5600-5-6 (2 mm × 2 mm, number of cells = 100).

  The case where the number of the non-peeled buns is 70-100, ◎, the case where the number of the non-peeled buns is 40-69, the number of the non-peeled bans is 20- The case of 39 was shown as Δ, and the case where the number of gouges that did not peel was 0-19 was shown as x.

  The results are shown in Table 5.

  From Table 5, compared with the coating film formed using the coating-film composition of Comparative Examples 1-5, the coating film formed using the coating composition (Examples 1-8) of this invention is new. It can be seen that the coating is sufficiently adhered on the old coating. This is because the coating films formed using the coating compositions of Comparative Examples 1 to 5 have poor initial coating solubility, so that slime adheres in a short period of time. This is because the coating film formed by use has sufficient coating film dissolution from the beginning, the coating film surface is renewed, and slime hardly adheres.

Test Example 10 (Anti-fouling test)
The coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied on both sides of a hard PVC plate (100 × 200 × 2 mm) so that the thickness as a dry coating film was about 200 μm. The obtained coated material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 200 μm. The test plate was immersed in 1.5 m below the sea surface in Owase City, Mie Prefecture, and the test plate was observed for 24 months for contamination by deposits.

  The results are shown in Table 6.

  In addition, the number in a table | surface represents the adhesion area (%) of a fouling organism.

  From Table 6, compared with the coating film formed using the coating-film composition of Comparative Examples 1-5, in the coating film formed using the coating composition (Examples 1-8) of this invention, it is almost. It can be seen that the waterpox fouling organisms are not attached. This is because the coating film formed using the coating composition of the present invention has a hydrolysis rate suppressed to some extent and dissolves stably at a constant rate for a long period of time.

Claims (23)

(A) a polymer having a number average molecular weight of 1,000 to 20,000, obtained by polymerizing a polymerizable unsaturated carboxylic acid triorganosilyl;
(B) An antifouling paint composition containing at least one zinc salt selected from rosin zinc salts and zinc salts of rosin derivatives,
(1) The weight ratio ((A) / (B)) between the content of the polymer (A) and the content of the zinc salt (B) is 45/55 to 10/90,
(2) The non-volatile content is 75% by weight or more,
(3) substantially free of rosin and rosin derivatives having a free carboxyl group,
Antifouling paint composition. The antifouling paint composition according to claim 1, wherein the polymer (A) has a number average molecular weight of 2,000 to 15,000 and a molecular weight dispersity of less than 2.5. The antifouling paint composition according to claim 1 or 2, wherein the polymer (A) has a glass transition temperature of 20 to 70 ° C. The antifouling paint composition according to any one of claims 1 to 3, wherein the polymer (A) is a triisopropylsilyl (meth) acrylate copolymer. The (meth) acrylic acid triisopropylsilyl copolymer comprises (a) 30 to 60% by weight of triisopropylsilyl (meth) acrylate, (b) 10 to 50% by weight of methyl methacrylate, and (c) (a). And an antifouling paint composition according to any one of claims 1 to 4, which is obtained by copolymerizing 0 to 60% by weight of (meth) acrylic acid ester other than (b). The rosin zinc salt is at least one zinc salt selected from the group consisting of gum rosin zinc salt, wood rosin zinc salt and tall oil rosin zinc salt, and the zinc salt of the rosin derivative is a hydrogenated rosin zinc salt and a disproportionated rosin. The antifouling paint composition according to claim 1, which is at least one zinc salt selected from the group consisting of zinc salts. The antifouling paint composition according to claim 1, wherein the content of nonvolatile components is 80% by weight or more, and the viscosity at 25 ° C. measured using a Stormer viscometer is 80 to 100 KU. The antifouling paint composition according to any one of claims 1 to 7, wherein the content of the volatile organic compound is less than 400 g / L. The antifouling paint composition according to any one of claims 1 to 8, further comprising 10 to 100 parts by weight of zinc oxide based on 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B). . Furthermore, the antifouling paint composition of Claims 1-9 which contains a cuprous oxide 100-400 weight part with respect to 100 weight part of total amounts of the said polymer (A) and the said zinc salt (B). The antifouling paint composition according to claim 10, wherein the cuprous oxide is cuprous oxide having an average particle diameter of 8 to 20 μm. The antifouling paint composition according to claim 1, further comprising 1 to 100 parts by weight of an organic antifouling agent relative to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B). . Furthermore, the antifouling paint composition of Claims 1-12 which contains a plasticizer 1-50 weight part with respect to 100 weight part of total amounts of the said polymer (A) and the said zinc salt (B). The antifouling paint composition according to claim 13, wherein the plasticizer is an epoxidized oil or fat. Furthermore, the antifouling paint composition of Claims 1-14 which contains 1-50 weight part of dehydrating agents with respect to 100 weight part of total amounts of the said polymer (A) and the said zinc salt (B). The antifouling paint composition according to claim 15, wherein the dehydrating agent is at least one water binder selected from alkoxysilanes and alkyl orthoformate. Furthermore, 1-50 weight part of fatty-acid amide type dispersing agents are included with respect to 100 weight part of total amounts of the said polymer (A) and the said zinc salt (B), The antifouling paint composition of Claims 1-16. . The antifouling processing method which forms an antifouling coating film on the surface of a to-be-coated-film formation object using the antifouling coating material composition of Claims 1-17. The antifouling coating film formed using the antifouling paint composition according to claim 1. A coated product having the antifouling coating film according to claim 19 on a surface thereof. A method for producing an antifouling paint composition, comprising:
(A) a polymer having a number average molecular weight of 1,000 to 20,000, obtained by polymerizing a polymerizable unsaturated carboxylic acid triorganosilyl;
(B) mixing at least one zinc salt selected from rosin zinc salts and zinc salts of rosin derivatives;
(1) The weight ratio ((A) / (B)) between the content of the polymer (A) and the content of the zinc salt (B) is 45/55 to 10/90,
(2) The non-volatile content is 75% by weight or more,
(3) substantially free of rosin and rosin derivatives having a free carboxyl group,
A method for producing an antifouling paint composition. In addition to the polymer (A) and the zinc salt (B), after further mixing cuprous oxide having an average particle size of 3 to 10 µm, the resulting mixture is mixed and dispersed using a disperser. The manufacturing method of the antifouling coating composition of 21. A mixture obtained by mixing the polymer (A) and the zinc salt (B) is mixed and dispersed using a disperser, and then cuprous oxide having an average particle size of 10 to 20 μm is added and mixed. The manufacturing method of the antifouling paint composition of Claim 21.