Antifouling coating composition, antifouling coating film and antifouling substrate, and method for producing antifouling substrate

Abstract

The antifouling coating composition according to the present invention includes a silylacrylic copolymer including a structural unit (1) derived from triisopropylsilyl methacrylate (i), a structural unit (2) derived from triisopropylsilyl acrylate (ii) and a structural unit (3) derived from a polymerizable monomer having a polymerizable double bond (iii), which excludes the above (i) and (ii), the silylacrylic copolymer satisfies specific requirements. Thus, an antifouling coating composition that is excellent in long-term storage stability and gives a coating film excellent in long-term antifouling properties and long-term water resistance can be provided.

Claims

1. An antifouling coating composition, comprising a silylacrylic copolymer (A) which comprises: a structural unit (1) derived from triisopropylsilyl methacrylate (i); a structural unit (2) derived from triisopropylsilyl acrylate (ii); and a structural unit (3) derived from a polymerizable monomer having a polymerizable double bond (iii), which excludes the (i) and (ii), wherein a content weight ratio ([(1)+(2)]/(3)) of a total weight ((1)+(2)) of the structural unit (1) and the structural unit (2) to a content weight of the structural unit (3) is from 50/50 to 90/10, and a content weight ratio ((1)/(2)) of the content weight of the structural unit (1) to the content weight of the structural unit (2) is more than 50/50 and not more than 95/5.

2. The composition according to claim 1, wherein the polymerizable monomer (iii) is an ester having a polymerizable double bond, or a carboxylic acid having a polymerizable double bond.

3. The composition according to claim 1, further comprising a rosin, a monocarboxylic acid compound (B), or both.

4. The composition according to claim 3, wherein a content weight ratio (W.sub.A/W.sub.B) of a content weight (W.sub.A) of the silylacrylic copolymer (A) to a content weight (W.sub.B) of the rosin, monocarboxylic acid compound (B), or both, is from 99.9/0.1 to 30/70.

5. The composition according to claim 1, further comprising at least one component selected from the group consisting of a copper compound (C), an organic antifouling agent (D), a solvent (F), and an additive (E) selected from the group consisting of a plasticizer (e1), an extender pigment (e2), a pigment dispersant (e3), a coloring pigment (e4), an anti-sagging agent (e5), an anti-settling agent (e6) and a dehydrating agent (e7).

6. An antifouling coating film formed by curing the antifouling coating composition according to claim 1.

7. An antifouling substrate formed by a method comprising: coating or impregnating a substrate with the antifouling coating composition according to claim 1; and curing the coating composition, to thereby form an antifouling coating film on the substrate.

8. The substrate according to claim 7, wherein the substrate is in contact with seawater or fresh water.

9. The substrate according to claim 7, wherein the substrate is at least one selected from the group consisting of an underwater structure, a ship and a fishing gear.

10. A method for producing an antifouling substrate, comprising: coating or impregnating a substrate with the antifouling coating composition according to claim 1; and curing the coating composition, to thereby form an antifouling coating film on the substrate.

11. A silylacrylic copolymer, comprising: a structural unit (1) derived from triisopropylsilyl methacrylate (i); a monomer structural unit (2) derived from triisopropylsilyl acrylate (ii); and a structural unit (3) derived from a polymerizable monomer having a polymerizable double bond (iii), which excludes (i) and (ii), wherein a content weight ratio ([(1)(2)]/(3)) of a total weight ((1)+(2)) of the structural unit (1) and the structural unit (2) to a content weight of the structural unit (3) is from 50/50 to 90/10, and a content weight ratio ((1)/(2)) of the content weight of the structural unit (1) to the content weight of the structural unit (2) is more than 50/50 and not more than 95/5.

Description

EMBODIMENTS OF THE INVENTION

(1) Hereinafter, the antifouling coating composition, the antifouling coating film and the antifouling substrate, and the antifouling substrate production method, according to the present invention, are described in detail.

(2) [Antifouling Coating Composition]

(3) The antifouling coating composition of the present invention (antifouling paint) comprises a specific silylacrylic copolymer (A). The antifouling paint of the present invention may contain an optional component according to purpose.

(4) 1. Silylacrylic Copolymer (A)

(5) The silylacrylic copolymer (A) comprises a structural unit (1) derived from triisopropylsilyl methacrylate (i), a monomer structural unit (2) derived from triisopropylsilyl acrylate (ii) and a structural unit (3) derived from a polymerizable monomer (iii) having a polymerizable double bond, which excludes the above (i) and (ii).

(6) This silylacrylic copolymer satisfies the following Requirements 1 and 2.

(7) Requirement 1: the content weight ratio ([(1)+(2)]/(3)) of the total weight ((1)+(2)) of the structural unit (1) and the structural unit (2) to the content weight of the structural unit (3) is 50/50 to 90/10, desirably 60/40 to 80/20, in terms of improving coating film hydrolyzability (consumption property), static antifouling properties and the like.

(8) Requirement 2: the content weight ratio ((1)/(2)) of the content weight of the structural unit (1) to the content weight of the structural unit (2) is more than 50/50 and not more than 95/5, desirably 60/40 to 90/10, in terms of improving coating film water resistance (mechanical properties), coating film hydrolyzability (consumption property), static antifouling properties, storage stability and the like.

(9) For convenience sake, the content weight ratios in the Requirement 1 and the Requirement 2 are also called the content weight ratio (I) and the content weight ratio (II), respectively.

(10) It is preferred that the silylacrylic copolymer (A) is contained in the antifouling coating composition of the present invention usually in an amount of 10 to 50% by weight, preferably 15 to 30% by weight, in terms of improving coating workability, long-term storage stability, coating film water resistance (mechanical properties), coating film hydrolyzability (consumption property), static antifouling properties, coating film appearance and the like. It is preferred that the silylacrylic copolymer (A) is contained, with respect to 100% by weight of the solid content (heat residue or non-volatile content) of the antifouling coating composition of the present invention, usually in an amount of about 5 to 50% by weight, preferably about 10 to 30% by weight, in terms of improving coating workability, long-term storage stability, coating film water resistance (mechanical properties), coating film hydrolyzability (consumption property), static antifouling properties and coating film appearance. The solid content (heat residue) contained in the antifouling coating composition is obtained by keeping 1.5 g of the antifouling coating composition in a thermostat chamber at 125 C. for 1 hour to remove volatile contents.

(11) The polymerizable monomer having a polymerizable double bond (iii) refers to a monomer excluding the triisopropylsilyl methacrylate (i) and the triisopropylsilyl acrylate (ii) and having a polymerizable double bond (for example, vinyl group, (meth)acryloyl group), and is copolymerized with the above (i), (ii) or the monomer (iii).

(12) The polymerizable monomer (iii) is preferably an ester having a polymerizable double bond, or a carboxylic acid having a polymerizable double bond. The polymerizable monomer (iii), by being such compounds, achieves good compatibility with the triisopropylsilyl methacrylate (i) and the triisopropylsilyl acrylate (ii), and has reactivity with the triisopropylsilyl methacrylate (i) that is a similar degree to reactivity with the triisopropylsilyl acrylate (ii). Therefore, the produced silylacrylic copolymer (A) has structural units derived from respective monomers which are uniformly (randomly) incorporated, and has good compatibility also with respect to a solvent. In other words, when the polymerization reactivity is extremely different among respective monomers and the copolymerization of respective monomers is difficult, a problem such that copolymers having structural units in a non-uniform manner or homopolymers are obtained is caused. By contrast, when the polymerizable monomer (iii) is the compounds described above, the occurrence of the above problem is reduced, and stable production of the silylacrylic copolymer (A) is achieved.

(13) Examples of the ester and the carboxylic acid used as the polymerizable monomer (iii), which exclude the triisopropylsilyl methacrylate (i) and the triisopropylsilyl acrylate (ii), include (meth)acrylic acid esters, monocarboxylic acids, dicarboxylic acids and half-esters (monoester), diesters and vinyl esters thereof. Examples of the polymerizable monomer (iii) other than the esters and the carboxylic acids include styrenes.

(14) Specific examples of the polymerizable monomer (iii) include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, allyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobonyl (meth)acrylate, methoxy (meth)acrylate, ethoxy (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate;

(15) monocarboxylic acids such as (meth)acrylic acids;

(16) dicarboxylic acids such as itaconic acid, maleic acid and succinic acid, and half-esters (monoesters) and diesters thereof;

(17) styrenes such as styrene and -methyl styrene; and

(18) vinyl esters such as vinyl acetate and vinyl propionate.

(19) These are used singly, or two or more kinds thereof may be combined.

(20) The silylacrylic copolymer (A) preferably has a weight average molecular weight of 5000 to 100000, more preferably 10000 to 60000. By employing the silylacrylic copolymer (A) having a weight average molecular weight falling within these ranges, the antifouling coating composition gives a coating film that has good hydrolyzability and has much improved static antifouling properties and further excellent long-term mechanical properties (e.g. adhesion of the antifouling coating film of the present invention to a substrate, an under-coating film and the like, and appearance properties such as cracking of the antifouling coating film, in the case of immersion in water for a long term).

(21) The value of the weight average molecular weight is that as measured by gel permeation chromatography (GPC), and determined by using standard polystyrene calibration curve. The GPC conditions in molecular weight measurement are as follows.

(22) GPC Conditions

(23) Pump: HLC-8120GPC (manufactured by Tosoh Corporation)

(24) Column: SuperH2000+H4000 (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length) for each column)

(25) Eluent: tetrahydrofran (THF)

(26) Other Conditions

(27) Flow rate: 0.500 ml/min.

(28) Detector: RI

(29) Column thermostat chamber temperature: 40 C.

(30) Standard substance: polystyrene

(31) Sample preparation method: To a solution containing the copolymer (A), a small amount of calcium chloride is added to dehydrate the solution, which is followed by filtration with a membrane filter. The obtained filtered material is used as a sample for GPC measurement.

(32) In the silylacrylic copolymer (A), the content weight ratio ([(1)+(2)]/(3)) (the content weight ratio (I)) of the total weight ((1)+(2)) of the structural unit (1) and the structural unit (2) to the content weight of the structural unit (3) is 50/50 to 90/10, preferably 55/45 to 85/15, more preferably 60/40 to 80/20.

(33) When the content weight ratio (I) is within the above range, it is possible to obtain an antifouling coating composition having good coating film hydrolyzability (consumption property), static antifouling properties and coating film water resistance (mechanical properties).

(34) The content weight ratio ((1)/(2)) (the content weight ratio (II)) of the content weight of the structural unit (1) to the content weight of the structural unit (2) is more than 50/50 and not more than 95/5, preferably 55/45 to 90/10, more preferably 60/40 to 85/15, particularly preferably 65/35 to 80/20.

(35) When the content weight ratio (II) is within the above range, the antifouling coating film formed from the antifouling coating composition, when immersed in water, particularly seawater, exhibits sufficient coating film consumption property (renewability), and therefore exhibits good long-term antifouling properties such as static antifouling properties, making it possible for cracking to occur less often for a long term.

(36) The silylacrylic copolymer (A) is prepared by copolymerizing the triisopropylsilyl methacrylate (i), the triisopropylsilyl acrylate (ii) and the polymerizable monomer having a polymerizable double bond (iii) by a known polymerization method. An exemplary polymerization method is a radical or ionic polymerization in solution polymerization, bulk polymerization, semi-batch polymerization, suspension polymerization, coordination polymerization, living polymerization or emulsification polymerization.

(37) In particular, in terms of improving the productivity and manufacturing workability of the silylacrylic copolymer (A) as well as preparing the copolymer (A) having low viscosity, it is preferable to subject the above (i)-(iii) to solution polymerization by using an organic solvent commonly used such as toluene, xylene, methyl isobutyl ketone and n-butyl acetate. When the copolymer (A) has a low viscosity as described above, the amount of a solvent added to reduce the viscosity of the antifouling coating composition can be lowered, leading to the decrease in the VOC value. The reduced viscosity of the antifouling coating composition can enhance the coating workability of the coating composition, and the appearance properties (leveling properties) and the like of the antifouling coating film.

(38) As radical polymerization catalysts, known ones can be widely used, such as azo compounds such as 2,2-azobis(2-methylbutyronitrile) (AMBN), 2,2-azobis(2,4-dimethylvaleronitrile) and 2,2-azobis-isobutyronitrile; and peroxides such as benzoylperoxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t-butylperoxyoctoate, as described in JP-A-2001-151830, paragraph [0099] and the like.

(39) The ratio of charge (weight) of the above (i) to (iii), which are monomers subjected to polymerization reaction, tends to correspond to the content (weight) ratio of the structural units (1) to (3) contained in the resultant copolymer, respectively. Thus, regarding the Requirements 1 and 2, the content weight ratio (I) and the content weight ratio (II) can be controlled to be desired ones, based on the amounts (weights) of charge of (i) to (iii) and on the weight ratio of charge ((i)/(ii) or ((i)+(ii))/((i)+(ii)+(iii))).

(40) 2. Rosin or Monocarboxylic Acid Compound (B)

(41) The antifouling coating composition of the present invention may comprise a rosin or a monocarboxylic acid compound (B), in terms of promoting the elution of the antifouling agent from the antifouling coating film formed from the composition in order to improve particularly static antifouling properties. Examples of the rosin used herein include rosins such as gum rosin, wood rosin and tall oil rosin, and rosin derivatives such as a hydrogenated rosin and a disproportionated rosin. Examples of the monocarboxylic acid compound include aliphatic or alicyclic monocarboxylic acids, monocarboxylic acid derivatives thereof and metal salts thereof.

(42) Specific examples of the monocarboxylic acid compounds include naphthenic acid, cycloalkenylcarboxylic acids, bicycloalkenylcarboxylic acids, versatic acid, trimethyl isobutenyl cyclohexene carboxylic acid, stearic acid, hydroxystearic acid, salicylic acid, and metal salts thereof.

(43) In the antifouling coating composition of the present invention, the content weight ratio (W.sub.A/W.sub.B) of the content weight (W.sub.A) of the copolymer (A) to the content weight (W.sub.B) of the rosin or monocarboxylic acid compound (B) is preferably 99.9/0.1 to 30/70, more preferably 95/5 to 35/65, still more preferably 90/10 to 40/60. When the content weight ratio is within these ranges, the grindability (coating film consumption property) of the antifouling coating film formed from the antifouling coating composition is increased, and thereby the antifouling properties (in particular static antifouling properties) can be enhanced.

(44) 3. Copper Compound (C)

(45) The antifouling coating composition of the present invention, in order to provide an antifouling coating film formed from the antifouling coating composition that has further improved antifouling properties, may further comprise a copper compound (C). The copper compound may be any of organic or inorganic copper compounds, with examples thereof including cuprous oxide, copper thiocyanate, cupronickel and copper pyrithione.

(46) In the antifouling coating composition of the present invention, the content of the copper compound (C), with respect to 100 parts by weight of the copolymer (A), is preferably 10 to 800 parts by weight, more preferably 100 to 750 parts by weight, in terms of improving long-term antifouling properties of the antifouling coating film. The content of the copper compound (C), with respect to 100% by weight of the antifouling coating composition (containing a solvent), is usually about 0.1 to 70% by weight, preferably about 0.1 to 60% by weight.

(47) It is preferable that these copper compounds are copper compounds that do not contain 2% or more of metallic copper based on their total weight.

(48) 4. Organic Antifouling Agent (D)

(49) The antifouling coating composition of the present invention may further comprise an organic antifouling agent (D), in order to provide the antifouling coating film formed from the antifouling coating composition that has further improved antifouling properties, particularly improved antifouling effects on plant marine organism. The organic antifouling agent (D) is not particularly limited as long as being organic compounds that provide the antifouling coating film with antifouling properties, excluding the above-mentioned organic copper compounds.

(50) Examples of the organic antifouling agent (D) include metal pyrithiones such as zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, pyridinetriphenylborane, N,N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2,4,5,6-tetrachloroisophthalnitrile, bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate, chloromethyl-n-octyldisulfide, N,N-dimethyl-N-phenyl-(N-fluorodichloromethylthio)sulfamide, tetraalkylthiuramdisulfide, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 2,3-dichloro-N-(2,6-diethylphenyl)maleimide and 2,3-dichloro-N-(2-ethyl-6-methylphenyl)maleimide.

(51) In the antifouling coating composition of the present invention, the content of the organic antifouling agent (D), with respect to 100 parts by weight of the copolymer (A), is preferably 0.1 to 500 parts by weight, more preferably 0.5 to 300 parts by weight, in terms of allowing the antifouling coating film formed from the antifouling coating composition to have improved maintenance of long-term antifouling properties and coating film water resistance (maintaining of mechanical properties). The content of the organic antifouling agent (D), with respect to 100% by weight of the antifouling coating composition (containing a solvent), is usually about 0.1 to 30% by weight, preferably about 0.1 to 20% by weight.

(52) 5. Other Additive(s) (E)

(53) The antifouling coating composition of the present invention may comprise at least one additive (E) selected from the group consisting of a plasticizer (e1), an extender pigment (e2), a pigment dispersant (e3), a coloring pigment (e4), an anti-sagging agent (e5), an anti-settling agent (e6) and a dehydrating agent (e7). Hereinafter, these additives (E) are described in detail.

(54) Plasticizer (e1)

(55) It is preferable that the antifouling coating composition of the present invention comprises a plasticizer (e1) in order to give an antifouling coating film that has improved crack resistance. Examples of the plasticizer (e1) include paraffin chloride (chlorinated paraffin), petroleum resins, ketone resins, TCP (tricresyl phosphate), polyvinyl ethyl ether and dialkylphthalate. In terms of allowing the antifouling coating film formed from the antifouling coating composition to have improved coating film water resistance (mechanical properties) and coating film hydrolyzability (consumption property), the plasticizer (e1), among these, is preferably paraffin chloride (chlorinated paraffin), petroleum resins or ketone resins. The plasticizer (e1) may be used singly, or two or more kinds thereof may be combined.

(56) Paraffin chloride may have any of linear molecular structure or branched molecular structure, and may be at a liquid state or a solid state (for example: powder state) under room temperature (for example: 23 C.) condition.

(57) Paraffin chloride has carbons in which the average number of carbons in one molecule is usually 8 to 30, preferably 10 to 26. An antifouling coating composition containing such paraffin chloride can form an antifouling coating film that has less cracking (fracture) and peeling. If the average number of carbons is less than 8, the effect of suppressing the occurrence of cracks in the antifouling coating film may become insufficient. On the other hand, if the average number of carbons is more than 30, an antifouling coating film may have decreased hydrolyzability (renewability, grindability), thus having deteriorated antifouling properties.

(58) The paraffin chloride usually has a viscosity (unit: Poise, measurement temperature: 25 C.) of 1 or more, preferably 1.2 or more, and usually has a specific gravity (25 C.) of 1.05 to 1.80, preferably 1.10 to 1.70.

(59) The paraffin chloride usually has a chlorination percentage (chlorine content) with respect to 100% by weight of paraffin chloride, of 35 to 70% by weight, preferably 35 to 65% by weight. By containing the paraffin chloride having such chlorination percentage, the antifouling coating composition can form a coating film that has less cracking (fracture), peeling and the like. Specific examples of such paraffin chloride include TOYOPARAX 150 and TOYOPARAX A-70 (both of which are manufactured by Tosoh Corporation).

(60) Examples of the petroleum resins include C5-based ones, C9-based ones, styrene-based ones, dichloropentadiene-based ones, and hydrogenated products thereof. Specific examples of the petroleum resins include Quintone 1500 and Quintone 1700 (both of which are manufactured by Zeon Corporation).

(61) In the antifouling coating composition of the present invention, the content of the plasticizer (e1), with respect to 100 parts by weight of the copolymer (A), is preferably 0.1 to 300 parts by weight, more preferably 0.1 to 200 parts by weight, still more preferably 0.1 to 150 parts by weight, in terms of allowing the antifouling coating film formed from the antifouling coating composition to have improved coating film hydrolyzability (consumption property), antifouling properties and coating film water resistance (mechanical properties).

(62) The content of the plasticizer (e1), with respect to 100% by weight of the antifouling coating composition (containing a solvent), is usually about 0.1 to 30% by weight, preferably about 0.1 to 20% by weight.

(63) Extender Pigment (e2)

(64) The extender pigment (e2) can provide the antifouling coating film formed from the antifouling coating composition with improved coating film properties such as crack resistance.

(65) Examples of the extender pigment (e2) include talc, silica, mica, clay, potassium feldspar, zinc oxide, calcium carbonate, kaolin, aluminum white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate and barium sulfate. Among these, preferred are talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, potassium feldspar and zinc oxide. Calcium carbonate and white carbon are used also as an anti-settling agent (e6) described later and a matting agent.

(66) In the antifouling coating composition of the present invention, the content of the extender pigment (e2), with respect to 100 parts by weight of the copolymer (A), is preferably 0.1 to 500 parts by weight, more preferably 50 to 300 parts by weight, in view of allowing the antifouling coating film formed from the antifouling coating composition to have improved coating film water resistance (mechanical properties) and antifouling properties and coating film hydrolyzability (consumption property).

(67) The content of the extender pigment (e2) is, with respect to 100% by weight of the antifouling coating composition (containing a solvent), usually about 0.1 to 50% by weight, preferably about 0.1 to 40% by weight.

(68) Pigment Dispersant (e3)

(69) Examples of the pigment dispersant (e3) include known various organic and inorganic pigment dispersants. Examples of the pigment dispersants include aliphatic amines or organic acids (Duomeen TDO manufactured by Lion Co., Ltd.; Disperbyk-101 manufactured by BYK CHEMIE).

(70) In the antifouling coating composition of the present invention, the content of the pigment dispersant (e3), with respect to 100 parts by weight of the copolymer (A), is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 50 parts by weight in terms of improving the effect of reducing the coating material viscosity of the antifouling coating composition and the effect of preventing the flooding of the antifouling coating film.

(71) The content of the pigment dispersant (e3), with respect to 100% by weight of the antifouling coating composition (containing a solvent), is usually about 0.1 to 10% by weight, preferably about 0.1 to 5% by weight.

(72) Coloring Pigment (e4)

(73) The antifouling coating composition of the present invention may comprise a coloring pigment (e4) in order to provide the antifouling coating film formed from the antifouling coating composition with controlled hue and desired hue.

(74) Examples of the coloring pigment (e4) include various known organic and inorganic coloring pigments. Examples of the organic coloring pigments include carbon black, naphthol red and phthalocyanine blue. Examples of the inorganic coloring pigments include red iron oxide, barite powder, titanium white, and yellow iron oxide.

(75) The antifouling coating composition of the present invention may comprise, together with the coloring pigment (e4) or instead of the coloring pigment (e4), a colorant excluding the coloring pigment (e4), such as dyes.

(76) In the antifouling coating composition of the present invention, the content of the coloring pigment (e4), with respect to 100 parts by weight of the copolymer (A), is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 10 parts by weight, in terms of allowing the antifouling coating film formed from the antifouling coating composition to have improved coloring properties, shielding properties, exposure discoloration properties, antifouling properties, and coating film water resistance (mechanical properties).

(77) The content of the coloring pigment (e4), with respect to 100% by weight of the antifouling coating composition (containing a solvent), is usually about 0.1 to 30% by weight, preferably about 0.1 to 20% by weight.

(78) Anti-Sagging Agent (e5)

(79) The antifouling coating composition of the present invention may comprise an anti-sagging agent (e5) (also called an anti-running agent) in terms of reducing the occurrence of the sagging of the coating composition upon coating the substrate with the antifouling coating composition.

(80) Examples of the anti-sagging agent (e5) include amide wax, hydrogenated castor oil-based wax, mixtures thereof and synthetic fine powder silica. The anti-sagging agent (e5) is particularly preferably amide wax or synthetic fine powder silica. By using amide wax or synthetic fine powder silica as the anti-sagging agent (e5), it is possible to improve the storage stability of the antifouling coating composition; and moreover when the formation of the antifouling coating film is followed by the formation, on such an antifouling coating film, of a coating film (over-coating film) made of the same kind of coating composition (antifouling coating composition) or different kinds of coating compositions, it is possible to prevent decrease of adhesion between the antifouling coating film and the over-coating film (interlayer adhesion, over coating properties).

(81) Examples of commercially available products of the anti-sagging agent (e5) include DISPARLON A630-20XC manufactured by KUSUMOTO CHEMICALS, CO., LTD. and ASAT-250F manufactured by ITO OIL CHEMICALS CO., LTD.

(82) In the antifouling coating composition of the present invention, the content of the anti-sagging agent (e5), with respect to 100 parts by weight of the copolymer (A), is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight. The content of the anti-sagging agent (e5), with respect to 100% by weight of the antifouling coating composition (containing a solvent), is usually about 0.1 to 20% by weight, preferably about 0.1 to 10% by weight. When the content of the anti-sagging agent (e5) is set at the range described above, it is possible to allow the antifouling coating composition to have improved storage stability; and moreover when the formation of the antifouling coating film is followed by the formation, on such an antifouling coating film, of a coating film (over-coating film) made of the same kind of coating composition (antifouling coating composition) or different kinds of coating compositions, it is possible to prevent decrease of adhesion between the antifouling coating film and the over-coating film (interlayer adhesion, over coating properties).

(83) Anti-Settling Agent (e6)

(84) The antifouling coating composition of the present invention may comprise an anti-settling agent (e6) in terms of preventing the coating composition during storage from having precipitates and allowing the coating composition to have improved stirring properties.

(85) Examples of the anti-settling agent (e6) include amine salts of Al, Ca or Zn of organoclay, polyethylene wax and polyethylene oxide-based wax. In particular, the anti-settling agent (e6) is preferably polyethylene oxide-based wax. An example of commercially available products of the polyethylene oxide-based wax is DISPARLON4200-20X (manufactured by Kusumoto Chemical Ltd.).

(86) In the antifouling coating composition of the present invention, the content of the anti-settling agent (e6), with respect to 100 parts by weight of the copolymer (A), is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight. The content of the anti-settling agent (e6), with respect to 100% by weight of the antifouling coating composition (containing a solvent), is usually about 0.1 to 20% by weight, preferably about 0.1 to 10% by weight. When the content of the anti-settling agent (e6) is set within these ranges, it is possible to improve the storage stability of the antifouling coating composition; and moreover when the formation of the antifouling coating film is followed by the formation, on such an antifouling coating film, of a coating film (over-coating film) composed of the same kind of coating composition (antifouling coating composition) or different kinds of coating compositions, it is possible to prevent the decrease in the adhesion between the antifouling coating film and the over-coating film (interlayer adhesion, over coating properties).

(87) Dehydrating Agent (e7)

(88) By employing the copolymer (A), which has good storage stability, the antifouling coating composition of the present invention has excellent storage stability, and as needed, may have a dehydrating agent (e7) added therein in order to have further excellent long-term storage stability. The dehydrating agent (e7) is preferably at least one dehydrating agent selected from the group consisting of synthetic zeolite, anhydrous gypsum and gypsum hemihydrate, as an inorganic dehydrating agent; and alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and trimethylethoxysilane, their condensation products, i.e., polyalkoxysilanes, orthoformic acid alkyl esters such as methyl orthoformate and ethyl orthoformate, as an organic dehydrating agent. The content of these dehydrating agents (e7), with respect to 100 parts by weight of the copolymer (A), is preferably 0.1 to 50 parts by weight.

(89) 6. Solvent (F)

(90) The antifouling coating composition of the present invention may comprise a solvent (F) such as water and organic solvents in order to allow the copolymer (A) and the like to have increased dispersibility and to control the viscosity of the composition. As the solvent (F), the antifouling coating composition of the present invention may comprise a solvent employed when preparing the copolymer (A), or a solvent separately added when mixing the copolymer (A) with other optional components.

(91) Examples of the organic solvent include aromatic organic solvents such as xylene, toluene and ethylbenzene; ketones such as methylethylketone, methylisobutylketone and cyclohexanone; aliphatic (the number of carbon atoms: about 1 to 10, preferably about 2 to 5) monovalent alcohols such as ethanol, isopropyl alcohol, n-butanol and isobutanol; ester solvents such as ethyl acetate and butyl acetate.

(92) The content of the solvent (F) in the antifouling coating composition of the present invention, with respect to 100% by weight of the antifouling coating composition, is usually 20 to 80% by weight, preferably 30 to 70% by weight.

(93) [Production Method for Antifouling Coating Composition]

(94) The antifouling coating composition of the present invention may be produced through the appropriate use of a known method. An exemplary method is such that the copolymer (A), and components (B) to (F) as needed are added to a stirring container at a time or in an arbitrary order, and then these components are mixed by known stirring and mixing means to disperse or dissolve the components in a solvent.

(95) As described above, it is preferable that after the copolymer (A) and the like are dispersed or dissolved in a solvent, amide wax (for example, DISPARLON630-20X and the like) is added, and dispersed for example for about 10 to 20 min, to prepare the antifouling coating composition. This is preferable because upon applying the resultant antifouling coating composition on a substrate, the occurrence of sagging can be decreased.

(96) Examples of the stirring and mixing means include a high-speed disperser and a sand-grinding mill, a basket mill, a ball mill, a three-roll mill, a Ross mixer and a planetary mixer and a universal Shinagawa agitator.

(97) [Antifouling Coating Film and Antifouling Substrate]

(98) The antifouling coating film of the present invention is prepared by letting the antifouling coating composition of the present invention dry naturally or subjecting the antifouling coating composition of the present invention to drying means such as a heater, to thereby cure the composition.

(99) The antifouling substrate of the present invention is formed by coating a substrate (target, material to be coated) with the antifouling coating composition of the present invention by coating means such as an air spray, an airless spray, a brush and a roller, or by impregnating a substrate with the antifouling coating composition of the present invention, and subjecting the coating composition, which is used to coat or impregnate the substrate, to, for example, natural drying (temperature of about room temperature) or drying means such as a heater, to dry and cure the composition to thereby form the antifouling coating film on the substrate.

(100) The substrate used herein, which is not particularly limited, is preferably a substrate contacting with seawater or fresh water. Specific examples thereof include underwater structures such as supply and exhaust ports of various power plants (thermal power plants and nuclear power plants), coastal roads, undersea tunnels, harbor facilities, and sludge-diffusion prevention films employed for various ocean/river civil engineering works such as canals and water channels; ships such as FRP ship (particularly, a part of a ship ranging from its waterline part to its ship bottom); and fishing materials such as fishing gear such as rope and fishing nets, floats and buoys.

(101) Examples of materials for these substrates, particularly for ships, are steel, aluminum and wood. Examples of materials for fishing nets are natural or synthetic fibers. Examples of materials for floats and buoys are synthetic resins. The material of the substrate is not particularly limited as long as antifouling properties and the like in water are required for the substrate.

(102) In the case of the surface of these substrates, particularly that of a ship bottom and the like, usually, a steel-made substrate surface is under-coated with a primer such as an anticorrosive coating material to give a primer-treated substrate, and the surface of the primer-treated substrate surface is coated by the method as described above one time or plural times with the antifouling coating composition of the present invention (antifouling paint). Then, the antifouling coating composition used for coating or impregnating (in particular when a substrate is fishing net or the like) is cured to form an antifouling coating film. As a result, the antifouling coating film is provided which is excellent in properties preventing the adherence of aquatic creatures such as sea lettuce, barnacle, green layer, serpula, oyster and bryozoans for a long term (antifouling properties, particularly static antifouling properties); and particularly when the antifouling coating film contains an antifouling component (for example, copper or copper compounds (component C), organic antifouling agents (component D)), the antifouling component can be gradually released over a long period of time.

(103) When the substrate is a ship (particularly its bottom), an underwater structure or the like (generally, the substrate surface may be primer-treated or have a layer formed from any of epoxy resins, vinyl resin-based paints, acrylic resin-based paints and urethane resin-based paints), such a substrate surface is coated with the antifouling coating composition plural times (thick-coating: thickness of the film dried: about 100 to 600 m), and thereby the resultant antifouling substrate exhibits excellent antifouling properties as well as appropriate plasticity and excellent crack resistance with good balance.

(104) Regarding the production of the antifouling substrate, when the substrate is, for example, a steel plate or fishing net with a deteriorated antifouling coating film, the substrate surface may be directly coated with the antifouling coating composition of the present invention, or may be directly impregnated with the antifouling coating composition of the present invention (when the substrate is fishing net or the like). When the substrate is made of a steel, the substrate surface may be previously coated with a base material such as an anticorrosive and a primer to form a base layer, and then the surface of the base layer may be coated with the coating composition of the present invention. For the purpose of repairing, the antifouling coating film of the present invention may further be formed on the surface of a substrate on which the antifouling coating film of the present invention or a conventional antifouling coating film has been formed.

(105) The thickness of the antifouling coating film, which is not particularly limited, is for example about 30 to 250 m per coating operation when the substrate is a ship or an underwater structure.

(106) As described above, the underwater structure having the antifouling coating film of the present invention can prevent aquatic creatures from adhering thereto over a long period of time, and as a result thereof, the underwater structure can maintain its functions over a long period of time. The fishing net having the antifouling coating film of the present invention has less possibility of environmental pollution, and is prevented from clogging as a result of the prevention of the adherence of aquatic creatures.

EXAMPLES

(107) Hereinafter, with reference to Examples, the present invention is further specifically described, but the present invention is limited in no way with these Examples. In the section of Example, % denotes % by weight unless otherwise noted.

Production Example A1

(108) A reaction vessel equipped with a stirring device, a reflux condenser, a thermometer, a nitrogen-introducing tube and a dropping funnel was charged with xylene in an amount of 53 parts. Under nitrogen atmosphere, while xylene was stirred with the stirring device, under an atmospheric pressure, the reaction vessel was heated until the temperature of xylene in the reaction vessel reached 85 C. While keeping the temperature of xylene in the reaction vessel at 85 C., a monomer mixture composed of 75 parts by weight of TIPSMA (triisopropylsilyl methacrylate), 5 parts by weight of TIPSA (triisopropylsilyl acrylate), 10 parts by weight of EA (ethyl acrylate), 10 parts by weight of MMA (methyl methacrylate) and 1 part by weight of AMBN (2,2-azobis(2-methylbutyronitrile)) was added into the reaction vessel with the dropping funnel over a period of 2 hours.

(109) Subsequently, 0.5 parts by weight of t-butylperoxyoctoate was further added to the reaction vessel. Under atmospheric pressure, while the liquid temperature in the reaction vessel was kept at 85 C., stirring was performed for 2 hours with the stirring device. Then, the liquid temperature in the reaction vessel was raised from 85 C. to 110 C., and heating was performed for 1 hour. Thereafter, into the reaction vessel, 14 parts by weight of xylene was added and the liquid temperature in the reaction vessel was lowered. When the liquid temperature reached 40 C., stirring was stopped. Thereby, a copolymer solution (A1) containing a silyl(meth)acrylate copolymer (polymer (A)) was prepared.

(110) In accordance with test conditions in Evaluation of properties of (co)polymer solution and (co)polymer described later, the heat residue content (% by weight) of the resultant copolymer solution (A1) was calculated, and the weight average molecular weight (Mw) of the polymer contained in the solution was measured (Results are set forth in Table 1).

(111) TABLE-US-00001 TABLE 1 Resin Production Example A1 A2 A3 A4 A5 A6 A7 A8 Polymer Solution A1 A2 A3 A4 A5 A6 A7 A8 Monomer (i) TIPSMA(part by weight) 75 70 60 50 50 45 42 60 mixture (ii) TIPSA(part by weight) 5 10 20 30 30 35 38 10 (iii) EA(part by weight) 10 10 10 10 0 10 10 10 MMA(part by weight) 10 10 10 10 10 10 10 20 BA(part by weight) 10 Reaction AMBN(part by weight) 1 1 1 1 1 1 1 1.2 Initiator Reaction Initiator t-butylperoxyoctoate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (part by weight) Properties Percentage of heat residue in polymer solution 59.5 59.7 59.8 59.6 59.3 59.4 59.7 59.3 Evaluation (wt %) Weight average molecular weight Mw 31,151 32,404 30,228 28,507 31,293 30,334 31,383 31,975 Viscosity of Polymer solution (mPa .Math. s) 1,108 1,027 793 618 721 586 566 1,566 (i)/(ii) (weight ratio) *1 93.8 87.5 75.0 62.5 62.5 56.3 52.5 85.7 6.3 12.5 25.0 37.5 37.5 43.8 47.5 14.3 ((i) + (ii)) content (wt %) *2 80 80 80 80 80 80 80 70 Resin Production Example A9 A10 A11 A12 A13 A14 A15 A16 Polymer Solution A9 A10 A11 A12 A13 A14 A15 A16 Monomer (i) TIPSMA(part by weight) 50 40 37 55 50 40 35 32 mixture (ii) TIPSA(part by weight) 20 30 33 5 10 20 25 28 (iii) EA(part by weight) 10 10 10 10 10 10 10 10 MMA(part by weight) 20 20 20 30 30 30 30 10 BA(part by weight) Reaction AMBN(part by weight) 1.2 1.2 1.2 1.3 1.4 1.4 1.4 1.4 Initiator Reaction Initiator t-butylperoxyoctoate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (part by weight) Properties Percentage of heat residue in polymer solution 59.5 59.7 60.1 59.8 59.4 59.5 59.8 59.7 Evaluation (wt %) Weight average molecular weight Mw 32,741 27,770 30,333 30,251 29,766 31,561 30,012 28,321 Viscosity of Polymer solution (mPa .Math. s) 1,347 1,112 1,099 2,335 2,238 1,952 1,888 1,733 (i)/((ii) (weight ratio) *1 71.4 57.1 52.86 91.7 83.3 66.7 58.3 53.33 28.6 42.9 47.14 8.3 16.7 33.3 41.7 46.67 ((i) + (ii)) content (wt %) *2 70 70 70 60 60 60 60 60 $^{*} 1 (i) / (ii) = \frac{Amount of charge of (i)}{Amount of charge of (ii)}$ $^{*} 2 ((i) / (ii)) Content (wt %) = \frac{\begin{matrix} Amount of charge (i) + \\ Amount of charge of (ii) \end{matrix}}{\begin{matrix} Amoung of charge of (i) + \\ Amount of charge of (ii) + \\ Amount of charge of (iii) \end{matrix}} 100$

Production Examples A2 to A16 and Production Examples B1 to B7

(112) The same procedure as in Production Example A1 was performed except that a monomer mixture having a formulation shown in Table 1 or Table 2 was used instead of the monomer mixture used in Production Example A1. Thereby, a silyl(meth)acrylate (co)polymer solution (A1) containing a silyl(meth)acrylate copolymer (polymer (A)) was prepared, and its heat residue was calculated, and the weight average molecular weight (Mw) of the (co)polymer was measured.

(113) In Tables 1 to 4, (co)polymer solutions A2 to A16 and (co)polymer solutions B1 to B7 refer to solutions containing (co)polymers obtained in Production Examples A2 to A16 and Production Examples B1 to B7, respectively.

(114) TABLE-US-00002 TABLE 2 Resin Production Example B1 B2 B3 B4 B5 B6 B7 Polymer Solution B1 B2 B3 B4 B5 B6 B7 Monomer (i) TIPSMA(part by weight) 70 35 20 10 20 30 mixture (ii) TIPSA(part by weight) 70 35 50 60 40 50 (iii) EA(part by weight) 10 10 10 10 10 10 10 MMA(part by weight) 20 20 20 20 20 30 10 BA(part by weight) Reaction AMBN(part by weight) 1 1.2 1.2 1 1 1.4 0.7 Initiator Reaction Initiator t-butylperoxyoctoate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (part by weight) Properties Percentage of heat residue in polymer solution 59.8 60.4 59.8 60.2 60.6 59.1 60.9 Evaluation (wt %) Weight average molecular weight Mw 29,223 28,578 28,921 30,002 29,256 29,506 27,774 Viscosity of Polymer solution (mPa .Math. s) 1,924 484 992 808 563 1,254 561 (i)/(ii) (weight ratio) *1 100.0 0.0 50.0 28.6 14.3 33.3 37.5 0.0 100.0 50.0 71.4 85.7 66.7 62.5 ((i) + (ii)) content (wt %) *2 70 70 70 70 70 60 80

Example 1

Preparation of Antifouling Coating Composition

(115) A plastic container (volume: 1000 ml) was charged with xylene in an amount of 18.2 parts by weight as a solvent, and trimethyl isobutenyl cyclohexene carboxylic acid (50% xylene solution) as the component B in an amount of 4.0 parts by weight. These components were mixed with a paint shaker until trimethyl isobutenyl cyclohexene carboxylic acid became uniformly dissolved in xylene.

(116) Subsequently, to the plastic container, the polymer solution A1 in an amount of 18 parts by weight was added and mixed with a paint shaker until uniformly dispersed or dissolved. Thereafter, to the plastic container, additives (1) (3.0 parts by weight of talc FC-1, 4.0 parts by weight of zinc oxide (zinc oxide No. 3), 45 parts by weight of cuprous oxide NC301, 0.3 part by weight of Novoperm Red F5RK, 2.0 parts by weight of titanium white R-5N, 1.0 part by weight of copper omadine (copper pyrithione) and 2.0 parts by weight of DISPARLON 4200-20X) were added and stirred with a paint shaker for 1 hour to disperse these components.

(117) After dispersing, 2.5 parts by weight of DISPARLON 630-20X was added and stirred for 20 minutes with a paint shaker. Then, the mixture was filtered with a filtering net (opening: 80 mesh), and the residue was removed to obtain a filtered material (coating composition A1). Manufacturers and the like of the above various additives are set forth in Table 8.

(118) Using the resultant coating composition, in accordance with test conditions described in Evaluation of coating material properties, various properties were evaluated. Results are set forth in Table 5.

Examples 2 to 24 and Comparative Examples 1 to 9

(119) The same procedure was performed as in Example 1 except that the solvent, the polymer solution, the component B and the additives (1) that were used in Example 1 were changed as shown in Tables 3 and 4, to prepare a coating composition, and various coating material properties were evaluated. Results are set forth in Tables 5 and 6.

(120) The coating compositions A2 to A24 and the coating compositions B1 to B9 that are shown in Table 5 and 6 are the coating compositions obtained in Examples 2 to 24 and Comparative Examples 1 to 9, respectively.

(121) TABLE-US-00003 TABLE 3 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 1 2 3 4 5 6 7 8 9 10 11 12 Coating Composition A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 Polymer A1 18 Solution A2 18 A3 18 18 16 A4 18 18 16 18 18 16 16 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 Compo- Trimethylisobutenyl 4 4 4 4 4 7 nent cyclohexenecarboxylic acid B (50% xylene solution) Versatic acid 2 Rosin 2 3.5 2 3.5 3.5 Other Zinc oxide No. 3 4 4 4 4 4 4 4 4 4 4 4 4 Additives Naphthol Red F5RK 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Titanium white R-5N 2 2 2 2 2 2 2 2 2 2 2 2 Disparlon 4200-20X 2 2 2 2 2 2 2 2 2 2 2 2 Talc FC-1 3 3 3 3 3 3 3 3 3 3 3 3 Copper pyrithione 1 1 1 1 1 1 1 1 1 1 1 1 Cuprous oxide NC301 45 45 45 45 45 45 45 45 45 45 45 45 4,5-dichloro-2-n-octyl- 5 5 4-isothiazoline-3-one Xylene 18.2 18.2 18.2 20.2 20.7 18.2 13.2 17.2 20.2 20.2 20.7 15.7 Disparlon A630-20X 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Total 100 100 100 100 100 100 100 100 100 100 100 100 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 13 14 15 16 17 18 19 20 21 22 23 24 Coating Composition A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 Polymer A1 Solution A2 A3 A4 A5 18 A6 18 A7 18 A8 18 A9 18 A10 18 A11 18 A12 18 A13 18 A14 18 A15 18 A16 18 Compo- Trimethylisobutenyl 4 4 4 4 4 4 4 4 4 4 4 4 nent cyclohexenecarboxylic acid B (50% xylene solution) Versatic acid Rosin Other Zinc oxide No. 3 4 4 4 4 4 4 4 4 4 4 4 4 Additives Naphthol Red F5RK 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Titanium white R-5N 2 2 2 2 2 2 2 2 2 2 2 2 Disparlon 4200-20X 2 2 2 2 2 2 2 2 2 2 2 2 Talc FC-1 3 3 3 3 3 3 3 3 3 3 3 3 Copper pyrithione 1 1 1 1 1 1 1 1 1 1 1 1 Cuprous oxide NC301 45 45 45 45 45 45 45 45 45 45 45 45 4,5-dichloro-2-n-octyl- 4-isothiazoline-3-one Xylene 18.2 18.2 18.2 18.2 18.2 18.2 18.2 18.2 18.2 18.2 18.2 18.2 Disparlon A630-20X 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Total 100 100 100 100 100 100 100 100 100 100 100 100

(122) TABLE-US-00004 TABLE 4 Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Coating Composition B1 B2 B3 B4 B5 B6 B7 B8 B9 Polymer B1 18 9 Solution B2 18 9 B3 18 B4 18 B5 18 B6 18 18 B7 18 Component Trimethylisobutenyl 4 4 4 4 4 4 4 B cyclohexenecarboxylic acid (50% xylene solution) Versatic acid 2 Rosin 2 Other Zinc oxide No. 3 4 4 4 4 4 4 4 4 4 Additives Naphthol Red F5RK 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Titanium white R-5N 2 2 2 2 2 2 2 2 2 Disparlon 4200-20X 2 2 2 2 2 2 2 2 2 Talc FC-1 3 3 3 3 3 3 3 3 3 Copper pyrithione 1 1 1 1 1 1 1 1 1 Cuprous oxide NC301 45 45 45 45 45 45 45 45 45 4,5-dichloro-2-n-octyl- 5 5 5 5 4-isothiazoline-3-one Xylene 18.2 18.2 18.2 18.2 13.2 15.2 15.2 13.2 18.2 Disparlon A630-20X 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Total 100 100 100 100 100 100 100 100 100

(123) TABLE-US-00005 TABLE 5 Example 1 2 3 4 5 6 7 8 9 10 11 12 Coating Composition A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 Coating film Immersion 1 month Appearance (crack) 0 0 0 0 0 0 0 0 0 0 0 0 deterioration period Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 acceleration 2 months Appearance (crack) 0 0 0 0 0 0 0 0 0 0 0 0 test Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 3 months Appearance (crack) 0 0 0 0 0 0 0 0 0 0 0 0 Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 4 months Appearance (crack) 0 0 0 0 0 0 0 0 0 0 0 0 Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 5 months Appearance (crack) 0 0 0 0 0 0 0 0 0 0 0 0 Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 Coating film Immersion 1 month 2.1 3.3 4.1 3.7 5.7 3.7 3.7 4.5 4 4.2 5.9 6.1 consumption period 2 months 3.6 4 5.1 5.9 9.8 5.7 5.5 8.9 7 7.7 9.9 10.4 property test 3 months 4.5 5.3 5.9 7.9 14.3 6.8 7.5 13.3 8.3 9.8 14.7 15.7 4 months 5.1 7 9.1 10.3 19.7 9.8 9.9 18.9 10.8 12.3 19.7 21.3 5 months 7 10.3 13.5 14.2 25.7 14 13.3 24.5 14.2 15.7 24.8 26.7 6 months 8.6 13.7 18.3 18.5 30.5 19.7 18.3 29.8 17.9 20.2 29.8 33.5 7 months 11.4 15.7 22.3 23.5 36.7 23 22.1 35.6 23.5 24.5 36.6 40.9 8 months 13.9 18.7 26.7 28.7 42.3 27.5 26.3 40.3 28.6 29.8 42.3 46.8 9 months 16.5 22.3 31.5 34.5 48.9 32.5 29.5 46.5 33.9 35.7 47.8 53.2 10 months 22.3 28.3 36.7 39.8 55.8 37.8 35.7 52.3 39.9 40.1 53.1 59.8 11 months 25 36.9 40.8 44.3 61.3 42.1 44.5 59.8 47.3 45.6 59.9 65.8 12 months 27.3 42.4 46.3 49.8 68.8 48.9 51.8 67.8 53.2 50.8 66.5 72.3 Monthly average coating film consumption 2.3 3.5 3.9 4.2 5.7 4.1 4.3 5.7 4.4 4.2 5.5 6.0 amount (m) Coating film appearance of after 12 months AA AA AA AA AA AA AA AA AA AA AA AA Static Immersion 1 month 0 0 0 0 0 0 0 0 0 0 0 0 antifouling period 2 months 0 0 0 0 0 0 0 0 0 0 0 0 property test 3 months 0.5 0 0 0 0 0 0 0 0 0 0 0 4 months 0.5 0 0 0 0 0 0 0 0 0 0 0 5 months 0.5 0.5 0 0 0 0 0 0 0 0 0 0 6 months 0.5 0.5 0 0.5 0 0 0 0.5 0 0.5 0 0 Storage Initial viscosity (Ku) 86 85 82 84 81 84 85 83 82 86 83 81 stability Viscosity after storage at 50 C. for 3 87 86 83 85 83 86 87 86 86 86 84 83 test months Increase of viscosity (Ku) +1 +1 +1 +1 +2 +2 +2 +3 +4 0 +1 +2 Example 13 14 15 16 17 18 19 20 21 22 23 24 Coating Composition A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 Coating film Immersion 1 month Appearance (crack) 0 0 0 0 0 0 0 0 0 0 0 0 deterioration period Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 acceleration test 2 months Appearance (crack) 0 0 0 0 0 0 0 0 0 0 0 0 Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 3 months Appearance (crack) 0 0 0 0 0 0 1 0 0 0 0 1 Adhesion 0 0 0 0 0 0 1 0 0 0 0 1 4 months Appearance (crack) 0 0 1 0 0 0 1 0 0 0 0 1 Adhesion 0 0 1 0 0 0 1 0 0 0 0 1 5 months Appearance (crack) 0 0 1 0 0 0 1 0 0 0 0 1 Adhesion 0 0 1 0 0 0 1 0 0 0 0 1 Coating film Immersion 1 month 2.5 4.5 4.7 3.2 3.1 3.5 3.7 1.2 1.2 1.4 1.8 2 consumption period 2 months 3.8 6.9 7.1 3.9 3.9 4.1 4.5 3.5 3.6 3.6 4 3.9 property test 3 months 5.1 10.1 10.5 5.1 5.5 5.6 5.8 4.2 4.5 4.9 5.2 5.5 4 months 7.8 13.7 14.1 7.3 7.6 8 9.1 4.9 5.1 5.3 7.4 7.8 5 months 11.1 16.9 17.5 9.9 10.6 10.9 11.3 6.7 6.8 7 8.8 9.2 6 months 14.6 21.2 24.9 11 12.3 13.1 13.8 8.3 8.7 9.5 9.9 10.5 7 months 18.2 26.3 30.1 15.5 17.2 18.8 19.3 10.9 11.3 12.1 13.8 13.9 8 months 22.4 30.9 33.5 18.4 19.8 20.5 21 13.5 13.7 14.3 15.8 16.6 9 months 26.8 34.2 38.9 22 23.6 24.6 26.6 15.9 16.3 17.4 18.3 19.1 10 months 30.3 38.3 43.3 27.9 28.8 30 32.8 20.1 20.4 22 23.1 24.8 11 months 36.3 45.8 50.3 34.8 35.5 36.9 38.6 22.6 22.9 24.8 26.9 28.5 12 months 44.1 54.5 56.3 40.7 42.1 44.3 46.3 24.9 25.3 27.5 28.9 30 Monthly average coating film consumption 3.7 4.5 4.7 3.4 3.5 3.7 3.9 2.1 2.1 2.3 2.4 2.5 amount (m) Coating film appearance of after 12 months AA AA AA AA AA AA AA AA AA AA AA AA Static Immersion 1 month 0 0 0 0 0 0 0 0 0 0 0 0 antifouling period 2 months 0 0 0 0 0 0 0 0 0 0 0 0 property test 3 months 0 0 0 0 0 0 0 0.5 0.5 0 0 0 4 months 0 0 0 0.5 0 0 0 0.5 0.5 0.5 0 0 5 months 0.5 0 0 0.5 0.5 0 0 0.5 0.5 0.5 0.5 0.5 6 months 0.5 0 0 0.5 0.5 0 0 0.5 0.5 0.5 0.5 0.5 Storage Initial viscosity (Ku) 81 83 83 83 83 82 81 84 85 86 86 81 stability Viscosity after storage at 50 C. for 3 85 89 93 84 87 90 98 85 86 88 92 98 test months Increase of viscosity (Ku) +4 +6 +10 +1 +4 +8 +17 +1 +1 +2 +6 +17

(124) TABLE-US-00006 TABLE 6 Comparative Example 1 2 3 4 5 6 7 8 9 Coating Composition B1 B2 B3 B4 B5 B6 B7 B8 B9 Coating film Immersion 1 month Appearance (crack) 3 0 0 0 0 0 0 0 0 deterioration period Adhesion 2 0 0 0 0 0 0 0 0 acceleration 2 months Appearance (crack) 3 0 0 0 2 0 0 0 0 test Adhesion 2 0 0 0 2 0 0 0 0 3 months Appearance (crack) 3 3 1 2 2 3 0 3 3 Adhesion 2 2 1 2 2 2 0 2 2 4 months Appearance (crack) 3 3 2 2 2 3 1 3 3 Adhesion 2 2 2 2 2 2 1 2 2 5 months Appearance (rack) 3 3 3 3 3 3 3 3 3 Adhesion 2 2 2 2 2 2 2 2 2 Coating film Immersion 1 month 1.7 5.5 3.6 4.9 5.2 2.7 3.1 2.9 3.3 consumption period 2 months 3.2 11.3 4.3 9.3 10.3 5.5 4.9 7.5 5.7 property test 3 months 3.9 18.7 5.6 15 16.2 10.1 8.9 11.9 8.7 4 months 4.7 25.3 8.2 20.9 23.1 12.7 11.3 13.8 12.3 5 months 6.7 31.9 11 29.1 29.8 18.1 15.4 18.9 15.7 6 months 8.3 38.7 13.9 34.1 36.4 20.7 18.9 22.2 20.5 7 months 10.7 46 19.3 40.2 44.6 26.3 23.4 27.5 24.3 8 months 12.3 55.3 22.1 46.9 52.7 32.3 28.8 34.1 31.6 9 months 14.7 68.3 26 55.3 64.7 38.7 34.7 40.1 36.7 10 months 16.7 91.3 32.3 72.5 87.5 51.2 39.8 53.2 43.5 11 months 19.3 122.5 37.9 93.1 105.9 62.8 43.6 66.6 50.5 12 months 22.8 151.3 47.5 118.5 129.5 83.2 49.7 85.8 58.9 Monthly average coating film consumption 1.9 12.6 4.0 9.9 10.8 6.9 4.1 7.2 4.9 amount (m) Coating film appearance of after 12 months Crack- Crack- Crack- Crack- Crack- Crack- Crack- Crack- Crack- ing ing ing ing ing ing ing ing ing Static Immersion 1 month 0 0 0 0 0 0 0 0 0 antifouling period 2 months 0.5 0 0 0 0 0 0 0 0 property test 3 months 0.5 0.5 0 0 0 0 0 0 0.5 4 months 1 0.5 0 0 0 0.5 0 0.5 0.5 5 months 2 0.5 0 0 0.5 0.5 0.5 0.5 0.5 6 months 3 0.5 0.5 0 0.5 0.5 0.5 0.5 0.5 Storage Initial viscosity (Ku) 87 82 82 81 84 83 84 83 84 stability Viscosity after storage at 50 C. for 3 88 116 110 114 112 113 108 109 113 test months Increase of viscosity (Ku) +1 +34 +28 +33 +28 +30 +24 +26 +29
[Evaluation of Properties of (Co)Polymer Solution and (Co)Polymer]
(1) Content of Heat Residue in (Co)Polymer Solution

(125) 1.5 g (X.sub.1 (g)) of the (co)polymer solution was kept in a thermostat chamber at 1 atmospheric pressure at 108 C. for 3 hours to remove volatile contents, whereby a heat residue (non-volatile contents) was obtained. Subsequently, the amount (X.sub.2 (g)) of the resultant heat residue (non-volatile contents) was measured. Based on the following equation, the content (%) of the heat residue contained in the (co)polymer solution was calculated.
Content (%) of heat residue=X.sub.2/X.sub.1100
(2) Average Molecular Weight of (Co)Polymer

(126) The weight average molecular weight (Mw) of the (co) polymer was measured by GPC (gel permeation chromatography) under the following conditions.

(127) GPC Conditions

(128) Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)

(129) Column: SuperH2000+H4000 (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length) for each column)

(130) Eluent: tetrahydrofran (THF)

(131) Flow rate: 0.500 ml/min

(132) Detector: RI

(133) Column thermostat chamber temperature: 40 C.

(134) Standard substance: polystyrene

(135) Sample preparation method: to the (co)polymer solution prepared in each Production Example, a small amount of calcium chloride was added to dehydrate the solution, which was followed by filtration with a membrane filter. The obtained filtered material was defined as a sample for GPC measurement.
(3) Viscosity of (Co)Polymer Solution

(136) By using an E-type viscometer (manufactured by TOKI SANGYO CO., LTD.), the viscosity (unit: mPa.Math.s) at a liquid temperature 25 C. of the (co)polymer solution was measured.

(137) (4) Coating Film Deterioration Acceleration Test (Evaluation of Coating Film Appearance and Adhesion)

(138) A sandblasted plate (150 mm70 mm1.6 mm) was coated by using an applicator with an epoxy-based coating material (epoxy AC coating material, product name: Bannoh 500, manufactured by Chugoku Marine Paints, Ltd.) such that the thickness of the film dried would be 150 m, followed by curing, to form a cured coating film (150 m). Subsequently, the cured coating film was coated by using an applicator with an epoxy binder coating material (product name: Bannoh 500N, manufactured by Chugoku Marine Paints, Ltd.) such that the thickness of the film dried would be 100 m, followed by curing, to form a cured coating film (100 m). Thereby, a test plate was prepared.

(139) Subsequently, the test plate (surface of the cured coating film formed from epoxy binder coating material) was coated by using an applicator with the coating composition of any of the above Examples and Comparative Examples such that the thickness of the film dried would be 150 m, which was followed by drying at 23 C. for 1 day, to form an antifouling coating film (150 m). Further, this antifouling coating film surface was coated with the above coating composition such that the thickness of the film dried would be 150 m, which was followed by drying at 23 C. for 7 days, to form an antifouling coating film. Thereby, a test plate with an antifouling coating film was prepared.

(140) The resultant test plate with the antifouling coating film was immersed in artificial seawater at 50 C. Every one month after the immersion, the appearance and adhesion of the coating film were investigated based on the following evaluation criteria.

(141) Evaluation of Appearance

(142) The degree of fracture of the antifouling coating film surface of the test plate with the antifouling coating film was visually observed, and was evaluated in accordance with JIS K5600-8-4 shown in the following Table.

(143) TABLE-US-00007 TABLE 7 Evaluation Point (RN) Classification of Fracture Amount 0 None 1 Density 1 2 Density 2 3 Density 3
Evaluation of Adhesion

(144) The antifouling coating film surface of the test plate with the antifouling coating film was slit with an NT cutter so as to have four cut lines both in the longitudinal direction and the transverse direction with one line spaced from another line by 4 mm, and this resulted in the formation of 9 squares on the coating film surface. On the coating film surface having the squares, a Cellotape (trade mark) was press-contacted and then quickly peeled off. Then, the squares were observed. Subsequently, provided that the area of the 9 squares was 100%, the percentage (%) of the area of the coating film remaining on the squares (remaining area) after the peeling operation was calculated, and based on the following evaluation criteria, adhesion was evaluated.

(145) [Adhesion Evaluation Criteria]

(146) 0: the area of the remaining coating film is 95% or more.

(147) 1: the area of the remaining coating film is 75 to less than 95%.

(148) 2: the area of the remaining coating film is 50 to less than 75%.

(149) 3: the area of the remaining coating film is less than 50%.

(150) (5) Coating Film Consumption Property Test

(151) Each coating composition obtained in Examples and Comparative Examples was applied by using an applicator on a hard vinyl chloride plate (50 mm50 mm1.5 mm) such that the thickness of the film dried would be 150 m and dried, to prepare a test plate.

(152) The resultant test plate was attached to a rotating drum, and the rotating drum was immersed in seawater. At a seawater temperature of 30 C., the drum was rotated at a circumferential speed of 15 knots, and the thickness of the film consumed was measured every one month. In addition, the monthly average coating film consumption amount from the start of the immersion to 12 months thereafter was calculated. Further, coating film appearance after 12 months from the start of the immersion was observed and evaluated based on the following evaluation criteria.

(153) [Evaluation Criteria of Coating Film Appearance]

(154) AA: the antifouling coating film surface has no cracking.

(155) Cracking: the antifouling coating film surface has cracking.

(156) (6) Static Antifouling Properties Test

(157) A sandblasted plate (300 mm100 mm3.2 mm) was coated by using an air spray with an epoxy-based coating material (epoxy AC coating material, product name: Bannoh 500, manufactured by Chugoku Marine Paints, Ltd.) such that the thickness of the film dried would be 150 m, which was followed by curing, to form a cured coating film (150 m). Subsequently, the cured coating film was coated by using an air spray with an epoxy binder coating material (product name: Bannoh 500N, manufactured by Chugoku Marine Paints, Ltd.) such that the thickness of the film dried would be 100 m, which was followed by curing, to form a cured coating film (100 m), to thereby prepare a test plate.

(158) Subsequently, the test plate (surface of the cured coating film formed from the epoxy binder coating material) was coated by using an air spray with the coating composition of any of the Examples and Comparative Examples such that the thickness of the film dried would be 150 m, and then the composition was dried at 23 C. for 1 day to form an antifouling coating film (150 m). Further, the antifouling coating film surface was coated with the above coating composition such that the thickness of the film dried would be 150 m, and the then composition was dried at 23 C. for 7 days to form an antifouling coating film. Thereby, a test plate with an antifouling coating film was prepared.

(159) The resultant test plate with the antifouling coating film was stationarily immersed in Nagasaki bay, Nagasaki Prefecture. Every one month after the immersion, the percentage (%) of the area of the antifouling coating film on which aquatic creatures were adhered (adherence area) was measured wherein the total area of the antifouling coating film of the test plate is defined as 100%, and based on the following evaluation criteria the static antifouling properties were evaluated.

(160) [Evaluation Criteria]

(161) 0: the adherence area is 0%.

(162) 0.5: the adherence area is 0 to 10%.

(163) 1: the adherence area is 10 to less than 20%.

(164) 2: the adherence area is 20 to less than 30%.

(165) 3: the adherence area is 30 to less than 40%.

(166) 4: the adherence area is 40 to less than 50%.

(167) 5: the adherence area is 50 to 100%.

(168) (7) Storage Stability Test

(169) The viscosity at 23 C. of each coating composition immediately (within one day) after prepared in Examples and Comparative Examples (initial viscosity (Ku)) was measured in accordance with JIS K 5400 by using a stormer viscometer. Furthermore, after each coating composition was stored in a 50 C. thermostat for 3 months, the viscosity at 23 C. of each coating composition (viscosity after storage (Ku)) was measured in accordance with JIS K 5400 by using a stormer viscometer. Subsequently, increase of viscosity was calculated based on the following equation.
Viscosity Increase=Viscosity After Storage (Ku)Initial Viscosity (Ku)

(170) TABLE-US-00008 TABLE 8 Solid content Item Manufacturer Properties (wt %) Talc FC-1 Fukuoka Talc Co., Ltd. Extender pigment 100 Zinc oxide Kyushu Hakusui Kagaku Extender pigment 100 Novoperm Red Clariant North America Organic red pigment 100 F5RK Copper Arch Chemical, Inc. Organic antifouling 100 Omadine agent (copper pyrithione) 4,5-dichloro-2- Rohm & Haas Company Organic antifouling 30 n-octyl-4- agent isothiazoline-3- one Rosin Made in China Elution assistant 100 Dis630-20XC Kusumoto Chemicals, Anti-sagging agent 20 Ltd. Dis4200-20X Kusumoto Chemicals, Anti-settling agent 20 Ltd. Cuprous oxide Nissin Chemco Co., Ltd. Antifouling agent 100 NC-301 Titanium white Sakai Chemical Color pigment 100 R-5N Industry Co., Ltd. Versatic acid Resolution Nederland Elution assistant 100

(171) The present invention is described with reference to embodiments hereinabove, but the present invention is limited in no way by the above. The configuration and detail of the present invention can have various modifications comprehensible within the scope of the invention by a skilled person in the art.

(172) The present application claims priority from Japanese Patent Application No. 2011-248877 filed on Nov. 14, 2011, and all of the disclosure therein is incorporated hereto.

INDUSTRIAL APPLICABILITY

(173) The present invention is applicable to antifouling coating compositions and antifouling coating films, and is therefore employable for antifouling substrates.

Antifouling coating composition, antifouling coating film and antifouling substrate, and method for producing antifouling substrate

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Abstract

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