(Meth)acrylic copolymer, polymer solution, polymer-containing composition, anti-fouling coating composition, and method for producing (meth)acrylic copolymer

Abstract

First embodiment of a (meth)acrylic copolymer in the present invention includes following: a (meth)acrylic copolymer having at least one kind of constitutional unit selected from the group consisting of a constitutional unit (A1) having at least one kind of structure (I) selected from the group consisting of structures represented by the following formula (1), formula (2), or formula (3) and a constitutional unit (A2) having a triorganosilyloxycarbonyl group and a constitutional unit (B) derived from a macromonomer (b): ##STR00001## (where, X represents —O—, —S—, or —NR.sup.14—, R.sup.14 represents a hydrogen atom or an alkyl group, R.sup.1 and R.sup.2 each represent a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, R.sup.3 and R.sup.5 each represent an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, and R.sup.4 and R.sup.6 each represent an alkylene group having from 1 to 10 carbon atoms).

Claims

1. A polymer-containing composition comprising: a solvent; and a methacrylic copolymer comprising: at least one kind of constitutional unit selected from the group consisting of (i) a constitutional unit (A1) having at least one structure selected from the group consisting of structures represented by formula (1), formula (2), or formula (3); ##STR00016## wherein, X represents —O—, —S—, or —NR.sup.14—, R.sup.14 represents a hydrogen atom or an alkyl group, R.sup.1 and R.sup.2 each represent a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, R.sup.3 and R.sup.5 each represent an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, and R.sup.4 and R.sup.6 each represent an alkylene group having from 1 to 10 carbon atoms; (ii) a constitutional unit (A2) having a triorganosilyloxycarbonyl group; and (iii) a constitutional unit (A3) having at least one structure selected from the group consisting of structures represented by formula (4) or (5);
—COO-M-OCO  (4)
—COO-M-R.sup.32  (5) wherein, M represents Zn, Cu, Mg, or Ca and R.sup.32 represents an organic acid residue other than a (meth)acryloyloxy group; and a constitutional unit (B) derived from a macromonomer (b) having two or more constitutional units represented formula (b′) and a number average molecular weight of from 500 to 50000: ##STR00017## wherein, R.sup.41 represents a hydrogen atom, a methyl group, or CH.sub.2OH and R.sup.42 represents OR.sup.43, a halogen atom, COR.sup.44COOR.sup.45, CN, CONR.sup.46R.sup.47 or R.sup.48 where R.sup.43 to R.sup.47 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted nonaromatic heterocyclic group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, or an unsubstituted or substituted organosilyl group and R.sup.48 represents an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group; wherein a content of the organic solvent is 30% by mass or more with respect to a total amount of the polymer-containing composition excluding the (meth)acrylic copolymer, and wherein a water content is 15% by mass or less.

2. The polymer-containing composition according to claim 1, wherein a viscosity of the polymer solution at 25° C. is 5×10.sup.4 mPa.Math.s or less.

3. The polymer-containing composition according to claim 1, further comprising at least one kind of alkenyl compound selected from the group consisting of a compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following formula (13), wherein the (meth)acrylic copolymer has the constitutional unit (A1): ##STR00018## wherein X represents —O—, —S—, or —NR.sup.14—, R.sup.14 represents a hydrogen atom or an alkyl group, R.sup.7 represents a hydrogen atom or an alkyl group having from 1 to 9 carbon atoms, R.sup.8 represents a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, R.sup.9 and R.sup.11 each represent an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, R.sup.10 represents a single bond or an alkylene group having from 1 to 9 carbon atoms, and R.sup.12 represents an alkylene group having from 1 to 9 carbon atoms.

4. An anti-fouling coating composition comprising the polymer-containing composition according to claim 1.

5. The anti-fouling coating composition according to claim 4, further comprising an anti-fouling agent.

6. The anti-fouling coating composition according to claim 5, wherein the anti-fouling agent contains at least one kind selected from the group consisting of cuprous oxide, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, pyridine-triphenylborane, and medetomidine.

7. The anti-fouling coating composition according to claim 4, wherein a VOC content is 500 g/L or less.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these examples in any way. Incidentally, parts in Examples represent parts by mass.

(2) The evaluation in Examples was carried out by the following method.

(3) (Solid Content (Heating Residue))

(4) On an aluminum dish, 0.50 g of measurement sample (polymer solution, polymer-containing composition, anti-fouling coating composition, or the like) weighed was put, 3 mL of toluene was added thereto by using a dropping pipet, the mixture was uniformly spread on the bottom of the dish and subjected to preliminary drying. The preliminary drying is a treatment for spreading the measurement sample on the entire dish and facilitating the volatilization of the organic solvent in the main drying. In the preliminary drying, the measurement sample and toluene were heated and dissolved on a water bath at from 70° C. to 80° C. to be evaporated, dried, and hardened. After the preliminary drying, main drying was conducted in a hot air dryer at 105° C. for 2 hours. The heating residue was determined by the following formula from the mass (mass before drying) of the measurement sample before the preliminary drying and the mass (mass after drying) thereof after the main drying, and the value was taken as the solid content.
Heating residue (% by mass)=mass after drying/mass before drying×100

(5) (Gardner Viscosity)

(6) The measurement sample was filled in a dried Gardner bubble viscosity tube (hereinafter also simply referred to as a viscosity tube) to the pointing line of the viscosity tube, and of the viscosity tube was capped with a cork stopper. The viscosity tube containing the measurement sample was vertically immersed in a constant temperature water bath adjusted to a prescribed temperature (25.0±0.1° C.) for at least 2 hours so that the temperature of the measurement sample became constant, a viscosity tube serving as a reference tube and the viscosity tube containing the measurement sample were rotated at the same time by 180°, and the bubble rising rate of the measurement sample was compared to that of the reference tube, thereby determining the viscosity (Gardner viscosity).

(7) (B-Type Viscosity)

(8) The viscosity of the measurement sample was measured at 25° C. by using a B-type viscometer and the value was presented as the B-type viscosity.

(9) (Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn)) (Meth)acrylic copolymer containing constitutional unit (A-3):

(10) The measurement was conducted by using a gel permeation chromatographic (GPC) instrument (HLC-8220 manufactured by Tosoh Corporation). A N,N-dimethylformamide (DMF) solution was prepared so as to contain the (meth)acrylic copolymer at 0.4% by mass, 100 μl of the solution was injected into a device equipped with a column manufactured by Tosoh Corporation (TSK gel α-M (manufactured by Tosoh Corporation, 7.8 mm×30 cm), TSK guard column α (manufactured by Tosoh Corporation, 6.0 mm×4 cm)), and the measurement was conducted at 40° C. The weight average molecular weight (Mw) or the number average molecular weight (Mn) was calculated in terms of standard polystyrene. (Meth)acrylic copolymer containing at least one kind of constitutional unit selected from the group consisting of constitutional units (A1) and (A2) and macromonomer (b):

(11) The measurement was conducted by using a gel permeation chromatographic (GPC) instrument (HLC-8320 manufactured by Tosoh Corporation). A tetrahydrofuran solution was prepared so as to contain the copolymer and the macromonomer at 0.2% by mass, 10 μl of the solution was injected into a device equipped with a column manufactured by Tosoh Corporation (TSK gel Super HZM-M×HZM-M×HZ 2000, TSK guard column Super HZ-L), the measurement was conducted under the conditions of a flow rate: 0.35 ml/min, an eluent: tetrahydrofuran (stabilizer: BHT), and a column temperature: 40° C., and the weight average molecular weight (Mw) or the number average molecular weight (Mn) was calculated in terms of standard polystyrene.

(12) (Acid Value)

(13) About 0.5 g of the measurement sample was precisely weighed (A (g)) in a beaker, and 50 mL of a toluene/ethanol solution was added thereto. Several drops of phenolphthalein were added to the mixture, and the titration using 0.5 N KOH solution was conducted. (Titre=B (mL), potency of KOH solution=f). The blank measurement was conducted in the same manner (titre=C (mL)), and the calculation was conducted by the following formula.
Acid value (mg KOH/g)={(B−C)×0.2×56.11×f}/A/solid content

(14) (VOC Content)

(15) The VOC content in the measurement sample was calculated by the following formula.
VOC content (g/L)=specific gravity of measurement sample×1000×(100−solid content)/100

(16) The specific gravity of the measurement sample was calculated by filling the measurement sample in a specific gravity cup having a capacity of 100 mL at 25° C. and measuring the mass.

(17) (Hardness of Coating Film)

(18) The polymer-containing composition was coated on a glass substrate by using a 500 μm applicator and dried at 25° C. for 1 week to form a coating film, thereby obtaining a test plate. The Martens hardness (HM) of the coating film of this test plate was measured by using an ultramicro hardness meter (sample manufactured by FISCHER INSTRUMENTS K.K., trade name: HM 2000). The measurement conditions were dQRST(F)/dt=constant, F (test force)=10 mN/10 s, C (creep time at maximum load)=5 s, maximum indentation load=10 mN, and maximum indentation depth=6 μm. The Martens hardness was measured at three different places of the same coating film, and the average value thereof was taken as the hardness of the coating film.

(19) Incidentally, the Martens hardness (HM) is preferably in a range of from 1.2 to 15.0 N/mm.sup.2 and more preferably in a range of from 2.0 to 10.0 N/mm.sup.2.

(20) (Hardness of Coating Film After 1 Day)

(21) The hardness of coating film % as measured in the same manner as above except that the drying time was set to 1 day at 25° C.

(22) (Paintability)

(23) The smoothness of the coating film after painting was visually confirmed and paintability was evaluated according to the following criteria.

(24) ◯: coating film is smooth.

(25) Δ: coating film is slightly uneven.

(26) X: stripes remain on coating film.

(27) (Water Resistance 1 (Whitening))

(28) A sample (polymer-containing composition) was coated on a glass substrate by using a 500 μm applicator and dried at room temperature for 1 week to form a coating film, thereby obtaining a test plate. This test plate was immersed in the sterilized and filtered sea water for 1 month and then dried at room temperature of 20° C. for 1 week. With regard to the degree of whitening, the surface of coating film of the test plate was visually observed. The evaluation was carried out according to the following criteria.

(29) ◯: whitening is not observed.

(30) Δ: whitening is slightly observed.

(31) X: whitening is considerably observed.

(32) (Water Resistance 2 (Haze))

(33) A sample (polymer-containing composition or anti-fouling coating composition) was coated on a glass substrate by using a 500 μm applicator and dried at room temperature for 1 week to form a coating film, thereby obtaining a test plate. This test plate was immersed in the sterilized and filtered sea water for 1 month and then dried at room temperature of 20° C. for 1 week. The haze of the test plate after drying was measured by using a haze meter (manufactured by MURAKAMI COLOR RESEARCH LABORATORY CO., LTD., trade name: HM-150). It indicates that the degree of whitening of the surface of coating film is lower and the water resistance of coating film is superior as the haze value is smaller.

(34) (Degree of Consumption of Coating Film)

(35) The anti-fouling coating composition was coated on a hard vinyl chloride plate of 50 mm×50 mm×2 mm (thickness) by using an applicator so as to have a dry film thickness of 120 μm and dried to form a coating film, thereby obtaining a test plate. This test plate was attached to a rotating drum installed in the sea water and rotated at a peripheral speed of 7.7 m/s (15 knots), and the film thickness of the coating film after 3 months was measured. The film thickness consumed per month ((120 μm−measured film thickness (μm))/3) was calculated from the measured film thicknesses, and the value was taken as the degree of consumption. The degree of consumption is preferably from 1 to 30 μm/M.

(36) (Static Anti-Fouling Properties)

(37) The anti-fouling coating composition was coated on a sandblasted steel plate of 150 mm×70 mm×1.6 mm (thickness) coated with a rust proof coating in advance by using a brush so as to have a dry film thickness of 120 μm and dried to form a coating film, thereby obtaining a test plate. This test plate was immersed in the sea and allowed to stand still for 3 months, then the proportion (the area occupied by marine organisms) (%) of the area in which the marine organisms adhered with respect to the entire area of the coating film was determined, and it was judged that the static anti-fouling properties were favorable in a case in which the area occupied by marine organisms was 30% or less.

(38) The materials used in the following respective examples are as follows.

(39) Monomer (a1-1): 1-butoxyethyl methacrylate (synthetic product synthesized in Production Example a1-1 to be described later).

(40) Monomer (a1-2): 1-isobutoxyethyl methacrylate (synthetic product synthesized in Production Example a1-2 to be described later).

(41) Monomer (a1-3): 1-(2-ethylhexyloxy)ethyl methacrylate (synthetic product synthesized in Production Example a1-3 to be described later).

(42) Monomer (a2-1): triisopropylsilyl acrylate (TIPX).

(43) Monomer (a3-1): a metal-containing monomer mixture (a synthesized product synthesized in Production Example a3-1 to be described later).

(44) Monomer (a3-2): a metal-containing monomer mixture (synthetic product synthesized in Production Example a3-2 to be described later).

(45) Macromonomer (MM1): a macromonomer which had a number average molecular weight of 1600 and was obtained in Production Example MM1 to be described later.

(46) Macromonomer (MM2): a macromonomer which had a number average molecular weight of 2500 and was obtained in Production Example MM2 to be described later.

(47) Macromonomer (MM3): a macromonomer which had a number average molecular weight of 3,600 and was obtained in Production Example MM3 to be described later.

(48) Macromonomer (MM4): a macromonomer which had a number average molecular weight of 6700 and was obtained in Production Example MM4 to be described later.

(49) MMA: methyl methacrylate.

(50) MA: methyl acrylate.

(51) EA: ethyl acrylate.

(52) BA: n-butyl acrylate.

(53) MTMA: 2-methoxyethyl methacrylate.

(54) MTA: 2-methoxyethyl acrylate.

(55) MAA: methacrylic acid.

(56) AIBN: 2,2′-azobisisobutyronitrile.

(57) AMBN: 2,2′-azobis(2-methylbutyronitrile).

(58) NOFMER MSD: trade name, manufactured by NOF Corporation, α-methylstyrene dimer.

(59) Anti-fouling agent (1): 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile.

(60) Additive (1): TOYOPARAX (registered trademark) 150 (manufactured by Tosoh Corporation, chlorinated paraffin).

(61) Additive (2): DISPARLON (registered trademark) 4200-20 (manufactured by Kusumoto Chemicals, Ltd., oxidized polyethylene wax).

(62) Additive (3): DISPARLON A603-20X (manufactured by Kusumoto Chemicals, Ltd., polyamide wax).

(63) Additive (4): KF-56 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone oil).

Production Example a1-1

(64) With 150.2 parts (1.5 mol) of butyl vinyl ether, 0.24 part of hydroquinone, and 0.47 part of phenothiazine were stirred at room temperature and mixed until the mixture became homogeneous. While blowing air (10 mL/min), 86.1 parts (1.0 mol) of methacrylic acid was added dropwise to the mixture while keeping the temperature of the reaction solution at 60° C. or lower. After the dropwise addition, the temperature of the reaction solution was raised to 80° C. and the reaction was conducted for 5 hours. To the reaction solution, 264.5 parts (3.0 mol) of t-butyl methyl ether was added, these were mixed together, and the organic phase was washed with 350 parts of a 20% by mass aqueous solution of potassium carbonate one time. To the organic phase, 0.06 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added, and the low boiling point fraction was distilled off by using an evaporator. The residue thus obtained was distilled under reduced pressure, thereby obtaining 166.9 parts (0.91 mol) of 1-butoxyethyl methacrylate (monomer (a1-1)) having a boiling point of 70° C./5 torr (667 Pa).

Production Example a1-2

(65) With 90.1 parts (0.9 mol) of isobutyl vinyl ether, 0.14 parts of hydroquinone and 0.28 part of phenothiazine were stirred at room temperature and mixed until the mixture became homogeneous. While blowing air (10 mL/min), 51.7 parts (0.6 mol) of methacrylic acid was added dropwise to the mixture while keeping the temperature of the reaction solution at 60° C. or lower. After the dropwise addition, the temperature of the reaction solution was raised to 80° C., and the reaction was conducted for 6 hours. To the reaction solution, 158.7 parts (1.8 mol) of t-butyl methyl ether was added, these were mixed together, and the organic phase was washed with 200 parts of a 20% by mass aqueous solution of potassium carbonate one time. To the organic phase, 0.03 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added, and the low boiling point fraction was distilled off by using an evaporator. The residue thus obtained was distilled under reduced pressure, thereby obtaining 97.5 parts (0.52 mol) of 1-isobutoxyethyl methacrylate (monomer (a1-2)) having a boiling point of 60° C./3 torr.

Production Example a1-3

(66) With 171.9 parts (1.1 mol) of 2-ethylhexyl vinyl ether, 0.32 part of hydroquinone, and 0.61 part of phenothiazine were stirred at room temperature and mixed until the mixture became homogeneous. While blowing air (10 mL/min), 86.1 parts (1.0 mol) of methacrylic acid was added dropwise to the mixture while keeping the temperature of the reaction solution at 60° C. or lower. After the dropwise addition, the temperature of the reaction solution was raised to 80° C., and the reaction was conducted for 5 hours. To the reaction solution, 264.5 parts (3.0 mol) oft-butyl methyl ether was added, these were mixed together, and the organic phase was washed with 135 parts of a 20% by mass aqueous solution of potassium carbonate one time. To the organic phase, 0.07 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added, and the low boiling point fraction was distilled off by using an evaporator. The residue thus obtained was distilled under reduced pressure, thereby obtaining 207.0 parts (0.85 mol) of 1-(2-ethylhexyloxy)ethyl methacrylate (monomer (a1-3)) having a boiling point of 99° C./3 torr.

Production Example a3-1

(67) In a four-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a stirrer, 85.4 parts of propylene glycol methyl ether (PGM) and 40.7 parts of zinc oxide were charged, and the temperature of the mixture was raised to 75° C. while stirring it. Subsequently, a mixture composed of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid, and 5 parts of water was added dropwise from the dropping funnel to the mixture at a constant rate over 3 hours. After the dropwise addition was completed, the state of the reaction solution changed from an opalescent state to a transparent state. After the reaction solution was further stirred for 2 hours, 36 parts of n-butanol was added thereto, thereby obtaining a metal-containing monomer mixture (monomer (a3-1)). The solid content therein was 44.8% by mass.

Production Example a3-2

(68) In a four-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a stirrer, 100 parts of propylene glycol methyl ether (PGM) and 40.7 parts of zinc oxide were charged, and the temperature of the mixture was raised to 75° C. while stirring it. Subsequently, a mixture composed of 30.1 parts of methacrylic acid, 25.2 parts of acrylic acid, and 43.3 parts of octylic acid was added dropwise from the dropping funnel to the mixture at a constant rate over 3 hours. After the dropwise addition was completed, the state of the reaction solution changed from an opalescent state to a transparent state. After the reaction solution was further stirred for 2 hours, 21.3 parts of propylene glycol methyl ether (PGM) was added thereto, thereby obtaining a metal-containing monomer mixture (monomer (a3-2)). The solid content therein was 55.0% by mass.

Production Example MM1

(69) (Production of Dispersing Agent 1)

(70) In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 900 parts of deionized water, 60 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate, and 12 parts of methyl methacrylate (MMA) were charged and stirred, and the temperature of the mixture was raised to 50° C. while purging the interior of the polymerization apparatus with nitrogen. To this, 0.08 part of 2,2′-azobis(2-methylpropionamidine) dihydrochloride was added as a polymerization initiator, and the temperature of the mixture was further raised to 60° C. After the temperature was raised, MMA was continuously added dropwise to the mixture at a rate of 0.24 part/min for 75 minutes by using a dropping pump. The reaction solution was kept at 60° C. for 6 hours and then cooled to room temperature, thereby obtaining a dispersing agent 1 having a solid content of 10% by mass of a transparent aqueous solution.

(71) (Production of Chain Transfer Agent 1)

(72) In a synthesis apparatus equipped with a stirring device, 1.00 g of cobalt(II) acetate tetrahydrate, 1.93 g of diphenyl glyoxime, and 80 ml of diethyl ether which was deoxidized in advance by nitrogen bubbling were charged in a nitrogen atmosphere and stirred at room temperature for 30 minutes. Subsequently, 10 ml of boron trifluoride-diethyl ether complex was added thereto, and the mixture was further stirred for 6 hours. The mixture was filtered, and the solid was washed with diethyl ether and dried in a vacuum for 15 hours, thereby obtaining 2.12 g of a chain transfer agent 1 of a reddish brown solid.

(73) (Production of Macromonomer (MM1))

(74) In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate, and 0.25 part of the dispersing agent 1 (solid content: 10% by mass) were charged and stirred to obtain a homogeneous aqueous solution. Next, 100 parts of MMA, 0.008 part of the chain transfer agent 1, and 0.8 part of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (PEROCTA O (registered trademark) manufactured by NOF CORPORATION) were added to the aqueous solution to prepare an aqueous suspension.

(75) Next, the interior of the polymerization apparatus was purged with nitrogen, the temperature of the aqueous suspension was raised to 80°, the reaction thereof was conducted for 1 hour, and the temperature of the resultant mixture was raised to 90° C. and kept at 90° C. for 1 hour in order to further increase the rate of polymerization. Thereafter, the reaction solution was cooled to 40° C. to obtain an aqueous suspension containing a polymer. This aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, the filtered product was washed with deionized water, dehydrated, and dried at 40° C. for 16 hours, thereby obtaining a macromonomer (MM1). The number average molecular weight of the macromonomer (MM1) was 1,600.

Production Example MM2

(76) In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate, and 0.25 part of the dispersing agent 1 (solid content: 10% by mass) were charged and stirred to obtain a homogeneous aqueous solution. Next, 100 parts of MMA, 0.004 part of the chain transfer agent 1, and 0.4 part of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (PEROCTA O manufactured by NOF CORPORATION) were added to the aqueous solution to prepare an aqueous suspension.

(77) Next, the interior of the polymerization apparatus was purged with nitrogen, the temperature of the aqueous suspension was raised to 800, the reaction thereof was conducted for 1 hour, and the temperature of the resultant mixture was raised to 90° C. and kept at 90° C. for 1 hour in order to further increase the rate of polymerization. Thereafter, the reaction solution was cooled to 40° C. to obtain an aqueous suspension containing a polymer. This aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, the filtered product was washed with deionized water, dehydrated, and dried at 40° C. for 16 hours, thereby obtaining a macromonomer (MM2). The number average molecular weight of the macromonomer (MM2) was 2,500.

Production Example MM3

(78) In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate, and 0.25 part of the dispersing agent 1 (solid content: 10% by mass) were charged and stirred to obtain a homogeneous aqueous solution. Next, 100 parts of MMA, 0.003 part of the chain transfer agent 1, and 0.3 part of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (PEROCTA O manufactured by NOF CORPORATION) were added to the aqueous solution to prepare an aqueous suspension.

(79) Next, the interior of the polymerization apparatus was purged with nitrogen, the temperature of the aqueous suspension was raised to 80°, the reaction thereof was conducted for 1 hour, and the temperature of the resultant mixture was raised to 90° C. and kept at 90° C. for 1 hour in order to further increase the rate of polymerization. Thereafter, the reaction solution was cooled to 40° C. to obtain an aqueous suspension containing a polymer. This aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, the filtered product was washed with deionized water, dehydrated, and dried at 40° C. for 16 hours, thereby obtaining a macromonomer (MM3). The number average molecular weight of the macromonomer (MM3) was 3,600.

Production Example MM4

(80) In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate, and 0.25 part of the dispersing agent 1 (solid content: 10% by mass) were charged and stirred to obtain a homogeneous aqueous solution. Next, 100 parts of MMA, 0.0015 part of the chain transfer agent 1, and 0.15 part of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (PEROCTA O manufactured by NOF CORPORATION) were added to the aqueous solution to prepare an aqueous suspension.

(81) Next, the interior of the polymerization apparatus was purged with nitrogen, the temperature of the aqueous suspension was raised to 80°, the reaction thereof was conducted for 1 hour, and the temperature of the resultant mixture was raised to 90° C. and kept at 90° C. for 1 hour in order to further increase the rate of polymerization. Thereafter, the reaction solution was cooled to 40° C. to obtain an aqueous suspension containing a polymer. This aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, the filtered product was washed with deionized water, dehydrated, and dried at 40° C. for 16 hours, thereby obtaining a macromonomer (MM4). The number average molecular weight of the macromonomer (MM4) was 6,700.

Production Example MM5

(82) In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate, and 0.25 part of the dispersing agent 1 (solid content: 10% by mass) were charged and stirred to obtain a homogeneous aqueous solution. Next, 75 parts of MMA, 25 parts of MTMA, 0.01 part of the chain transfer agent 1, and 1.5 parts of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (PEROCTA O manufactured by NOF CORPORATION) were added to the aqueous solution to prepare an aqueous suspension.

(83) Next, the interior of the polymerization apparatus was purged with nitrogen, the temperature of the aqueous suspension was raised to 80°, the reaction thereof was conducted for 1 hour, and the temperature of the resultant mixture was raised to 90° C. and kept at 90° C. for 1 hour in order to further increase the rate of polymerization. Thereafter, the reaction solution was cooled to 40° C. to obtain an aqueous suspension containing a polymer. This aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, the filtered product was washed with deionized water, dehydrated, and dried at 40° C. for 16 hours, thereby obtaining a macromonomer (MM5). The number average molecular weight of the macromonomer (MM5) was 2,000.

Example 1

(84) In a reaction vessel equipped with a stirrer, a temperature controller, and a dropping funnel, 48.3 parts of xylene was charged, and the temperature of the xylene was raised to 85° C. while stirring it in a nitrogen atmosphere. Subsequently, a mixture composed of 25 parts of the monomer (a1-1), 10 parts of the macromonomer (MM1), 7.5 parts of MMA, 20 parts of EA, 37.5 parts of MTMA, and 1.5 parts of AIBN was added dropwise thereto from the dropping funnel at a constant rate over 4 hours. In 30 minutes after the dropwise addition was competed, 2.0 parts of t-butylperoxy 2-ethylhexanoate and 9 parts of xylene were added dropwise to the resultant mixture four times at an interval of 30 minutes, and the mixture was further stirred for 1 hour, and 6.7 parts of butyl vinyl ether and 2 parts of butyl acetate were then added to the resultant mixture, thereby obtaining a polymer-containing composition (polymer solution) A-1 in the form of a solution having a solid content of 59.7% by mass and a Gardner viscosity of TU.

Examples 2 to 9 and Comparative Examples 1 and 2

(85) Polymer-containing compositions A-2 to A-11 in the form of a solution were produced in the same manner as in Example 1 except that the amounts (parts) of the monomer and the initiator AIBN charged were changed as presented in Table 1.

(86) The values of properties (solid content (% by mass), Gardner viscosity, B-type viscosity, and the number average molecular weight (Mn) and weight average molecular weight (Mw) of the copolymer contained in each of the polymer-containing compositions) of the polymer-containing compositions A-1 to A-11 thus obtained are presented in Table 1. The solid content in the polymer-containing compositions A-1 to A-11 is equal to the content of the copolymer. In addition, the performance (water resistance 1 and hardness) of the coating films formed of the polymer-containing compositions are presented in Table 1.

(87) TABLE-US-00001 TABLE 1 Compa- Compa- Exam- Exam- Exam- Exam- Exam- rative Exam- Exam- Exam- Exam- rative ple 1 ple 2 ple 3 ple 4 ple 5 Example 1 ple 6 ple 7 ple 8 ple 9 Example 2 Polymer-containing composition A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 Monomer (a1) M1 (BEMA) 25 25 25 25 25 25 25 50 — — 25 M2 (IBEMA) — — — — — — — — 25 — — M3 (EHEMA) — — — — — — — — — 32.5 — Macro- MM1 (low Mn 1600) 10 — 17.5 — 17.5 — 36 22 36 36 — monomer (b) MM3 (high Mn 3600) — 10 — 17.5 — — — — — — — Monomer (c) MMA 7.5 7.5 — — — 17.5 — — — — 36 EA 20 20 20 20 20 20 39 28 39 32.5 39 MTMA 37.5 37.5 37.5 37.5 37.5 37.5 — — — — — Initiator AIBN 1.5 1.5 1.5 1.5 2.5 1.5 0.9 0.9 0.9 0.9 1.5 Alkenyl Butyl vinyl ether 6.7 6.7 6.7 6.7 6.7 6.7 6.7 7.3 — — 6.7 compound Isobutyl vinyl ether — — — — — — — — 6.7 — — 2-Ethylhexyl vinyl — — — — — — — — — 10.5 — ether Values of Solid content (% 59.7 59.8 59.3 59.7 59.2 59.5 54.8 54.9 55.3 55 55.1 by mass) properties Gardner viscosity TU −W PQ +V N −X +I LM K +J P B-type viscosity 620 990 420 910 340 1250 230 330 300 260 400 (mPa .Math. s) Mn 4100 4800 3800 4800 2900 5400 5400 5200 5300 5000 7700 Mw 14000 18000 12000 16000 9400 22000 13000 13000 13000 12000 21000 Performance of Water resistance 1 ◯ ◯ ◯ ◯ ◯ Δ ◯ ◯ ◯ ◯ Δ coating film Hardness (N/mm.sup.2) 1.49 1.96 1.26 2.24 1.23 1.52 2.4 2.8 3.2 2.6 0.2

(88) In Table 1, the numerical values described in the columns for the monomer (a1), the macromonomer, the monomer (c), and the initiator indicate the charged amount (parts). The content of butyl vinyl ether in each polymer-containing composition is 50% by mole with respect to the sum of the structure (I) of the copolymer contained in each polymer-containing composition.

(89) The polymer-containing compositions A-1 to A-5 and A-7 to A-10 of Examples 1 to 9 had a low viscosity while having a high solid content. In addition, the hardness and water resistance of the coating film formed were favorable.

(90) The polymer-containing compositions A-6 and A-11 of Comparative Examples 1 and 2 in which the macromonomer was not used had a higher viscosity as compared to those of Examples 1 to 9 although these had a solid content at the same level as those of Examples 1 to 9. In addition, the coating film formed exhibited a low hardness and poor water resistance.

Examples 10 to 20 and Comparative Examples 3 to 4

(91) One obtained in advance by charging the respective components in a metal can according to the composition presented in Table 2, adding 70 g of glass beads thereto, and mixing them together by using a stirring rod was pigment-dispersed by using a rocking shaker, thereby obtaining an anti-fouling coating composition.

(92) The evaluation results for the anti-fouling coating composition thus obtained are presented in Table 2.

(93) TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Example 10 11 12 13 14 15 16 Compo- Polymer- A-1 42 — — — — — — sition containing A-2 — 42 — — — — — compo- A-3 — — 42 — — — — sition A-4 — — — 42 — 42 42 (solid A-5 — — — — 42 — — content of A-6 — — — — — — — polymer A-7 — — — — — — — charged A-8 — — — — — — — is 25 A-9 — — — — — — — parts) A-10 — — — — — — — A-11 — — — — — — — Pigment Talc — — — — — 20 20 Zinc oxide — — — — — 20 20 Anti- Cuprous oxide 48 48 48 48 48 — — fouling Zinc pyrithione 0.5 0.5 0.5 0.5 0.5 3 3 agent Copper pyri- — — — — — — — thione Medetomidine — — — — — — 5 Anti-fouling — — — — — 5 — agent (1) Thermo- Additive (1) 1 1 1 1 1 2 2 plastic Additive (2) 3 3 3 3 3 2 2 resin Additive (3) — — — — — 1.5 1.5 Organic Xylene 5.5 5.5 5.5 5.5 5.5 4.5 4.5 solvent Sum 100 100 100 100 100 100 100 Properties of Heating residue 77.7 77.7 77.7 77.7 77.7 77.7 77.7 coating (% by mass) B-type viscos- 3400 3920 1650 3590 1380 3600 3600 ity (mPa .Math. s) Paintability ◯ ◯ ◯ ◯ ◯ ◯ ◯ VOC (g/L) 306 386 386 386 386 386 386 Performance of Degree of 6.7 4.7 5.3 5.0 2.7 9.0 5.3 coating film consumption (3 months) (μm/M) Comparative Example Example Example Example Comparative Example 3 17 18 19 20 Example 4 Compo- Polymer- A-1 — — — — — — sition containing A-2 — — — — — — compo- A-3 — — — — — — sition A-4 — — — — — — (solid A-5 — — — — — — content of A-6 42 — — — — — polymer A-7 — 46 — — — — charged A-8 — — 46 — — — is 25 A-9 — — — 46 — — parts) A-10 — — — — 46 — A-11 — — — — — 46 Pigment Talc — — — — — — Zinc oxide — — — — — — Anti- Cuprous oxide 48 48 48 48 48 48 fouling Zinc pyrithione 0.5 — — — — — agent Copper pyri- — 0.5 0.5 0.5 0.5 0.5 thione Medetomidine — — — — — — Anti-fouling — — — — — — agent (1) Thermo- Additive (1) 1 1 1 1 1 1 plastic Additive (2) 3 3 3 3 3 3 resin Additive (3) — — — — — — Organic Xylene 5.5 1.5 1.5 1.5 1.5 1.5 solvent Sum 100 100 100 100 100 100 Properties of Heating residue coating (% by mass) 77.7 77.7 77.7 77.7 77.7 77.7 B-type viscos- 5300 3200 3800 3400 3300 5400 ity (mPa .Math. s) Paintability Δ ◯ ◯ ◯ ◯ Δ VOC (g/L) 386 386 386 386 386 386 Performance of Degree of 7.3 5.0 6.7 5.0 4.0 5.7 coating film consumption (3 months) (μm/M)

(94) In Table 2, the numerical values described in the column for the composition indicate the blended amount (parts). In Table 2, the amount of the polymer-containing composition blended is the total amount of the polymer-containing composition.

(95) The anti-fouling coating compositions of Examples 10 to 20 had a low viscosity while having a high solid content and a low VOC, and the paintability thereof was favorable. In addition, the degree of consumption of the coating films formed was favorable, and it can be judged that the hardness and water resistance of the coating films are also favorable from the results for Examples 1 to 9.

(96) The anti-fouling coating composition of Comparative Example 3 using a copolymer which did not contain a constitutional unit based on a macromonomer had a higher coating viscosity and poor paintability as compared to Examples 10 to 14 having the same composition except the polymer-containing composition although it had a heating residue and VOC at the same level as those of Examples 10 to 14. The same tendency was found in comparison between Comparative Example 4 and Examples 18 to 20 as well.

(97) The static anti-fouling properties of the anti-fouling coating compositions of Example 10 and Comparative Example 3 were evaluated, and the results for both of them were favorable.

Example 21

(98) In a reaction vessel equipped with a stirrer, a temperature controller, and a dropping funnel, 40 parts of xylene and 10 parts of macromonomer (MM2) were charged, and the temperature of the mixture was raised to 90° C. while stirring it. Subsequently, a mixture composed of 50 parts of TIPX, 25 parts of MMA, 10 parts of EA, 5 parts of MTA, and 1.0 part of AMBN was added dropwise thereto from the dropping funnel at a constant rate over 4 hours in a nitrogen atmosphere. In 30 minutes after the dropwise addition was competed, 1.0 part of t-butylperoxy 2-ethylhexanoate and 10 parts of xylene were added dropwise to the resultant mixture over 1.5 hours, and the mixture was further stirred for 1 hour, thereby obtaining a polymer-containing composition (polymer solution) A-12 in the form of a solution having a solid content of 61.1% by mass and a B-type viscosity of 760 mPa.Math.s.

Examples 22 to 23 and Comparative Example 5

(99) Polymer-containing compositions A-13, A-14, and A-16 were produced in the same manner as in Example 21 except that the amounts (parts) of the monomer and the initiator AMBN charged were changed as presented in Table 3.

Example 24

(100) In a reaction vessel equipped with a stirrer, a temperature controller, and a dropping funnel, 40 parts of xylene was charged, and the temperature of the xylene was raised to 90° C. while stirring it. Subsequently, a mixture composed of 50 parts of TIPX, 10 parts of macromonomer (MM2), 25 parts of MMA, 10 parts of EA, 5 parts of MTA, and 1.0 part of AMBN was added dropwise thereto from the dropping funnel at a constant rate over 4 hours funnel in a nitrogen atmosphere. In 30 minutes after the dropwise addition was competed, 1.0 part of t-butylperoxy 2-ethylhexanoate and 26 parts of xylene were added dropwise to the resultant mixture over 1.5 hours, and the mixture was further stirred for 1 hour, thereby obtaining a polymer-containing composition (polymer solution) A-15 in the form of a solution having a solid content of 61.1% by mass and a B-type viscosity of 690 mPa.Math.s.

(101) The values of properties (solid content (% by mass), amount of organic solvent (% by mass), B-type viscosity, and the number average molecular weight (Mn), weight average molecular weight (Mw), and acid value of the copolymer contained in each of the polymer-containing compositions) of the polymer-containing compositions A-12 to A-16 thus obtained are presented in Table 3. The solid content in the polymer-containing compositions A-12 to A-16 is equal to the content of the copolymer. In addition, the performance (hardness, hardness after 1 day, and water resistance 2) of the coating films formed of the polymer-containing compositions are presented in Table 3.

(102) TABLE-US-00003 TABLE 3 Comparative Example 21 Example 22 Example 23 Example 24 Example 5 Polymer-containing composition A-12 A-13 A-14 A-15 A-16 Monomer (a2) TIPX 50 50 50 50 50 Macromonomer (b) MM1 (low Mn 1600) — — 20 — — MM2 (high Mn 2500) 10 20 — 10 — Monomer (c) MMA 25 15 15 25 35 EA 10 10 10 10 10 MTA 5 5 5 5 5 Initiator AMBN 1 1 1 1 1 Values of properties Solid content (% by mass) 61.1 61.2 61.1 61.1 61.8 Amount of organic solvent (% by mass) 38.9 38.8 38.9 38.9 38.2 B-type viscosity (mPa .Math. s) 760 870 720 690 1010 Mw 19200 15500 13300 19000 25000 Mn 6400 6000 4900 6500 7600 Performance of Acid value (mgKOH/g) 0.4 0.6 0.6 0.6 0.53 coating film Hardness (N/mm.sup.2) 7.4 9.0 7.3 7.5 6.2 Hardness after 1 day (N/mm.sup.2) 3.6 4.3 3.8 3.8 2.9 Water resistance 2 7 6.4 6.8 7.2 14.7 (haze value (%))

(103) In Table 3, the numerical values described in the columns for the monomer (a2), the macromonomer, the monomer (c), and the initiator indicate the charged amount (parts). Incidentally, the amount of xylene to be finally added was adjusted so as to have the amount of organic solvent and the solid content described in the table.

(104) The polymer-containing compositions A-12 to A-15 of Examples 21 to 24 had a low viscosity while having a high solid content. In addition, the hardness and water resistance of the coating films formed were favorable.

(105) The polymer-containing composition A-16 of Comparative Example 5 in which a macromonomer was not used had a higher viscosity as compared to those of Examples 21 to 24 although it had a solid content at the same level as those of Examples 21 to 24. In addition, the hardness of coating film and the hardness of coating film in 1 day after painting were low. The water resistance of the coating film was favorable but inferior to those of Examples 21 to 24.

Examples 25 to 28 and Comparative Example 6

(106) One obtained in advance by charging the respective components in a metal can according to the composition presented in Table 4, adding 70 g of glass beads thereto, and mixing them together by using a stirring rod was pigment-dispersed by using a rocking shaker, thereby obtaining an anti-fouling coating composition.

(107) The evaluation results for the anti-fouling coating composition thus obtained are presented in Table 4.

(108) TABLE-US-00004 TABLE 4 Comparative Example 25 Example 26 Example 27 Example 28 Example 6 Composition Polymer-containing A-12 100 — — — — composition A-13 — 100 — — — A-14 — — 100 — — A-15 — — — 100 — A-16 — — — — 100 Anti-fouling agent Cuprous oxide 150 150 150 150 150 Copper pyrithione 6.9 6.9 6.9 6.9 6.9 Medetomidine 0.1 0.1 0.1 0.1 0.1 Additive Additive (1) 1 1 1 1 1 Additive (2) 2 2 2 2 2 Solvent Xylene 10 10 10 10 10 Properties of coating Heating residue (% by mass) 78.8 78.9 79.1 78.1 80.2 B-type viscosity (mPa .Math. s) 3900 4000 3500 3400 5100 VOC (g/L) 377 377 377 377 377 Performance of coating film Degree of consumption 1.8 1.5 1.7 1.9 2.3 (3 months) (μm/M)

(109) In Table 4, the numerical values described in the column for the composition indicate the blended amount (parts). In Table 4, the amount of the polymer-containing composition blended is the total amount of the polymer-containing composition.

(110) The anti-fouling coating compositions of Examples 25 to 28 had a sufficient degree of consumption. In addition, it can be judged that the hardness, hardness after 1 day, and water resistance of the coating films are excellent from the results for Examples 21 to 24.

(111) The coating film formed of the anti-fouling coating composition of Comparative Example 6 had a sufficient degree of consumption, but it can be judged that the hardness, hardness after 1 day, and water resistance of the coating film are inferior to those of Examples 25 to 28 from the results for Comparative Example 5.

(112) The static anti-fouling properties of the anti-fouling coating compositions of Examples 25 to 28 and Comparative Example 6 were evaluated, and the results for all of them were favorable.

Example 29

(113) In a four-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a stirrer, 15 parts of PGM (propylene glycol methyl ether), 30 parts of xylene, and 4.0 parts of EA were charged, and the temperature of the mixture was raised to 100° C. while stirring it. Subsequently, a mixture composed of 23.0 parts of MMA methyl methacrylate, 10 parts of EA, 30 parts of BA, 28.8 parts (total amount including organic solvent) of the monomer (a3-1) obtained in Production Example a3-1, 20 parts of the macromonomer (MM1) obtained in Production Example MM1, 1.5 parts of a chain transfer agent (NOFMER (registered trademark) MSD manufactured by NOF CORPORATION), and 13.0 parts of AMBN was added dropwise thereto from the dropping funnel at a constant rate over 6 hours. After the dropwise addition was completed, 0.5 part of t-butyl peroctoate and 8 parts of xylene were added dropwise to the resultant mixture over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, thereby obtaining a polymer-containing composition (polymer solution) A-17 in the form of a solution having a solid content of 57.2% by mass and a B-type viscosity of 390 mPa.Math.s.

Examples 30 to 34 and 42 to 46 and Comparative Example 7

(114) Polymer-containing compositions (polymer solutions) A-18 to A-22. A-30 to A-33, A-35, and A-36 in the form of a solution were produced in the same manner as in Example 29 except that the amounts of the monomers charged were changed as presented in Tables 5 to 6.

(115) Incidentally, only the solid amount is described as the amount of the monomer (a3) blended in Tables 5 to 6.

Example 35

(116) In a pressure-polymerizable autoclave equipped with a condenser, a thermometer, a dropping tank, and a stirrer, 15 parts of PGM (propylene glycol methyl ether), 30 parts of xylene, and 4 parts of EA were charged, and the pressure in the autoclave was increased to 350 kPa and the temperature of the mixture was raised to 145° C. while stirring the mixture. Subsequently, a transparent mixture composed of 35 parts of MMA, 5 parts of EA, 30 parts of BA, 28.8 parts (total amount including organic solvent) of the monomer (a3-1) obtained in Production Example a3-1, 1.5 parts of a chain transfer agent (NOFMER MSD manufactured by NOF Corporation), and 6 parts of AMBN was added dropwise thereto from the dropping tank at a constant rate over 4 hours. After the dropwise addition was completed, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise to the resultant mixture over 30 minutes, the mixture was further stirred for 1 hour 30 minutes, 8 parts of xylene was then added to the resultant mixture, and the resultant mixture was filtered through a 300 mesh, thereby obtaining a polymer-containing composition (polymer solution) A-23 in the form of a solution.

Examples 36 to 41 and 47

(117) Polymer-containing compositions (polymer solutions) A-24 to A-29 and A-37 in the form of a solution were produced in the same manner as in Example 35 except that the amounts of the monomers charged were changed as presented in Tables 5 to 6.

(118) Incidentally, only the solid amount is described as the amount of the monomer (a3) blended in Tables 5 to 6.

Comparative Example 8

(119) In a reaction vessel equipped with a stirrer, a temperature controller, and a dropping device, 15 parts of xylene was charged, and the temperature of the xylene was raised to 130° C. while stirring it. Thereafter, a mixture composed of the following raw materials was added dropwise thereto at a constant rate over 2 hours, and the copolymerization reaction was further conducted for 0.5 hour.

(120) Macromonomer (MM1): 20 parts

(121) BA: 20 parts,

(122) MAA: 7 parts, and

(123) AMBN: 3 parts.

(124) Subsequently, a mixture composed of the following raw materials was added dropwise to the resultant mixture at a constant rate over 3 hours, and the copolymerization reaction was further conducted for 0.5 hour.

(125) Monomer (a3-1): 28.8 parts

(126) MMA: 16 parts,

(127) EA: 9 parts,

(128) BA: 10 parts.

(129) NOFMER MSD (manufactured by NOF Corporation): 1.5 parts, and

(130) AMBN: 10 parts.

(131) Subsequently, 0.5 part of PERBUTYL O was added to the resultant mixture, and the polymerization reaction was continuously conducted for 1 hour, the resultant mixture was then heated to 80° C., 7.0 parts of dimethylethanolamine (DMEA) was added thereto, and the mixture was mixed until to be homogeneous, thereby obtaining a polymer solution. The B-type viscosity of this polymer solution at 25° C. was 2000 Pa-s or more. Thereafter, 110 parts of deionized water was gradually added to this polymer solution to obtain an aqueous polymer-containing composition A-33.

(132) The kinds and amounts of the materials used in the production of the polymer-containing compositions and the values of properties (solid content (% by mass), amount of organic solvent (% by mass), B-type viscosity, and the number average molecular weight (Mn), weight average molecular weight (Mw), and acid value of the copolymer contained in each of the polymer-containing compositions) of the polymer-containing compositions A-17 to A-37 thus obtained are presented in Tables 5 to 6. The solid content in the polymer-containing compositions A-17 to A-37 is equal to the content of the copolymer. In addition, the performance (hardness, hardness after 1 day, and water resistance 2) of the coating films formed of the polymer-containing compositions are presented in Tables 5 to 6.

(133) TABLE-US-00005 TABLE 5 Example Example Example Example Example Example Example Example Example Example Example 29 30 31 32 33 34 35 36 37 38 39 Polymer-containing composition A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 Monomer (a3) a3-1 13 13 13 13 13 13 6 18 21 13 18 a3-2 — — — — — — — — — — — Macromono- MM1 (low Mn 20 — — — — — 20 20 20 20 5 mer (b) 1600) MM2 (High Mn — 20 — 40 40 40 — — — — — 2500) MM4 (high Mn — — 20 — — — — — — — — 6700) Monomer (c) MMA 23 23 23 — — — 35 23 23 — 38 EA 14 14 14 17 17 17 9 8 5 13 8 BA 30 30 30 30 30 30 30 30 30 21.5 30 MA — — — — — — — — — 30.7 — Initiator AMBN 13 13 13 13 7 18 6 6 6 6 6 Chain trans- NOFMER MSD 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 fer agent Values of Solid content 57.2 57.3 52.2 57.0 57.3 56.4 56.0 55.9 56.0 57.9 55.9 properties (% by mass) Amount of or- 41.9 41.8 46.9 42.1 41.8 42.7 43.6 43.2 42.6 41.2 42.9 ganic solvent (% by mass) B-type viscosity 390 600 1200 480 840 350 300 670 1100 430 610 (mPa .Math. s ) Mw 4000 4800 6000 5700 6300 5200 4500 4200 4100 4300 4200 Mn 1500 1700 2300 1700 2300 1500 1300 1300 1200 1300 1300 Acid value 31.6 32.5 31.1 32.4 32.3 32.1 16.4 46.2 53.8 37.3 45.3 (mgKOH/g) Hardness 18 24.0 31.0 33.0 38.0 30.0 10.0 18.0 31.0 20.0 5.7 (N/mm.sup.2) Performance Hardness after 8.9 13.0 17.0 18.0 20.0 15.0 6.7 9.7 14.0 10.9 3.1 of coating 1 day film Water resistance 9.7 8.4 7.6 7.2 7.4 7.1 9.1 7.0 6.8 12.2 22.2 2 (haze value (%))

(134) TABLE-US-00006 TABLE 6 Exam- Exam- Exam- Exam- Exam- Comparative Comparative Exam- Exam- Exam- ple 40 ple 41 ple 42 ple 43 ple 44 Example 7 Example 8 ple 45 ple 46 ple 47 Polymer-containing composition A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 Monomer (a3) a3-1 18 18 18 13 — 13 13 13 18 13 a3-2 — — — — 21 — — — — — Monomer (a2) TIPX — — — — — — — — — 10 Macromono- MM1 (low Mn 1600) 10 15 20 20 20 0 20 — 20 20 mer (b) MM5 (MMA/MTMA) — — — — — — — 20 — — Monomer (c) MMA 33 28 — 15 23 10 16 23 — 19 EA 8 8 26.5 27 8 62 14 14 56.6 8 BA 30 30 — 25 30 15 30 30 — 30 MTA — — 30 — — — — — — — MAA — — — — — — 7 — — — Initiator AMBN 6 6 11 16 4 13 13 13 12 6 Chain transfer NOFMER MSD 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 agent Values of Solid content (% by 56.1 57.5 56.8 61.0 56.0 56.0 40.0 56.0 56.8 56.2 properties mass) Amount of organic 42.7 41.3 42.0 38.1 43.1 43.1 1.5 43.1 42.0 42.9 solvent (% by mass) B-type viscosity 530 480 1300 800 820 1300 940 600 960 620 (mPa .Math. s) Mw 4300 4700 5200 4800 5500 3600 5800 4600 4800 4300 Mn 1300 1400 1600 1700 1700 1300 2300 1600 1700 1300 Acid value (mgKOH/g) 45.8 46.0 45.8 33.3 44.9 31.0 43.0 32.5 46.1 30.3 Hardness (N/mm.sup.2) 7.4 14.0 14.0 19.0 21.0 1.8 4.9 28.0 13.0 16.0 Performance Hardness after 1 day 3.8 6.7 8.1 9.9 10.1 0.9 1.5 16.0 7.8 8.2 of coating Water resistance 2 14.5 10.1 14.1 10.1 9.6 65.1 70.4 9.0 12.2 6.5 film (haze value (%))

(135) In Tables 5 to 6, the numerical values described in the columns for the monomer and the initiator indicate the charged amount (parts). Only the solid amount is described as the amount of the monomer (a3) blended. Incidentally, an organic solvent is contained in the monomers (a3-1) and (a3-2), the amount of xylene to be finally added was thus adjusted so as to have the amount of organic solvent and the solid amount described in the table.

(136) The coating films formed of the polymer-containing compositions of Examples 29 to 47 exhibited excellent hardness and water resistance. In addition, the hardness of coating films after 1 day was high.

(137) The coating film formed of the resin composition of Comparative Example 7 in which a macromonomer was not used exhibited poor hardness and water resistance. In addition, the viscosity of the polymer-containing composition was high.

(138) The coating film formed of the polymer-containing composition of Comparative Example 8 which was an aqueous dispersion obtained by dispersing a polymer solution having a B-type viscosity of higher than 5×10.sup.4 mPa.Math.s at 25° C. in water and had a content of organic solvent to be less than 30% by mass with respect to the total amount of the polymer-containing composition excluding the copolymer exhibited a low hardness after 1 day and poor water resistance. In addition, the polymer solution had a high viscosity and low handling properties.

(139) It is required to decrease the viscosity of the polymer-containing composition when it is attempted to decrease the VOC of the anti-fouling coating composition and the like. However, the water resistance and hardness of the coating film decrease as in Comparative Example 7 when the molecular weight of the polymer is decreased or the glass transition temperature (Tg) is decreased in order to decrease the viscosity of the polymer-containing composition. By using a macromonomer, it is possible to decrease the viscosity of the polymer-containing composition and to form a coating film exhibiting a high hardness and favorable water resistance.

Examples 48 to 68 and Comparative Examples 9 to 10

(140) Anti-fouling coating compositions were obtained by mixing the respective components according to the composition presented in Tables 7 to 8 by using a high-speed disperser. The evaluation results on the performance (degree of consumption) of the coating films formed of the anti-fouling coating compositions thus obtained are presented in Tables 7 to 8.

(141) TABLE-US-00007 TABLE 7 Example Example Example Example Example Example 48 49 50 51 52 53 Compo- Polymer- A-17 100 — — — — — sition containing A-18 — 100 — — — — composi- A-19 — — 100 — — — tion A-20 — — — 100 — — A-21 — — — — 100 — A-22 — — — — — 100 A-23 — — — — — — A-24 — — — — — — A-25 — — — — — — A-26 — — — — — — A-27 — — — — — — A-28 — — — — — — Pigment Talc 30 30 30 30 30 30 Zinc oxide 60 60 60 60 60 60 Anti- Zinc pyrithione 5 5 5 5 5 5 fouling Medetomidine 0.1 0.1 0.1 0.1 0.1 0.1 agent Anti-fouling 8 8 8 8 8 8 agent (1) Additive Additive (1) 1 1 1 1 1 1 Additive (2) 2 2 2 2 2 2 Solvent BuOH 5 5 5 5 5 5 Properties of coating Heating residue 72 72.2 70.1 70.1 70.5 72.1 (% by mass) B-type viscosity 1500 2200 3900 1600 2500 1200 (mPa .Math. s) VOC (g/L) 395 395 430 395 395 395 Performance of Degree of consumption 2.4 2.3 2.3 2.2 2.1 2.1 coating film (3 months) (μm/M) Example Example Example Example Example Example 54 55 56 57 58 59 Compo- Polymer- A-17 — — — — — — sition containing A-18 — — — — — — composi- A-19 — — — — — — tion A-20 — — — — — — A-21 — — — — — — A-22 — — — — — — A-23 100 — — — — — A-24 — 100 — — — — A-25 — — 100 — — — A-26 — — — 100 — — A-27 — — — — 100 — A-28 — — — — — 100 Pigment Talc 30 30 30 30 30 30 Zinc oxide 60 60 60 60 60 60 Anti- Zinc pyrithione 5 5 5 5 5 5 fouling Medetomidine 0.1 0.1 0.1 0.1 0.1 0.1 agent Anti-fouling 8 8 8 8 8 8 agent (1) Additive Additive (1) 1 1 1 1 1 1 Additive (2) 2 2 2 2 2 2 Solvent BuOH 5 5 5 5 5 5 Properties of coating Heating residue 71.4 73.5 71.1 72.6 73.1 72.9 (% by mass) B-type viscosity 1200 2200 3700 1800 1800 1800 (mPa .Math. s) VOC (g/L) 395 395 395 395 395 395 Performance of Degree of consumption 1.6 3.6 4.7 5.2 2.1 2.2 coating film (3 months) (μm/M)

(142) TABLE-US-00008 TABLE 8 Comparative Example Example Example Example Example Example 60 61 62 63 64 ple 9 Compo- Polymer- A-17 — — — — 100 — sition containing A-29 100 — — — — — composi- A-30 — 100 — — — — tion A-31 — — 100 — — — A-32 — — — 100 — — A-33 — — — — — 100 A-34 — — — — — — A-35 — — — — — — A-36 — — — — — — A-37 — — — — — — Pigment Talc 30 30 30 30 — 30 Zinc oxide 60 60 60 60 — 60 Anti- Cuprous oxide — — — — 120 — fouling Copper pyrithione — — — — 1.5 — agent Zinc pyrithione 5 5 5 5 — 5 Medetomidine 0.1 0.1 0.1 0.1 — 0.1 Anti-fouling agent (1) 8 8 8 8 — 8 Pyridine-triphenylborane — — — — — — Additive Additive (1) 1 1 1 1 2 1 Additive (2) 2 2 2 2 5 2 Additive (4) — — — — — — Organic BuOH 5 5 5 5 5 5 solvent Water — — — — — — Properties of coating Heating residue 71.3 70.9 75.1 72.4 73.5 70.7 (% by mass) B-type viscosity 1600 4400 2300 2300 4400 4400 (mPa .Math. s) VOC (g/L) 395 395 375 395 420 395 Performance of Degree of consumption 2.4 20.0 2.4 2.1 1.7 4.9 coating film (3 months) (μm/M) Comparative Example Example Example Example Example ple 10 65 66 67 68 Compo- Polymer- A-17 — — — — 100 sition containing A-29 — — — — — composi- A-30 — — — — — tion A-31 — — — — — A-32 — — — — — A-33 — — — — — A-34 100 — — — — A-35 — 100 — — — A-36 — — 100 — — A-37 — — — 100 — Pigment Talc 30 30 30 30 30 Zinc oxide 60 60 60 60 60 Anti- Cuprous oxide — — — — — fouling Copper pyrithione — — — — — agent Zinc pyrithione 5 5 5 5 5 Medetomidine 0.1 0.1 0.1 0.1 0.1 Anti-fouling agent (1) 8 8 8 8 — Pyridine-triphenylborane — — — — 8 Additive Additive (1) 1 1 1 1 1 Additive (2) 2 2 2 2 2 Additive (4) — — — — 1 Organic solvent BuOH — 5 5 5 5 Water 5 — — — — Properties of coating Heating residue 65.1 73.5 70.8 70.7 70.7 (% by mass) B-type viscosity 4000 2000 3100 1900 1500 (mPa .Math. s) VOC (g/L) 270 395 395 395 395 Performance of Degree of consumption 1.4 3.2 10.1 3.1 2.0 coating film (3 months) (μm/M)

(143) In Tables 7 to 8, the numerical values described in the column for the composition indicate the blended amount (parts). In Tables 7 to 8, the amount of the polymer-containing composition blended is the total amount of the polymer-containing composition.

(144) The coating films formed of the anti-fouling coating compositions of Examples 48 to 68 had a sufficient degree of consumption. In addition, it can be judged that the hardness, the hardness after 1 day, and water resistance of the coating films are excellent from the results for Examples 29 to 47.

(145) The coating film formed of the anti-fouling coating composition of Comparative Example 9 had a sufficient degree of consumption, but it can be judged that the hardness, hardness after 1 day, and water resistance of the coating film are low from the results for Comparative Example 7.

(146) The coating film formed of the anti-fouling coating composition of Comparative Example 10 had a lower degree of consumption as compared to those of Examples 48 to 68. Hence, it can be judged that the anti-fouling properties are poor. In addition, it can be judged that the water resistance is low from the result for Comparative Example 8.

(147) The static anti-fouling properties of the anti-fouling coating compositions of Examples 48 and 51 and Comparative Example 6 were evaluated, and the results for all of them were favorable.

INDUSTRIAL APPLICABILITY

(148) The (meth)acrylic copolymer, the polymer solution, and the polymer-containing composition of the present invention can be used in anti-fouling coating compositions, anti-fogging coating compositions, and the like, and these can be suitably used particularly in anti-fouling coating compositions.