WO2019198630A1 - 防汚塗料組成物 - Google Patents
防汚塗料組成物 Download PDFInfo
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- WO2019198630A1 WO2019198630A1 PCT/JP2019/015087 JP2019015087W WO2019198630A1 WO 2019198630 A1 WO2019198630 A1 WO 2019198630A1 JP 2019015087 W JP2019015087 W JP 2019015087W WO 2019198630 A1 WO2019198630 A1 WO 2019198630A1
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- monomer
- copolymer
- antifouling
- monomers
- antifouling coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
Definitions
- the present invention relates to an antifouling paint composition.
- Aquatic fouling organisms such as barnacles, cell plastics, blue mussels, scallops, sea squirts, blue sea breams, blue sea breams, slime, etc., become submarine structures such as ships (especially ship bottoms), fishing nets, fishing net accessories, etc. Adhering causes problems such as damage to the functions of the ship and the like, and the appearance.
- an antifouling coating composition is applied to a ship or the like to form an antifouling coating, and the antifouling agent is gradually released from the antifouling coating, thereby preventing the antifouling over a long period of time.
- Patent Document 1 A technique for demonstrating performance is known (Patent Document 1).
- the present invention has been made in view of such circumstances, and can form an antifouling coating film that can exhibit good long-term antifouling performance even in a bay where the attachment of fouling organisms is very severe and has excellent seawater resistance.
- a copolymer for a possible antifouling coating composition is provided.
- an antifouling paint composition containing a copolymer P and an antifouling agent
- the copolymer P includes a monomer (a), a monomer (b), a monomer (c), and an ethylenically unsaturated monomer other than the monomers (a) to (c).
- the monomer (a) is represented by the general formula (1), The content of the monomer (a) is 25 to 50% by mass with respect to the total mass of the monomers (a) to (d),
- the monomers (b) and (c) are monomers having a common logarithm log P of n-octanol / water partition coefficient P of 0.00 to 0.59 and 0.60 to 0.95, respectively.
- An antifouling coating composition is provided in which the monomer (c) is a monomer having only one unsaturated bond.
- R 1 is a methyl group
- R 2 , R 3 and R 4 are the same or different and each represents a branched alkyl group having 3 to 8 carbon atoms or a phenyl group
- an antifouling coating film formed using an antifouling coating composition using a predetermined copolymer has a very severe adhesion of fouling organisms, and the pH of seawater is low.
- the present inventors have found that excellent long-term antifouling performance can be exhibited and that seawater resistance is excellent, and the present invention has been completed.
- the antifouling paint composition of the present invention comprises a copolymer P and an antifouling agent.
- Copolymer P comprises monomer (a), monomer (b), monomer (c), and an ethylenically unsaturated monomer other than the monomers (a) to (c). It is a copolymer with (d).
- the monomer (a) is a triorganosilyl methacrylate monomer and is represented by the general formula (1).
- R 1 is a methyl group
- R 2 , R 3 and R 4 are the same or different and each represents a branched alkyl group having 3 to 8 carbon atoms or a phenyl group
- Examples of the monomer (a) include triisopropylsilyl methacrylate, triisobutylsilyl methacrylate, tris-butylsilyl methacrylate, triisoamylsilyl methacrylate, tris (2-ethylhexyl) silyl methacrylate, and triphenyl methacrylate.
- the content of the monomer (a) is 25 to 50% by mass with respect to the total mass of the monomers (a) to (d) from the viewpoint of long-term stationary antifouling performance and no coating film abnormality. 30 to 50% by mass is particularly preferable.
- the monomer (b) is a monomer copolymerizable with the monomers (a), (c), and (d), and the common logarithm logP of the partition coefficient P between n-octanol / water is 0. 0.000 to 0.59.
- the distribution coefficient P is a value of the ratio of the distribution concentration of a substance to each phase of a two-phase solvent system composed of n-octanol and water, and log P is a common logarithm of the distribution coefficient P.
- a larger value of log P means higher lipophilicity (lower hydrophilicity).
- log P means a value calculated based on the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)). LogP by this method can be calculated by using, for example, a program of ChemDraw Professional 17 Suite from PerkinElmer.
- Examples of the monomer (b) include 2- [2- (2-hydroxyethoxy) ethoxy] ethoxy] ethyl methacrylate, mono (2- (meth) acryloyloxyethyl) succinate, N- (3-dimethyl).
- the monomer (b) preferably has a log P of 0.20 to 0.59 and has a log P of 0 because it can exhibit good long-term stationary antifouling performance even in bays where the attachment of fouling organisms is very severe. More preferred is 40 to 0.50.
- the value of logP is, for example, 0.00, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45. , 0.50, 0.55, 0.59, and may be within a range between any two of the numerical values exemplified here.
- the content of the monomer (b) is 5 to 30% by mass with respect to the total mass of the monomers (a) to (d) from the viewpoint of long-term stationary antifouling performance and no coating film abnormality. 10 to 25% by mass is more preferable.
- the monomer (c) is a monomer copolymerizable with the monomer (a), the monomer (b) and the monomer (d), and has a log P of 0.60 to 0.95. . Moreover, the monomer (c) has only one unsaturated bond.
- Examples of the monomer (c) include 4-hydroxybutyl acrylate glycidyl ether, N-isopropyl acrylamide, 2- (dimethylamino) ethyl acrylate, methyl acrylate, 2- (2-ethoxyethoxy) acrylate Ethyl, 2- (2-methoxyethoxy) ethyl methacrylate, methacrylic acid, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-ethoxyethyl acrylate, methacrylic acid Hydroxypropyl, 2-methoxyethyl methacrylate, 2- [2- (2-ethoxyethoxy) ethoxy] ethyl methacrylate, N, N′-diethylacrylamide, 3-methoxybutyl acrylate, 2-hydroxybutyl acrylate, etc.
- Acrylic acid esthetics And vinyl compounds having a functional group
- the monomer (c) preferably has a log P of 0.60 to 0.95 and has a log P of 0 because it can exhibit good long-term stationary antifouling performance even in bays where the attachment of fouling organisms is very severe. More preferred is .70 to 0.90. Specifically, the value of logP is, for example, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, and the numerical values exemplified here It may be within the range between any two.
- the content of the monomer (c) is 5 to 35% by mass with respect to the total mass of the monomers (a) to (d) from the viewpoint of preventing long-term stationary antifouling performance and coating film abnormality. Preferably, 10 to 30% by mass is more preferable.
- the monomer (d) is an ethylenically unsaturated monomer monomer copolymerizable with the monomer (a), the monomer (b) and the monomer (c).
- the monomer (d) for example, methyl methacrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
- Examples include lauryl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and the like.
- the copolymer (P) of the present invention can be obtained by copolymerizing a mixture of monomers (a) to (d). The copolymerization is performed, for example, in the presence of a polymerization initiator.
- the weight average molecular weight (Mw) of the copolymer is desirably 5000 to 300,000. If the molecular weight is less than 5,000, the antifouling paint film becomes brittle and easily peels and cracks. If it exceeds 300,000, the viscosity of the copolymer solution increases and handling becomes difficult. .
- this Mw is, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, and between any two of the numerical values exemplified here. It may be within the range.
- the copolymer may be a random copolymer of monomers (a) to (d), an alternating copolymer, a periodic copolymer, or a block copolymer.
- polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile). ), Dimethyl-2,2′-azobisisobutyrate, dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (N-butyl-2-methylpropionamide) and the like; Oxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , Di-t-hexyl peroxide, t-butylperoxy-2-ethylhexyl monocarbonate Di-t-butyl peroxide, 1,1,3,3-tetramethylbutylper
- polymerization initiators can be used alone or in combination of two or more thereof.
- polymerization initiators in particular, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) Dimethyl 2,2′-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate are preferred.
- 2,2′-azobisisobutyronitrile 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) Dimethyl 2,2′-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate are preferred.
- polymerization method examples include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization.
- solution polymerization and non-aqueous dispersion polymerization are particularly preferable in that a copolymer can be obtained easily and with high accuracy.
- an organic solvent may be used as necessary.
- the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane, heptane and mineral spirit; ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, 2-acetate Ester solvents such as methoxy-1-methylethyl; alcohol solvents such as isopropyl alcohol, butyl alcohol and 1-methoxy-2-propanol; ether solvents such as dioxane, diethyl ether and dibutyl ether; methyl ethyl ketone, methyl isobutyl ketone, Examples include ketone solvents such as cyclohexanone.
- an aromatic hydrocarbon solvent is particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.
- the reaction temperature in the polymerization reaction may be appropriately set according to the kind of the polymerization initiator and the like, and is usually 60 to 150 ° C., preferably 70 to 140 ° C.
- the reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 10 hours.
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.
- Antifouling agent examples include inorganic agents and organic agents.
- examples of the inorganic agent include cuprous oxide, copper thiocyanate (generic name: rhodan copper), copper powder, and the like. Of these, cuprous oxide and rhodan copper are particularly preferred, and cuprous oxide is surface-treated with glycerin, sucrose, stearic acid, lauric acid, lysine, mineral oil, etc., for long-term stability during storage. And more preferable.
- organic agents examples include 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylene bisdithiocarbamate (generic name: Genev).
- the antifouling coating resin of the present invention is protected by adding an elution regulator, plasticizer, pigment, dye, antifoaming agent, dehydrating agent, thixotropic agent, organic solvent, etc. as necessary.
- the elution regulator that can be used as a dirty paint include rosin, rosin derivatives, naphthenic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, versatic acid, trimethylisobutenyl cyclohexene carboxylic acid, and metal salts thereof.
- Monocarboxylic acid and a salt thereof, or the alicyclic hydrocarbon resin can be used alone or in combination of two or more.
- Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
- Examples of the alicyclic hydrocarbon resin include Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.) and the like as commercially available products.
- Examples of the plasticizer include phosphate esters, phthalates, adipic esters, sebacic esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, petrolatum, polybutene. , Trimellitic acid tris (2-ethylhexyl), silicone oil, liquid paraffin, chlorinated paraffin and the like. These can be used alone or in combination of two or more.
- dehydrating agent examples include calcium sulfate, synthetic zeolite-based adsorbent, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. These can be used alone or in combination of two or more.
- the antifouling paint composition of the present invention is prepared by, for example, mixing a mixed solution containing the copolymer (P), the antifouling agent and other additives using a disperser. It can be manufactured by dispersing.
- the mixed solution is preferably prepared by dissolving or dispersing various materials such as a copolymer and an antifouling agent in a solvent.
- the solvent the thing similar to the said organic solvent can be used.
- the disperser for example, one that can be used as a fine pulverizer can be suitably used. For example, a commercially available homomixer, sand mill, bead mill or the like can be used.
- the mixed solution may be mixed and dispersed using a container provided with a stirrer to which glass beads for mixing and dispersing are added.
- the antifouling treatment method of the present invention forms an antifouling coating film on the surface of a film-forming article using the antifouling coating composition.
- the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing the adhesion of chickenpox fouling organisms.
- the coating film formation include ships (particularly ship bottoms), fishing equipment, underwater structures, and the like. What is necessary is just to set the thickness of an antifouling coating film suitably according to the kind of coating-film formation thing, the navigation speed of a ship, seawater temperature, etc.
- the thickness of the antifouling coating film is usually 50 to 700 ⁇ m, preferably 100 to 600 ⁇ m.
- % In each production example, comparative production example, example and comparative example represents mass%.
- the viscosity is a measured value at 25 ° C., and is a value determined by a B-type viscometer.
- the weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC.
- the conditions of GPC are as follows. Equipment: HLC-8220GPC manufactured by Tosoh Corporation Column ... TSKgel SuperHZM-M 2 flow rate ... 0.35 mL / min Detector ... RI Column bath temperature ...
- the heating residue is a value measured according to JIS K 5601-1-2: 1999 (ISO 3251: 1993) “Paint component test method—heating residue”.
- logP is a value obtained using a program of ChemDraw Professional 17 Suite manufactured by PerkinElmer.
- surface is g.
- Example 1 Coating film solubility test (rotary test)> A rotating drum having a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank so that it could be rotated by a motor.
- two rotary test machines equipped with a cooling device for keeping the temperature of seawater constant and an automatic pH controller for keeping the pH of seawater constant were prepared.
- a test plate was prepared according to the following method. First, on a titanium plate (71 ⁇ 100 ⁇ 0.5 mm), an anticorrosive paint (epoxy vinyl A / C) was applied and dried so that the thickness after drying was about 100 ⁇ m. Thereafter, the coating compositions obtained in Examples and Comparative Examples were applied on the antirust coating film in the previous period so that the thickness after drying was about 200 ⁇ m, and dried at 40 ° C. for 3 days to obtain a test plate. Prepared. Two identical test plates were prepared for each coating composition. The produced test plate was fixed to the rotating drum of the rotating device of the above apparatus so as to be in contact with seawater, and the rotating drum was rotated at a speed of 20 knots.
- an anticorrosive paint epoxy vinyl A / C
- the temperature of the seawater was kept at 25 ° C.
- the pH of the first unit was kept at 7.7 to 7.9
- the pH of the second unit was kept at pH 8.0 to 8.2
- the seawater was changed every two weeks.
- the results are shown in Tables 5 to 10.
- the numerical values in the table are total dissolution amounts at the respective time points after 6 months and 9 months.
- ⁇ Test example 2 (antifouling test)> The antifouling paint compositions obtained in the examples and comparative examples were applied to both sides of a hard PVC plate (100 ⁇ 200 ⁇ 2 mm) so that the thickness as a dry coating film was about 200 ⁇ m and dried at room temperature for 3 days.
- a test plate was prepared. This test plate was immersed in 2.0m below the sea level in Osaka Bay and Ise Bay, where adhesion of fouling organisms was very severe for 12 months, and the test plate was observed for fouling after 6 and 12 months. Evaluation was judged by the following criteria by visually observing the state of the coating film surface. The results are shown in Tables 5 to 10.
- ⁇ Level at which slime adheres without the attachment of fouling organisms such as shellfish and algae.
- ⁇ Level at which fouling organisms such as shellfish and algae partially adhere
- ⁇ Level at which fouling organisms such as shellfish and algae adhere to the entire surface
- ⁇ Test example 3 (seawater resistance test)> The coating state was simultaneously observed on the same test plate as in Test Example 2 and judged according to the following criteria. The results are shown in Tables 5 to 10. ⁇ : No blistering, cracking, peeling or the like is observed on the coating film. (Triangle
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Abstract
Description
前記共重合体Pは、単量体(a)と、単量体(b)と、単量体(c)と、前記単量体(a)~(c)以外のエチレン性不飽和単量体(d)との共重合体であり、
前記単量体(a)は、一般式(1)で表され、
前記単量体(a)の含有量は、前記単量体(a)~(d)の合計質量に対して25~50質量%であり、
前記単量体(b)及び(c)は、それぞれ、n-オクタノール/水間の分配係数Pの常用対数logPが0.00~0.59、及び0.60~0.95の単量体であり、
前記単量体(c)は、不飽和結合を1つしか有さない単量体である、防汚塗料組成物が提供される。
1.防汚塗料組成物
本発明の防汚塗料組成物は、共重合体Pと、防汚薬剤を含む。
共重合体Pは、単量体(a)と、単量体(b)と、単量体(c)と、前記単量体(a)~(c)以外のエチレン性不飽和単量体(d)との共重合体である。
単量体(a)は、メタクリル酸トリオルガノシリル単量体であり、一般式(1)で表される。
単量体(a)の含有量は、長期静置防汚性能と塗膜異常を起こさない観点から、前記単量体(a)~(d)の合計質量に対して25~50質量%であり、30~50質量%が特に好ましい。
単量体(b)は、単量体(a)、(c)、及び(d)と共重合可能な単量体であり、n-オクタノール/水間の分配係数Pの常用対数logPが0.00~0.59である。
単量体(c)は、単量体(a)、単量体(b)および単量体(d)と共重合可能な単量体であり、logPが0.60~0.95である。また、単量体(c)は、不飽和結合を1つしか有さない。
単量体(d)は、単量体(a)、単量体(b)および単量体(c)と共重合可能なエチレン性不飽和単量体単量体である。
本発明の共重合体(P)は、単量体(a)~(d)の混合物を共重合することにより得ることができる。前記共重合は、例えば、重合開始剤の存在下で行われる。
防汚薬剤としては、例えば無機薬剤及び有機薬剤が挙げられる。
無機薬剤としては、例えば、亜酸化銅、チオシアン酸銅(一般名:ロダン銅)、銅粉等が挙げられる。この中でも特に、亜酸化銅とロダン銅が好ましく、亜酸化銅はグリセリン、ショ糖、ステアリン酸、ラウリン酸、リシチン、鉱物油などで表面処理されているものが、貯蔵時の長期安定性の点でより好ましい。
これらの防汚薬剤は1種又は2種以上併用して使用できる。
さらに本発明の防汚塗料用樹脂には、必要に応じて溶出調整剤、可塑剤、顔料、染料、消泡剤、脱水剤、揺変剤、有機溶剤等を添加して防汚塗料とすることができる
溶出調整剤としては、例えば、ロジン、ロジン誘導体、ナフテン酸、シクロアルケニルカルボン酸、ビシクロアルケニルカルボン酸、バーサチック酸、トリメチルイソブテニルシクロヘキセンカルボン酸、及びこれらの金属塩等の、モノカルボン酸及びその塩、又は前記脂環式炭化水素樹脂が挙げられる。これらは単独又は2種以上で使用できる。
前記ロジン誘導体としては、水添ロジン、不均化ロジン、マレイン化ロジン、ホルミル化ロジン、重合ロジン等を例示できる。前記脂環式炭化水素樹脂としては、市販品として、例えば、クイントン1500、1525L、1700(商品名、日本ゼオン社製)等が挙げられる。
可塑剤としては、例えば、燐酸エステテル類、フタル酸エステル類、アジピン酸エステル類、セバシン酸エステル類、エポキシ化大豆油、アルキルビニルエーテル重合体、ポリアルキレングリコール類、t-ノニルペンタスルフィド、ワセリン、ポリブテン、トリメリット酸トリス(2-エチルヘキシル)、シリコーンオイル、流動パラフィン、塩素化パラフィン等が挙げられる。これらは単独又は2種以上で使用できる。
本発明の防汚塗料組成物は、例えば、前記共重合体(P)、防汚薬剤及び他の添加剤等を含有する混合液を、分散機を用いて混合分散することにより製造できる。
前記混合液としては、共重合体及び防汚薬剤等の各種材料を溶媒に溶解または分散させたものであることが好ましい。前記溶媒としては、上記有機溶媒と同様のものを使用できる。
前記分散機としては、例えば、微粉砕機として使用できるものを好適に用いることができる。例えば、市販のホモミキサー、サンドミル、ビーズミル等を使用することができる。また、撹拌機を備えた容器に混合分散用のガラスビーズ等を加えたものを用い、前記混合液を混合分散してもよい。
本発明の防汚処理方法は、上記防汚塗料組成物を用いて被塗膜形成物の表面に防汚塗膜を形成する。本発明の防汚処理方法によれば、前記防汚塗膜が表面から徐々に溶解し塗膜表面が常に更新されることにより、水棲汚損生物の付着防止を図ることができる。
被塗膜形成物としては、例えば、船舶(特に船底)、漁業具、水中構造物等が挙げられる。
防汚塗膜の厚みは、被塗膜形成物の種類、船舶の航行速度、海水温度等に応じて適宜設定すればよい。例えば、被塗膜形成物が船舶の船底の場合、防汚塗膜の厚みは通常50~700μm、好ましくは100~600μmである。
各製造例、比較製造例、実施例及び比較例中の%は質量%を示す。粘度は、25℃での測定値であり、B形粘度計により求めた値である。重量平均分子量(Mw)は、GPCにより求めた値(ポリスチレン換算値)である。GPCの条件は下記の通りである。
装置・・・ 東ソー株式会社製 HLC-8220GPC
カラム・・・ TSKgel SuperHZM-M 2本
流量・・・ 0.35 mL/min
検出器・・・ RI
カラム恒温槽温度・・・ 40℃
溶離液・・・ THF
加熱残分は、JIS K 5601-1-2:1999(ISO 3251:1993)「塗料成分試験方法-加熱残分」に準拠して測定した値である。
表1~表4中のlogPは、PerkinElmer社のChemDraw Professional 17 Suiteのプログラムを用いて得られた値である。
また、表中の各成分の配合量の単位はgである。
温度計、冷却器、攪拌装置及び滴下ロートを備えた四ツ口フラスコに、キシレン61g(初期溶媒)を仕込み、窒素ガスを導入し、攪拌しながら88℃を保持した。そこへ、単量体(a)30g、メタクリル酸メチル31g、アクリル酸n-ブチル4g、アクリル酸2-メトキシエチル15g、メタクリル酸2-メトキシエチル20g、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエイト0.8g(初期添加)の混合液を88℃で保持しながら3時間かけて滴下した。その後、88℃で1時間攪拌を行った後、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエイト0.1g(後添加)を1時間毎に3回添加し、さらに同温度で2時間攪拌を行った後、キシレン39g(希釈溶媒)添加し室温に冷却し、共重合体溶液P1を得た。P1の加熱残分、Mw、粘度を表1に示す。
表1~表4に示す単量体、重合開始剤及び溶媒を用いて、各反応温度条件下、実施例1と同様の操作で重合反応を行うことにより共重合体溶液P2~P40およびT1~T10を得た。P2~P40およびT1~T10の加熱残分、Mw、粘度を表1~表4に示す。配合量についての表中の数値は質量部である。また、表中の単量体(a)の割合は、単量体(a)~(d)の合計質量を100質量%としたときの単量体(a)の質量%を示す。
温度計、還流冷却器、及び攪拌機を備えたフラスコに、中国産ガムロジン(WW)240gとキシレン360gをフラスコに入れ、更に、前記ロジン中の樹脂酸が全て亜鉛塩を形成するように酸化亜鉛120gを加え、70~80℃で3時間、減圧下で還流脱水した。その後、冷却しろ過を行うことにより、ロジン亜鉛塩のキシレン溶液(濃褐色透明液体、固形分50%)を得た。得られた溶液の加熱残分は、50.2%であった。
温度計、還流冷却器、及び攪拌機を備えたフラスコに、ハイペールCH(水添ガムロジン)240gとキシレン360gをフラスコに入れ、更に、前記ロジン中の樹脂酸が全て亜鉛塩を形成するように酸化亜鉛120gを加え、70~80℃で3時間、減圧下で還流脱水した。その後、濃縮、冷却しろ過を行うことにより、水添ロジン亜鉛塩のキシレン溶液(濃褐色液体、固形分65%)を得た。得られた溶液の加熱残分は、65.1%であった。
上記製造例で得られた共重合体溶液を用いて、実施例・比較例の防汚塗料組成物を表5~表10に示す配合により調製した。
亜酸化銅:商品名「NC-301」(日進ケムコ株式会社製)
銅ピリチオン:商品名「カッパーオマジン」(アーチケミカル株式会社製)
チオシアン酸銅(I):商品名「チオシアン酸銅(I)」(和光純薬工業株式会社製)
Zineb:商品名「ジネブ」(SIGMA-ALDRICH製)
SeaNine:商品名「Sea Nine211」4,5-ジクロロ-2-n-オクチル-3-イソチアゾロン(固形分30%キシレン溶液、ロームアンドハース社製)
Econea:商品名「Econea 028」2-(p-クロロフェニル)-3-シアノ-4-ブロモ-5-トリフルオロメチルピロール(ヤンセンPMP製)
medetomidine:商品名「4-(1-(2,3-Dimethylphenyl)ethyl)-1H-imidazole」(和光純薬工業株式会社製)
塩素化パラフィン:商品名「エンパラA-40S」(東ソー株式会社製)
トリメリット酸トリス(2-エチルヘキシル):商品名「トリメリット酸トリス(2-エチルヘキシル)」(東京化成工業株式会社製)
ロジン亜鉛塩溶液:製造例41で製造したものを使用
ガムロジン溶液:中国産ガムロジン(WW)の固形分50%キシレン溶液
水添ロジン溶液:商品名「ハイペールCH」(荒川化学工業株式会社製)の固形分50%キシレン溶液。
水添ロジン亜鉛塩溶液:製造例42で製造したものを使用
ベンガラ:商品名「ベンガラキンギョク」(森下弁柄工業株式会社製)
タルク:商品名「クラウンタルク3S」(松村産業株式会社製)
酸化亜鉛:商品名「酸化亜鉛2種」(正同化学工業株式会社製)
酸化チタン:商品名「FR-41」(古河機械金属株式会社製)
エチルシリケート28:テトラエトキシシラン:商品名「エチルシリケート28」(コルコート株式会社製)
無水石膏:「D-1」(株式会社ノリタケカンパニーリミテド製)
ディスパロンA603-20X:アマイド系チクソトロピック剤:商品名「ディスパロンA603-20X」(楠本化成株式会社製)
ディスパロン4200-20:酸化ポリエチレン系チクソトロピック剤:商品名「ディスパロン4200-20」(楠本化成株式会社製)
水槽の中央に直径515mm及び高さ440mmの回転ドラムを取付け、これをモーターで回転できるようにした。また、海水の温度を一定に保つための冷却装置、及び海水のpHを一定に保つためのpH自動コントローラーを取付けたロータリー試験機を2台用意した。
まず、チタン板(71×100×0.5mm)上に、防錆塗料(エポキシビニル系A/C)を乾燥後の厚みが約100μmとなるように塗布し乾燥させた。その後、実施例および比較例で得られた塗料組成物を、前期防錆塗膜上に、乾燥後の厚みが約200μmとなるよう塗布し、40℃で3日乾燥させることにより、試験板を用意した。試験板は同一のものを塗料組成物に対してそれぞれ2枚ずつ作製した。
作製した試験板を上記装置の回転装置の回転ドラムに海水と接触するように固定して、20ノットの速度で回転ドラムを回転させた。その間、海水の温度を25℃に、1台目はpHを7.7~7.9に保ち、2台目をpH8.0~8.2に保ち、二週間毎に海水を入れ換えた。
各試験板の初期の膜厚と6ヶ月後および9ケ月後の残存膜厚を株式会社キーエンス製の形状測定レーザマイクロスコープVK-X100で測定し、その差から溶解した塗膜厚を計算することにより塗膜溶解量を求めた。結果を表5~表10に示す。表中の数値は6ヶ月後および9ケ月後それぞれの時点での総溶解量である。
実施例および比較例で得られた防汚塗料組成物を、硬質塩ビ板(100×200×2mm)の両面に乾燥塗膜としての厚みが約200μmとなるよう塗布し室温で3日間乾燥させて試験板を作製した。この試験板を汚損生物の付着が非常に厳しい大阪湾、伊勢湾内の海面下2.0mに12ヶ月間浸漬して付着物による試験板の汚損を6ヶ月後および12ヶ月後に観察した。
評価は、塗膜表面の状態を目視観察することにより、以下の基準で判断した。結果を表5~表10に示す。
△:貝類、藻類などの汚損生物が部分的に付着したレベル
×:貝類、藻類などの汚損生物が全面に付着したレベル。
前記、試験例2と同じ試験板で同時に塗膜状態を観察し、以下の基準で判断した。結果を表5~表10に示す。
〇:塗膜に水ぶくれ、クラック、剥離等が認められない。
△:塗膜に水ぶくれが認められた。
×:塗膜に水ぶくれ、クラック、剥離等が認められた。
全ての実施例では、試験例1~3において良好な結果が得られた。
単量体(b)と(c)の一方のみを有する共重合体を用いた比較例1~8、及び単量体(a)の含有量が単量体(a)~(d)の合計質量に対して25~50質量%の範囲外である共重合体を用いた比較例9~11では、試験例1~3の少なくとも1つにおいて良好な結果が得られなかった。
Claims (1)
- 共重合体Pと、防汚薬剤を含有する防汚塗料組成物であって、
前記共重合体Pは、単量体(a)と、単量体(b)と、単量体(c)と、前記単量体(a)~(c)以外のエチレン性不飽和単量体(d)との共重合体であり、
前記単量体(a)は、一般式(1)で表され、
前記単量体(a)の含有量は、前記単量体(a)~(d)の合計質量に対して25~50質量%であり、
前記単量体(b)及び(c)は、それぞれ、n-オクタノール/水間の分配係数Pの常用対数logPが0.00~0.59、及び0.60~0.95の単量体であり、
前記単量体(c)は、不飽和結合を1つしか有さない単量体である、防汚塗料組成物。
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