WO2019198676A1 - 防汚塗料組成物 - Google Patents
防汚塗料組成物 Download PDFInfo
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- WO2019198676A1 WO2019198676A1 PCT/JP2019/015357 JP2019015357W WO2019198676A1 WO 2019198676 A1 WO2019198676 A1 WO 2019198676A1 JP 2019015357 W JP2019015357 W JP 2019015357W WO 2019198676 A1 WO2019198676 A1 WO 2019198676A1
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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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
-
- 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
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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, slimes, etc., become submarine structures such as vessels (especially the bottom of the ship), fishing nets, fishing net accessories, etc. and power plant conduits.
- 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).
- Patent Document 1 Even if the technology of Patent Document 1 is adopted, the dissolution of the coating film is secured to some extent under the seawater temperature from the normal temperature to the high temperature sea area. The soiling effect was not satisfactory. Moreover, after immersion in seawater, coating film abnormalities such as cracks may occur after a relatively short period of time, and further improvements are required.
- the present invention has been made in view of such circumstances, maintains a stable coating film dissolution rate over a long period of time in a low temperature sea area, and does not cause coating film abnormalities such as cracks, stable antifouling performance It is an object of the present invention to provide an antifouling paint composition capable of maintaining the above.
- an antifouling paint composition containing a copolymer A, a polymer B, and a plasticizer C
- the copolymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a)
- the monomer (a) is represented by the general formula (1),
- the content of the monomer (a) is 15 to 35% by mass with respect to the total mass of the monomer (a) and the monomer (b)
- the polymer B is a (meth) acrylic acid ester polymer other than the copolymer A, and has an antifouling coating composition having a weight average molecular weight of 20,000 to 100,000.
- R 1 is a methyl group
- R 2 to R 4 are the same or different and each represents a branched alkyl group having 3 to 8 carbon atoms or a phenyl group
- the antifouling paint composition of the present invention comprises a copolymer A, a polymer B, and a plasticizer C.
- Copolymer A is a copolymer of monomer (a) and ethylenically unsaturated monomer (b) other than monomer (a).
- Copolymer A includes monomer units derived from monomers (a) to (b).
- the monomer (a) is a triorganosilyl methacrylate monomer and is represented by the general formula (1). (Wherein R 1 is a methyl group, and R 2 to 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 branched alkyl group having 3 to 8 carbon atoms of R 2 to R 4 include isopropyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methyl Pentyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methyl Examples include heptyl group, 2-methylbutyl group, 2-ethylbutyl group, 2,2-dimethylpropyl group, cyclohexylmethyl group, 2-ethylhexyl group, 2-propylpentyl group, and 3-methylpentyl group.
- R2 to R4 are isopropyl group, s-butyl group, t-butyl group, phenyl group, and 2-ethylhexyl group. Particularly preferred are isopropyl group and 2-ethylhexyl group.
- Examples of the monomer (a) include triisopropylsilyl methacrylate, triisobutylsilyl methacrylate, tris-butylsilyl methacrylate, triisopentylsilyl methacrylate, triphenylsilyl methacrylate, diisopropylphenylsilyl methacrylate, methacrylic acid.
- Preferable examples include triisopropylsilyl methacrylate, tris-butylsilyl methacrylate, t-butyldiphenylsilyl methacrylate, tri-2-ethylhexylsilyl methacrylate and the like.
- These monomers (a) can be used alone or in combination of two or more.
- Monomer (b) is an ethylenically unsaturated monomer other than monomer (a), such as (meth) acrylic acid ester, vinyl compound, aromatic compound, dibasic acid dialkyl ester compound, etc. Is mentioned.
- (meth) acrylic acid ester means acrylic acid ester or methacrylic acid ester.
- (meth) acrylic acid esters examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, benzyl (meth) acrylate , Phenyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, propylene glycol monomethyl (meth) acrylate, 2-hydroxy (meth) acrylate Ethyl, 2-hydroxypropyl (meth) acrylate, (me
- vinyl compound examples include vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinyl pyrrolidone. It is done.
- aromatic compound examples include styrene, vinyl toluene, ⁇ -methyl styrene and the like.
- dibasic acid dialkyl ester compounds examples include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.
- these monomers (b) can be used alone or in combination of two or more.
- the monomer (b) is preferably a (meth) acrylic acid ester from the viewpoint of coating film properties, and particularly from the viewpoint of crack resistance, methyl methacrylate, butyl (meth) acrylate, (meth) acrylic.
- Isobutyl acid isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth More preferred are 2- (2-ethoxyethoxy) ethyl acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.
- the copolymer A is obtained by copolymerizing 15 to 35% by mass of the monomer (a) and 65 to 85% by mass of the monomer (b), and preferably the monomer (a) is 20%.
- the amount of the monomer (a) is 25% by mass to 35% by mass.
- the content of the monomer (a) is, for example, 15, 20, 25, 30, 35% by mass, and may be within a range between any two of the numerical values exemplified here. .
- the monomer (b) may contain a silyl ester other than the monomer (a) (acrylic acid silyl ester, methacrylic acid silyl ester other than the general formula (1)).
- the total silyl ester content with respect to the total mass of the monomer (a) and the monomer (b) is, for example, 15 to 50% by mass, specifically, for example, 15, 20, 25, 30 , 35, 40, 45, 50 mass%, and may be in a range between any two of the numerical values exemplified here.
- the content of the silyl ester other than the monomer (a) is preferably smaller than the content of the monomer (a), and is 1 ⁇ 2 or less of the content of the monomer (a). Is preferable, and it is more preferable that it is 1/5 or less.
- the coating film solubility is improved particularly in the low temperature sea area.
- the weight average molecular weight (Mw) of the copolymer A 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.
- Examples of the measuring method of Mw include gel permeation chromatography (GPC method).
- Copolymer A is a random copolymer of monomer (a) and monomer (b), an alternating copolymer, a periodic copolymer, or a block copolymer. May be.
- the copolymer A can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.
- polymerization initiator used in the polymerization reaction examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2 ′.
- -Azo compounds such as azobisisobutyrate, dibenzoyl peroxide, m-toluoyl peroxide, benzoyl m-methylbenzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxide Oxyisopropyl carbonate, tert-butyl peroctoate, tert-butyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1,3 , 3-tetramethylbutylperoxyneodecanoate, etc.
- polymerization initiators can be used alone or in combination of two or more.
- polymerization initiators include AIBN, dibenzoyl peroxide, m-toluoyl peroxide, benzoyl m-methylbenzoyl peroxide, tert-butyl peroctoate, and 1,1,3,3-tetramethylbutyl. Peroxy-2-ethylhexanoate is preferred.
- the molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.
- polymerization method examples include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization.
- solution polymerization or non-aqueous dispersion polymerization is preferable in that the copolymer A can be obtained easily and accurately.
- 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, octane and mineral spirit; ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, and the like.
- ester solvents examples include ester solvents; alcohol solvents such as isopropyl alcohol, butyl alcohol, and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether, and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
- alcohol solvents such as isopropyl alcohol, butyl alcohol, and propylene glycol monomethyl ether
- ether solvents such as dioxane, diethyl ether, and dibutyl ether
- ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
- aliphatic hydrocarbon solvents, ester solvents, alcohol solvents, and aromatic hydrocarbon solvents are preferable, and mineral spirit, butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, toluene,
- 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 70 to 140 ° C., preferably 80 to 130 ° C.
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.
- the polymer B is a (meth) acrylic acid ester polymer other than the copolymer A, and has a weight average molecular weight (Mw) of 20000 to 100,000 (GPC method).
- Polymer B may be a homopolymer of one type of monomer, but is preferably a copolymer of a plurality of types of monomers.
- the monomer that forms the polymer B includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, (meth) acrylic acid 4-methoxybutyl, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, propylene
- 2- (2-ethoxyethoxy) ethyl acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like are preferable.
- monomers that can be polymerized with the above monomers include, for example, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, Examples thereof include lauryl vinyl ether and N-vinyl pyrrolidone.
- aromatic compound examples include styrene, vinyl toluene, ⁇ -methyl styrene and the like.
- Dialkyl ester compounds of dibasic acids include dimethyl maleate, dibutyl maleate, dimethyl fumarate and the like.
- Examples of other ethylenically unsaturated compounds include ethylene, allyl alcohol, allyl glycidyl ether, (meth) acrylic acid, and the like. From the viewpoint of production cost and raw material availability, styrene, vinyl acetate, ( (Meth) acrylic acid and the like are preferred.
- the weight average molecular weight of the polymer B is 20000 to 100,000 (GPC method), preferably 20000 to 60000 (GPC method), and more preferably 20000 to 50000 (GPC method).
- the Mw is, for example, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, or 100,000, and may be within a range between any two of the numerical values exemplified here.
- the weight average molecular weight of the polymer B can be adjusted by appropriately setting the type and amount of the initiator and the reaction temperature as described above for the copolymer A.
- the crack resistance and adhesion particularly in a low temperature sea area are good.
- the content of the polymer B in the composition of the present invention is not particularly limited, but the content ratio with the copolymer A is a mass ratio (copolymer A / polymer B) in terms of solid content, usually 0. 0.01 to 15, preferably 0.05 to 10, and more preferably 0.1 to 5.
- the contents of the copolymer A and the polymer B are within the above range, the effect of improving the crack resistance and the coating film solubility in the low temperature sea area of the coating film comprising the coating composition of the present invention remarkably appears.
- Plasticizer C As the plasticizer C, for example, Chlorinated paraffin, Vegetable oil plasticizers such as linseed oil, epoxidized linseed oil, soybean oil, epoxidized soybean oil, Di-n-octyl phthalate, di-2-ethylhexyl phthalate, isononyl phthalate, diisodecyl phthalate, diisononyl 2,5-furandicarboxylate, diethyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, di-2 terephthalate -Aromatic diesters such as ethylhexyl, Aromatic triester plasticizers such as tributyl trimellitic acid, tri-2-ethylhexyl trimellitic acid, Aromatic tetraester plasticizers such as pyromellitic acid tetra-2-ethylhe
- Fatty acid ester plasticizers such as di-2-ethylhexyl succinate, di-2-butoxyethyl adipate, diisononyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate, Hydroxycarboxylic acid ester plasticizers such as tributyl citrate, acetyl triethyl citrate, tri-2-ethylhexyl acetyl citrate, Polyethylene alcohol diesters such as diethylene glycol dibutyl ether, triethylene glycol diacetate, diethylene glycol dibenzoate, triethylene glycol di (2-ethylhexanoate), propylene glycol dilaurate, monoolein, triacetin, tributyrin, etc., Decyl decanoate, geranyl acetate, isopropyl myristate, isopropyl palmitate,
- chlorinated paraffin, vegetable oil, aliphatic ester, and aromatic ester are preferable from the viewpoint of availability, and chlorinated paraffin and epoxidized soybean oil are particularly preferable from the viewpoint of crack resistance in low-temperature seawater.
- Diisononyl phthalate, diisononyl 1,2-cyclohexanedicarboxylate, di-2-ethylhexyl terephthalate, and tri-2-ethylhexyl trimellitic acid are more preferable, and chlorinated paraffin is more preferable in terms of cost.
- the content of the plasticizer in the composition of the present invention is not particularly limited, but is usually 0.01% by mass to 30% by mass in terms of solid content, and preferably 0.05 from the viewpoint of paint viscosity and coating film hardness.
- the content is from 25% by mass to 25% by mass, and more preferably from 0.1% by mass to 20% by mass.
- 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 paint resin of the present invention includes, if necessary, a copolymer other than copolymer A and polymer B, a resin component, an elution regulator, a pigment, a dye, an antifoaming agent, Add dehydrating agent, thixotropic agent, organic solvent, etc. to make antifouling paint
- copolymers and resin components other than copolymer A and polymer B include, for example, (meth) acrylic resins, polyester resins, vinyl resins, petroleum resins, metal-containing resins other than copolymer A and polymer B,
- the resin include a zwitterionic compound and a silicone resin.
- the elution regulator include monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof, and the like. Examples thereof include a salt or the alicyclic hydrocarbon resin.
- rosin derivatives include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
- alicyclic hydrocarbon resin examples include Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.) and the like as commercially available products. Among these, rosin, rosin derivatives, naphthenic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, or metal salts thereof are preferable.
- dehydrating agent examples include synthetic zeolite-based adsorbents, 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 using, for example, a mixed liquid containing the copolymer A, polymer B, plasticizer C and other additives, using a disperser. Can be produced by mixing and 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 disperser for example, one that can be used as a fine pulverizer can be suitably used.
- 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, 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 ... 40 ° C Eluent: THF
- the heating residue is a value measured according to JIS K 5601-1-2: 1999 (ISO 3251: 1993) “Paint component test method—heating residue”.
- the obtained polymer solution had a viscosity of 660 mPa ⁇ s (25 ° C.), a heating residue of 50.2%, and an Mw of 76,000.
- Examples 1 to 44 and Comparative Examples 1 to 8 Manufacture of coating compositions
- the components shown in Tables 3 to 9 were blended in the proportions (mass%) shown in these tables, and were mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to produce coating compositions.
- Example 1 (Rotary Test)> A rotating drum having a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and an automatic pH controller for keeping the pH of the seawater constant were attached.
- a test plate was prepared according to the following method. First, on a titanium plate (71 x 100 x 0.5 mm), a rust preventive paint (epoxy vinyl A / C) is applied so that the thickness after drying is about 100 ⁇ m and dried to form a rust preventive coating. did.
- the coating compositions obtained in Examples and Comparative Examples were each applied on the rust-proof coating film so that the thickness after drying was about 500 ⁇ m.
- the obtained coated material was dried at 40 ° C. for 3 days to prepare a test plate having a dry coating film having a thickness of about 500 ⁇ m.
- One of the produced test plates was fixed to the rotating drum of the rotating device of the apparatus so as to contact seawater, and the rotating drum was rotated at a speed of 20 knots. Meanwhile, the temperature of the seawater was maintained at 15 ° C. and the pH at 8.0 to 8.2, and the seawater was replaced every week.
- the initial film thickness of each test plate and the remaining film thickness after every 6 months were measured with a laser focus displacement meter, and the dissolved film thickness was calculated from the difference to determine the coating film dissolution amount.
- the amount of coating film dissolved was expressed as the amount of coating film dissolved per month ( ⁇ m / month).
- ⁇ When there is no abnormality ⁇ : Less than 10% of the total surface area of the coating film, and hair cracks are observed ⁇ : Hair cracking is observed in 10 to 30% of the total surface area of the coating film ⁇ : Surface of the coating film Hair cracks can be seen in more than 30% of the total area.
- XX Large cracks, blisters or peelings (only the surface of the coating film or part of the edge is peeled off), peeling (the whole coating film is peeled off, test coating) Abnormality is seen in the paint film such as no film remaining)
- Rosin zinc salt solution The one produced in Production Example 24 is used.
- Hydrogenated rosin solution a 50% solid content xylene solution of trade name “Hyper CH” (manufactured by Arakawa Chemical Industries, Ltd.).
- Rosin solution Chinese gum rosin (WW) 50% solids xylene solution
- NT-RMZ Hydrogenated rosin zinc salt solution: Trade name “NT-RMZ” (manufactured by Nitto Kasei Co., Ltd.) is used.
- Trimethylisobutenyl cyclohexene carboxylic acid solution Use the one produced in Production Example 25.
- Bengala Trade name “TODA COLOR EP-13D” (manufactured by Toda Pigment Corporation)
- Talc Trade name “Crown Talc 3S” (Matsumura Sangyo Co., Ltd.)
- Zinc oxide Trade name “Zinc oxide 2” (manufactured by Shodo Chemical Co., Ltd.)
- Titanium oxide Trade name “FR-41” (Furukawa Machine Metal Co., Ltd.)
- Tetraethoxysilane Trade name “Tetraethyl Orthosilicate” (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Anhydrite Trade name “D-1” (manufactured by Noritake Company Limited)
- Aliphatic amide type thixotropic agent Trade name “Disparon A603-20X” (manufactured by Enomoto Kasei Co., Ltd.)
- Denatured alcohol Trade name “Clin Ace High” (manufactured by Imazu)
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Abstract
Description
このような問題を防ぐために、船舶等に防汚塗料組成物を塗布して防汚塗膜を形成し、防汚塗膜から防汚薬剤を徐放させることによって、長期間に渡って防汚性能を発揮させる技術が知られている(特許文献1)。
前記共重合体Aは、単量体(a)と、前記単量体(a)以外のエチレン性不飽和単量体(b)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)と前記単量体(b)の合計質量に対して15~35質量%であり、
前記重合体Bは、前記共重合体A以外の(メタ)アクリル酸エステル重合体であって、重量平均分子量が20000~100000である、防汚塗料組成物が提供される。
本発明の防汚塗料組成物は、共重合体Aと、重合体Bと、可塑剤Cを含有する。
共重合体Aは、単量体(a)と、単量体(a)以外のエチレン性不飽和単量体(b)との共重合体である。共重合体Aは、単量体(a)~(b)に由来する単量体単位を含む。
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(b)は、単量体(a)以外のエチレン性不飽和単量体であり、例えば、(メタ)アクリル酸エステル、ビニル化合物、芳香族化合物、二塩基酸のジアルキルエステル化合物等が挙げられる。なお、本明細書において、(メタ)アクリル酸エステルは、アクリル酸エステル、又はメタアクリル酸エステルを意味する。
重合開始剤の使用量を適宜設定することにより、共重合体Aの分子量を調整することができる。
重合体Bは、共重合体A以外の(メタ)アクリル酸エステル重合体であり、重量平均分子量(Mw)が20000~100000(GPC法)である。
可塑剤Cとして、例えば、
塩素化パラフィン、
亜麻仁油、エポキシ化亜麻仁油、大豆油、エポキシ化大豆油等の植物油系可塑剤、
フタル酸ジn-オクチル、フタル酸ジ2-エチルヘキシル、フタル酸イソノニル、フタル酸ジイソデシル、2,5-フランジカルボン酸ジイソノニル、イソフタル酸ジエチル、イソフタル酸ジ2-エチルヘキシル、テレフタル酸ジエチル、テレフタル酸ジ2-エチルヘキシル等の芳香族ジエステル系、
トリメリット酸トリブチル、トリメリット酸トリ2-エチルヘキシル等の芳香族トリエステル系可塑剤、
ピロメリット酸テトラ2-エチルヘキシル等の芳香族テトラエステル系可塑剤、
4-シクロヘキセン-1,2-ジカルボン酸ジ2-エチルヘキシル、1,2-シクロヘキサンジカルボン酸ジイソノニル、1,3-シクロヘキサンジカルボン酸ジイソノニル、1,4-シクロヘキサンジカルボン酸ジイソノニル、4,5-エポキシシクロヘキサン-1,2-ジカルボン酸ジ2-エチルヘキシル、4,5-エポキシシクロヘキサン-1,2-ジカルボン酸ジステアリル、4,5-エポキシシクロヘキサン-1,2-ジカルボン酸ジエポキシステアリル等の脂環式エステル系可塑剤、
コハク酸ジ2-エチルヘキシル、アジピン酸ジ2-ブトキシエチル、アジピン酸ジイソノニル、アゼライン酸ジ2-エチルヘキシル、セバシン酸ジ2-エチルヘキシル等の脂肪酸エステル系可塑剤、
クエン酸トリブチル、アセチルクエン酸トリエチル、アセチルクエン酸トリ2-エチルヘキシル等のヒドロキシカルボン酸エステル系可塑剤、
ジエチレングリコールジブチルエーテル、トリエチレングリコールジアセテート、ジエチレングリコールジベンゾエート、トリエチレングリコールジ(2-エチルヘキサノエート)、プロピレングリコールジラウレート、モノオレイン、トリアセチン、トリブチリン、等の多価アルコールエーテル・エステル系可塑剤、
デカン酸デシル、酢酸ゲラニル、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、イソ吉草酸ベンジル、アセト酢酸ベンジル、n-オクタン酸 p-トリル、7,8-エポキシステアリン酸ベンジル、9,10-エポキシステアリン酸オクチル、ステアリン酸セチル、フェニル酢酸イソアミル、2-エチルヘキシルベンゾエート、4-ヒドロキシ安息香酸ヘキシル、3,4-エポキシシクロヘキシルメチル 3,4-エポキシシクロヘキサンカルボキシラート、3,7-ジメチル-6-オクテン-1-オールアセタート、テルピニルアセテート、4-tert-ブチルシクロヘキシルアセテート、メンチルアセテート、イソボルニルアセテート、イソボルニルエチレート、イソボルニルステアレート、ジヒドロジャスモン酸メチル、3,4-エポキシシクロヘキサンカルボン酸3,4-エポキシシクロヘキシルメチル、フルフリルアセテート、テトラヒドロフルフリルアセテート、エチル2-フランカルボキシレート、プロピオン酸テトラヒドロフルフリル、n-オクチル2-フランカルボキシレート、イソアミル2-フランカルボキシレート等のモノエステル系可塑剤、
リン酸トリメチル、リン酸トリクレジル等のリン酸エステル系可塑剤、
ルトナールM40、ルトナールA25等のポリビニルアルキルエーテル系可塑剤、
ポリエステル系可塑剤、
樟脳、テルペンフェノール、t-ノニルペンタスルフィド等
が挙げられる。これらは単独又は2種以上で使用できる。
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。
有機薬剤としては、例えば、2-メルカプトピリジン-N-オキシド銅(一般名:カッパーピリチオン)、2-メルカプトピリジン-N-オキシド亜鉛(一般名:ジンクピリチオン)、ジンクエチレンビスジチオカーバメート(一般名:ジネブ)、4,5-ジクロロ-2-n-オクチル-3-イソチアゾロン(一般名:シーナイン211)、3,4-ジクロロフェニル-N-N-ジメチルウレア(一般名:ジウロン)、2-メチルチオ-4-t-ブチルアミノ-6-シクロプロピルアミノ-s-トリアジン(一般名:イルガロール1051)、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(一般名:Econea28)、4-[1-(2,3-ジメチルフェニル)エチル]-1H-イミダゾール(一般名:メデトミジン)等が挙げられる。
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、共重合体A及び重合体B以外の共重合体や樹脂成分、溶出調整剤、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。
この中でもロジン、ロジン誘導体、ナフテン酸、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、又はこれらの金属塩が好ましい。
前記脱水剤としては、例えば、合成ゼオライト系吸着剤、オルソエステル類、テトラメトキシシラン、テトラエトキシシラン等のシリケート類やイソシアネート類、カルボジイミド類、カルボジイミダゾール類等が挙げられる。これらは単独または2種以上を組み合わせて使用することができる。
本発明の防汚塗料組成物は、例えば、前記共重合体A、重合体B、可塑剤C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、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。
<製造例1(共重合体A溶液の製造_A-1)>
温度計、還流冷却器、撹拌機及び滴下ロートを備えたフラスコに、キシレン260gを仕込み、窒素雰囲気下、85±5℃で攪拌しながら、メタクリル酸トリイソプロピルシリル175g、メタクリル酸メチル175g、アクリル酸n-ブチル25g、メタクリル酸イソブチル25g、アクリル酸2-メトキシエチル75g、メタクリル酸2-メトキシエチル25g、及び重合開始剤である1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート3gの混合液を2時間かけて滴下した。その後同温度で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-エチルヘキサノエート0.5gを1時間毎に5回添加して重合反応を完結した後、キシレン235gを添加し溶解させることにより、共重合体溶液A-1を得た。得られた共重合体溶液の粘度は560mPa・s(25℃)、加熱残分は49.6%、Mwは49,000であった。
表1に示す有機溶剤、反応温度、単量体及び重合開始剤をそれぞれ記載量用いて、製造例1と同様の操作で重合を行い、共重合体溶液A-2~A-8を得た。得られた各共重合体溶液の加熱残分、粘度、及び重量平均分子量を測定した。結果を表1に示す。
表1に示す有機溶剤、反応温度、単量体及び重合開始剤をそれぞれ記載量用いて、製造例1と同様の操作で重合を行い、共重合体溶液E-1、E-2を得た。得られた各共重合体溶液の加熱残分、粘度、及び重量平均分子量を測定した。結果を表1に示す。
<製造例11~20(重合体B溶液の製造_B-1~B-10)>
表2に示す有機溶剤、反応温度、単量体及び重合開始剤をそれぞれ記載量用いて、製造例1と同様の操作で重合を行い、重合体溶液B-1~B-10を得た。得られた各重合体溶液の加熱残分、粘度、及び重量平均分子量を測定した。結果を表2に示す。
温度計、還流冷却器、撹拌機及び滴下ロートを備えたフラスコに、ミネラルスピリット450gを仕込み、窒素雰囲気下、95~105℃で撹絆しながら、メタクリル酸n-ブチル500g、アクリル酸2-エチルヘキシル500g、及び重合開始剤であるt-ブチルパーオキシオクトエート3gの混合液を95~105℃に保ちながら、3時間かけて滴下した。滴下後、95~105℃に保ちながらt-ブチルパーオキシオクトエート2.5gを30分毎に2回添加後、更に2時間攪拌した後、ミネラルスピリット550gで希釈し、分散安定剤を得た。得られた重合体溶液の粘度は、660mPa・s(25℃)、加熱残分は50.2%、Mwは76,000であった。
温度計、還流冷却器、撹拌機及び滴下ロートを備えたフラスコに、分散安定剤(製造例21で製造したもの)133.4gを仕込み、窒素雰囲気下、100~110℃で撹絆しながら、メタクリル酸メチル16g、アクリル酸エチル7.2g、メタクリル酸10.2g、及び重合開始剤であるナイパーBMT-K40(ベンゾイル/m-トルオイルパーオキサイドの40%キシレン溶液、日本油脂(株)製)
を0.8gの混合液を100~110℃に保ちながら、3時間かけて滴下した。滴下後、100~110℃に保ちながらナイパーBMT-K40を0.2g、30分毎に2回添加後、更に2時間攪拌した後、ミネラルスピリット32gで希釈し、B-9を得た。得られた重合体溶液の粘度は、980mPa・s(25℃)、加熱残分は50.4%、Mwは68,000であった。
温度計、還流冷却器、撹拌機及び滴下ロートを備えたフラスコに、キシレン500gを仕込み、窒素雰囲気下、125~130℃で撹絆しながら、メタクリル酸メチル50g、アクリル酸n-ブチル120g、アクリル酸2一メトキシエチルアクリレート330g、及び重合開始剤であるt-ブチルパーオキシオクトエート15g、連鎖移動剤であるノフマーMSD(日本油脂(株)製)1gの混合液を125~130℃に保ちながら滴下した。滴下後、125~130℃に保ちながらt-ブチルパーオキシオクトエート1gを1時間毎に3回添加後、更に2時間攪拌しE-3を得た。得られた共重合体溶液の粘度は、60mPa・s(25℃)、加熱残分は52.4%、Mwは9,500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、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、50.4%であった。
温度計、還流冷却器、及び撹拌機を備えたフラスコに、アロオシメン320g、メタクリル酸175g及びMEHQ0.17gを入れ、35~45℃で24時間加熱攪拌した。その後、減圧下で未反応の原料を留去し、褐色粘調性のトリメチルイソブテニルシクロヘキセンカルボン酸73gを得た。これにキシレンを加え、トリメチルイソブテニルシクロヘキセンカルボン酸溶液(固形分50%)とした。
表3~表9に示す成分をこれらの表に示す割合(質量%)で配合し、直径1.5~2.5mmのガラスビーズと混合分散することにより塗料組成物を製造した。
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。
試験板を下記の方法に従って作製した。
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となるよう塗布し乾燥させることにより防錆塗膜を形成した。その後、実施例及び比較例で得られた塗料組成物を、それぞれ前記防錆塗膜の上に、乾燥後の厚みが約500μmとなるよう塗布した。得られた塗布物を40℃で3日間乾燥させることにより、厚みが約500μmの乾燥塗膜を有する試験板を作製した。
作製した試験板のうちの一枚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15℃、pHを8.0~8.2に保ち、一週間毎に海水を入れ換えた。
各試験板の初期の膜厚と毎6ケ月後の残存膜厚をレーザーフォーカス変位計で測定し、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。塗膜溶解量は、1ヶ月あたりの塗膜溶解量(μm/月)で表した。
ロータリー試験の12ヶ月後、24ヶ月後の試験板を乾燥後、各塗膜表面を肉眼観察し、塗膜の状態を評価した。評価は以下の方法で行った。
○ :塗膜表面全面積の1割未満、ヘアークラックが見られるもの
△ :塗膜表面全面積の1~3割に、ヘアークラックが見られるもの
× :塗膜表面全面積の3割以上に、ヘアークラックが見られるもの
××:大きなクラック、ブリスター又はハガレ(塗膜の表面のみや端の一部が剥がれる事)、剥離(塗膜全体が剥がれて、試験塗膜が残っていない状態)などの塗膜に異常が見られるもの
試験例1および2により、共重合体A、重合体B、可塑剤Cの三つの成分を含有する防汚塗膜が、15℃の海水中で、24ヶ月塗膜異常などを起こすことなく、良好な塗膜溶解性を示す事が明らかになった(実施例1等より)。この効果は本特許の必須三成分の内、いずれの成分が欠けても失われ、塗膜溶解量が減少し、24ヶ月後には、大きなクラックやハガレなどの塗膜異常が起こった(比較例1~3より)。
また、共重合体A中のトリオルガノシリル単量体成分割合が本発明の範囲を超えて、過剰に含まれた場合、共重合体Aと類似の構造であっても、溶解性が著しく低下することが判明した(比較例4、5より)。加えて、共重合体A中のトリオルガノシリル単量体成分割合が、本発明の範囲内であっても、メタクリル酸トリオルガノシリルの代替として、アクリル酸トリオルガノシリルを用いた場合、溶解性はあるものの、溶解安定性と耐クラック性が失われた(比較例6、7)。さらに、重合体Bと類似の(メタ)アクリルエステル共重合体であっても、Mwが小さい共重合体を重合体Bの代わりに使用した場合は、防汚塗膜が剥離するという不具合が発生した(比較例8)。
本発明の範囲内であれば、共重合体A、及び重合体Bは多様なモノマー組成が適用でき(表5及び表6)、また可塑剤についても種々の可塑剤が使用可能である事が分かる(表3より)。
また、共重合体A、重合体B、及び可塑剤を適切な量含有すれば、防汚薬剤や顔料成分、溶質調整剤成分などの配合量や種類を変更しても本効果を発揮できる事を見出した(表7~表9より)。
塩素化パラフィン:商品名「Paraffin Chlorinated (Cl:40%)」(和光純薬工業(株)製)
トヨパラックスA50:商品名「トヨパラックスA50」(東ソー(株)製)
E-2000H:エポキシ化大豆油:商品名「サンソサイザー E-2000H」(新日本理化(株)製)
ルトナールA25:商品名「Lutonal(登録商標) A25」(BASF社製)
DINP:フタル酸ジイソノニル:商品名「フタル酸ジイソノニル」(和光純薬工業(株)製)
DINCH:1,2-シクロヘキサンジカルボン酸ジイソノニル:商品名「HEXAMOLL(登録商標) DINCH(登録商標)」(BASF社製)
DEHT:テレフタル酸ジ2-エチルヘキシル:商品名「Bis(2-ethylhexyl) terephthalate」(SIGMA-ALDRICH社製)
TOTM:トリメリット酸トリ2-エチルヘキシル:商品名「Tris(2-ethylhexyl) Trimellitate」(東京化成(株)製)
ATBC:アセチルクエン酸トリブチル:商品名「Tributyl O-Acetylcitrate」(東京化成(株)製)
亜酸化銅:商品名「NC-301」(日進ケムコ(株)製)
ロダン銅:商品名「チオシアン酸銅(I)」(SIGMA-ALDRICH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)製)
亜鉛ピリチオン:商品名「ジンクオマジン」(アーチケミカル(株)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(2H)イソチアゾリン(固形分30%キシレン溶液、ロームアンドハース社製)
Econia: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) 製)
ロジン亜鉛塩溶液:製造例24で製造したものを使用
水添ロジン溶液:商品名「ハイペールCH」(荒川化学工業(株)製)の固形分50%キシレン溶液。
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
NT-RMZ:水添ロジン亜鉛塩溶液:商品名「NT-RMZ」(日東化成(株)製)を使用。固形分65%。
トリメチルイソブテニルシクロヘキセンカルボン酸溶液:製造例25で製造したものを使用。
ベンガラ:商品名「TODA COLOR EP-13D」(戸田ピグメント(株)製)
タルク:商品名「クラウンタルク3S」(松村産業(株)製)
酸化亜鉛:商品名「酸化亜鉛2」(正同化学(株)製)
酸化チタン:商品名「FR-41」(古河機械金属(株)製)
テトラエトキシシラン:商品名「Tetraethyl Orthosilicate」(東京化成(株)製)
無水石膏:商品名「D-1」(ノリタケカンパニーリミテド(株)製)
脂肪族アマイド系揺変剤:商品名「ディスパロンA603-20X」(楠本化成(株)製)
変性アルコール:商品名「クリンエース・ハイ」(今津薬品工業(株)製)
Claims (2)
- 前記可塑剤Cが、塩素化パラフィンを含有する請求項1に記載の防汚塗料組成物。
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JP2019528601A JP6647654B1 (ja) | 2018-04-12 | 2019-04-08 | 防汚塗料組成物 |
SG11202009384RA SG11202009384RA (en) | 2018-04-12 | 2019-04-08 | Antifouling coating composition |
KR1020207032612A KR20200143448A (ko) | 2018-04-12 | 2019-04-08 | 방오 도료 조성물 |
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US11472967B1 (en) | 2021-05-19 | 2022-10-18 | Nippon Paint Marine Coatings Co., Ltd. | Antifouling coating composition and coating film |
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KR20200143448A (ko) | 2020-12-23 |
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