WO2016063789A1 - 防汚塗料組成物用共重合体、防汚塗料組成物、防汚塗膜 - Google Patents
防汚塗料組成物用共重合体、防汚塗料組成物、防汚塗膜 Download PDFInfo
- Publication number
- WO2016063789A1 WO2016063789A1 PCT/JP2015/079173 JP2015079173W WO2016063789A1 WO 2016063789 A1 WO2016063789 A1 WO 2016063789A1 JP 2015079173 W JP2015079173 W JP 2015079173W WO 2016063789 A1 WO2016063789 A1 WO 2016063789A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating film
- copolymer
- antifouling
- monomer
- mass
- Prior art date
Links
Classifications
-
- 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
- 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
-
- 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
-
- 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
-
- 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
- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
-
- 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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
-
- 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
- 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
- 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
- C08F230/085—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 the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
Definitions
- the present invention relates to a copolymer for an antifouling paint composition, an antifouling paint composition, and an antifouling coating film.
- 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.
- Triorganosilyl group-containing copolymers and metal-containing copolymers with low toxicity and low environmental impact have been developed and used in antifouling paints since the ban on the use of conventionally used organotin-containing copolymers. I came.
- triorganosilyl group-containing copolymer use of a tri-n-butylsilyl ester-containing copolymer, a triphenylsilyl ester-containing copolymer, or a triisopropylsilyl ester-containing copolymer has been studied (patents). References 1-6). Further, various studies have been made on the metal-containing copolymer such as a zinc-containing copolymer and a copper-containing copolymer (Patent Documents 7 to 10).
- the dissolution rate in seawater at the initial stage is very large, and after a long period of time, the dissolution rate of the coating film becomes too small, and the coating design There is a problem that is difficult. Further, as the dissolution rate decreases, long-term antifouling performance may not be maintained.
- the present invention is specific for forming a highly environmentally safe antifouling coating film that maintains stable coating film solubility and antifouling performance for a long period of time in seawater and is unlikely to cause coating film abnormalities such as cracks. It is an object to provide a copolymer for an antifouling coating composition having a structure.
- the present inventor has found that a monomer mixture obtained by mixing a triorganosilyl group-containing polymerizable monomer and a metal-containing polymerizable monomer at a specific ratio.
- the present inventors have found that the polymer can compensate for the respective drawbacks and solve the above problems, and have completed the present invention. That is, the present invention includes (a) 10 to 25% by mass of a triorganosilyl group-containing monomer represented by the following general formula (I), and (b) represented by the following general formula (II) or (III).
- the present invention provides a copolymer for an antifouling coating composition comprising a copolymer obtained by copolymerization.
- the slow dissolution rate in seawater at the initial stage and the use of the metal-containing copolymer are used. It is possible to compensate for the slow dissolution rate of the antifouling paint coating film in the latter half and to maintain a stable coating film dissolution rate over a long period of time.
- the antifouling paint composition of the present invention contains a copolymer A for an antifouling paint composition.
- Copolymer A for the antifouling coating composition of the present invention comprises: (A) 10-25% by mass of a triorganosilyl group-containing monomer represented by the following general formula (I), (B) 2 to 10% by mass of at least one metal-containing polymerizable monomer represented by the following general formula (II) or (III), and (c) the monomers (a) and (b) 65-88% by mass of ethylenically unsaturated monomer other than A copolymer for an antifouling coating composition, comprising a copolymer obtained by copolymerizing the above.
- the monomer (a) is preferably 15 to 20% by mass.
- the monomer (b) is preferably 4 to 7% by mass, and the mass ratio represented by the monomer (a) / monomer (b) is preferably 2 or more.
- R 1 is a group selected from a hydrogen atom or a methyl group
- R 2 to R 4 are all groups selected from an alkyl group and an aryl group, and are the same group as each other). Or a different group.
- R 5 is a group selected from a hydrogen atom or a methyl group
- M represents a metal atom of Mg, Zn, or Cu
- R 6 represents an organic acid residue.
- R 7 and R 8 are groups selected from a hydrogen atom or a methyl group, and M represents a metal atom of Mg, Zn, or Cu.
- Copolymer A comprises monomer (a) 10 to 25% by mass, monomer (b) 2 to 10% by mass, and ethylenically unsaturated monomers other than the monomers (a) and (b). It is obtained by copolymerizing 65 to 88% by mass of the monomer (c).
- Copolymer A By using Copolymer A, the dissolution rate of the coating film in seawater and the water permeability to the coating film can be balanced, and the formation of a swelling layer can be suppressed, and stable surface renewability can be maintained over a long period of time. The desired antifouling effect can be effectively exhibited. Moreover, the recoat performance which was excellent in the coating film can be exhibited.
- the alkyl group or aryl group represented by R 2 to R 4 has, for example, 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
- Examples of the alkyl group or aryl group include a methyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, cyclohexyl group, and phenyl group.
- a triisopropyl group, a tri-n-butyl group, and a triphenyl group are preferable from the viewpoint of production cost and raw material availability / reason, and a triisopropyl group is particularly preferable.
- Examples of the monomer (a) include triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, and triphenylsilyl (meth) acrylate.
- the production process, production cost, and raw material acquisition Triisopropylsilyl (meth) acrylate is preferable from the viewpoints of ease, environmental safety, and physical properties of the coating film.
- These monomers (a) can be used alone or in combination of two or more.
- the monomer (b) is composed of one or more monomers represented by the general formula (II) or (III).
- examples of the metal atom represented by M include zinc, magnesium, and copper.
- the carbon number of the organic acid residue represented by R 6 is, for example, 6-20, preferably 7-15, and more preferably 7-12.
- examples of the organic acid include versatic acid, octylic acid, lauric acid, stearic acid, naphthenic acid, and the like.
- Versatic acid is preferable from the viewpoint of availability of raw materials and physical properties of the coating film.
- Examples of the compound represented by the formula (II) include zinc versatate (meth) acrylate, magnesium versatate (meth) acrylate, copper versatate (meth) acrylate, zinc octylate (meth) acrylate, and magnesium octylate ( (Meth) acrylate, copper octylate (meth) acrylate, zinc laurate (meth) acrylate, magnesium laurate (meth) acrylate, copper laurate (meth) acrylate, zinc stearate (meth) acrylate, magnesium stearate (meth) Examples thereof include acrylate, copper stearate (meth) acrylate, zinc naphthenate (meth) acrylate, magnesium naphthenate (meth) acrylate, and copper naphthenate (meth) acrylate.
- zinc versatate (meth) acrylate in particular, from the viewpoints of production process, production cost, raw material availability, environmental safety, and coating film physical properties, zinc versatate (meth) acrylate, copper versatate (meth) acrylate, zinc ( (Meth) acrylate and copper (meth) acrylate are preferred. These can be used alone or in combination of two or more.
- Examples of the monomer (c) include (meth) acrylate compounds, vinyl compounds, aromatic compounds, dialkyl ester compounds of dibasic acids, and the like.
- Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl ( (Meth) acrylate, 4-methoxybutyl (meth) acrylate, polyethylene glycol methyl ether (meth) acrylate, 2-hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, poly Examples include caprolactone-modified hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and acrylamide.
- 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.
- Dialkyl ester compounds of dibasic acids include dimethyl maleate, dibutyl maleate, dimethyl fumarate and the like.
- the monomer (c) is preferably (meth) acrylate, more preferably methyl methacrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, or the like, from the viewpoint of coating film properties / reasons.
- These monomers (c) can be used alone or in combination of two or more.
- a preferred embodiment of the copolymer A contained in the composition of the present invention is at least one monomer (a) selected from triisopropylsilyl (meth) acrylate, zinc versatate (meth) acrylate, versatic acid From at least one monomer (b) selected from copper (meth) acrylate, zinc (meth) acrylate, and copper (meth) acrylate, and methyl methacrylate, butyl (meth) acrylate, and 2-methoxyethyl (meth) acrylate It is a copolymer with at least one monomer (c) selected.
- the weight average molecular weight (Mw) of the copolymer A is preferably 2,000 to 100,000, and particularly preferably 4,000 to 50,000.
- Mw is from 2,000 to 100,000, the coating film does not become brittle and the coating film is moderately dissolved, so that a desired antifouling effect can be effectively exhibited.
- Examples of the method for measuring Mw include gel permeation chromatography (GPC).
- Copolymer A is any of random copolymer, alternating copolymer, periodic copolymer, or block copolymer of monomer (a), monomer (b) and monomer (c). The copolymer may be used.
- the copolymer A can be obtained, for example, by polymerizing the monomer (a), the monomer (b) and the monomer (c) in the presence of a polymerization initiator.
- the same polymerization initiators as those exemplified above can be used alone or in combination of two or more.
- the polymerization initiator AIBN and t-butylperoxy 2-ethylhexanoate are particularly preferable.
- the molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used. At this time, a chain transfer agent such as mercaptan or ⁇ -methylstyrene dimer can also be used.
- Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like.
- the solution polymerization is particularly preferable because the copolymer A can be obtained simply 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 and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; isopropyl
- examples include alcohol solvents such as 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.
- xylene, butyl alcohol, and propylene glycol monomethyl ether are 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 70 to 140 ° C., preferably 80 to 120 ° 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 8 hours.
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.
- the content of copolymer A in the composition of the present invention is not particularly limited, but is usually 20 to 70% by mass, preferably 40 to 60% by mass, based on the solid content of the composition of the present invention.
- the content of the copolymer A is 20% by mass to 70% by mass, the formation of the swelling layer can be suppressed by balancing the dissolution rate of the coating film in seawater and the water permeability to the coating film. Long-term stable surface renewability can be maintained, and a desired antifouling effect can be effectively exhibited. Moreover, the recoat performance which was excellent in the coating film can be exhibited.
- antifouling agent B In addition to copolymer A, antifouling agent B, elution regulator C, plasticizer D, other resin E, and the like can be blended with the antifouling coating composition of the present invention, if necessary. Thereby, the outstanding antifouling effect can be exhibited.
- the antifouling agent B is not particularly limited as long as it is a substance having a killing or repelling action against a marine fouling organism.
- medical agent are mentioned.
- inorganic agents include cuprous oxide, copper thiocyanate (generic name: rhodan copper), cupronickel, copper powder, and the like. Of these, cuprous oxide and rhodan copper are particularly preferred.
- organic agents examples include organic copper compounds such as 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate.
- organic copper compounds such as 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate.
- zinc pyrithione, copper pyrithione, pyridine triphenylborane, dineb, sea nine 211, and irgarol 1051 are preferable, and copper pyrithione, zinc pyrithione, and sea nine 211 are more preferable.
- Antifouling agent B is preferably cuprous oxide, rhodan copper, zinc pyrithione, copper pyrithione, pyridine triphenylborane, dinebu, sea nine 211 and irgarol 1051, trifluanid, diclofluuride, cuprous oxide, copper pyrithione, zinc pyrithione and Sea nine 211 is more preferable.
- These antifouling agents can be used alone or in combination of two or more.
- the content of the antifouling agent B in the composition of the present invention is not particularly limited, but is usually 0.1 to 75% by mass, preferably 1 to 60% by mass in the solid content of the composition of the present invention.
- the content of the antifouling agent B is less than 0.1% by mass, a sufficient antifouling effect may not be obtained.
- the content of the antifouling agent B exceeds 75% by mass, the formed coating film is fragile, and further, the adhesion to the coating film formation is weak and the function as the antifouling coating film cannot be sufficiently performed. .
- ⁇ Elution regulator C examples include rosin, rosin derivatives and their metal salts, monocarboxylic acids and salts thereof, or alicyclic hydrocarbon resins.
- the elution regulator C can be used alone or in combination of two or more.
- Examples of the rosin include tall oil rosin, gum rosin, and wood rosin.
- Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
- As the metal salt of rosin and the metal salt of rosin derivative a reaction product of a metal compound and rosin can be used.
- Examples of the metal salt of rosin include gum rosin zinc (or copper) salt, wood rosin zinc (or copper) salt, Examples include tall oil rosin zinc (or copper) salt.
- rosin zinc (or copper) salt hydrogenated rosin zinc (or copper) salt, disproportionated rosin zinc (or copper) salt, maleated rosin zinc (or copper) salt, formylated rosin zinc (or copper) salt, polymerization Examples include rosin zinc (or copper) salt.
- Examples of the monocarboxylic acid include fatty acids having about 5 to 30 carbon atoms, synthetic fatty acids, and naphthenic acids.
- Examples of the monocarboxylic acid salt include a copper salt, a zinc salt, a magnesium salt, and a calcium salt.
- 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.
- the composition of the present invention is at least one selected from the group consisting of rosin, rosin derivatives, and metal salts thereof, as the elution modifier C, in that it can impart moderate elution promoting properties to the composition of the present invention. It is preferable to contain From the viewpoint of improving crack resistance and water resistance, it is particularly preferable to contain a copper salt or a zinc salt of rosin or a rosin derivative.
- the content of the elution regulator C in the composition of the present invention is usually 1 to 80 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the copolymer A.
- the elution control agent C is less than 1 part by mass, the effect of preventing the adhesion of waterpox fouling organisms, particularly the effect of preventing the attachment of waterfouling fouling organisms during the outfitting period cannot be expected.
- the content of the elution regulator C exceeds 80 parts by mass, defects such as cracks and peeling are likely to occur in the coating film, and there is a possibility that the effect of preventing the adhesion of water-soil-fouling organisms may not be exhibited sufficiently.
- plasticizer D By including the plasticizer D in the antifouling coating composition of the present invention, the plasticity of the composition can be improved, and as a result, a tough coating film can be suitably formed.
- plasticizer D examples include phosphate esters such as tricresyl phosphate, trioctyl phosphate and triphenyl phosphate, phthalates such as dibutyl phthalate and dioctyl phthalate, and adipine such as dibutyl adipate and dioctyl adipate.
- phosphate esters such as tricresyl phosphate, trioctyl phosphate and triphenyl phosphate
- phthalates such as dibutyl phthalate and dioctyl phthalate
- adipine such as dibutyl adipate and dioctyl adipate.
- Acid esters sebacic acid esters such as dibutyl sebacate, dioctyl sebacate, epoxidized soybean oil, epoxidized oils such as epoxidized linseed oil, methyl vinyl ether polymers, alkyl vinyl ether polymers such as ethyl vinyl ether polymers, Polyalkylene glycols such as polyethylene glycol and polypropylene glycol, t-nonyl pentasulfide, petrolatum, polybutene, trimellitic acid tris (2-ethylhexyl), silicone oil , Liquid paraffin, and chlorinated paraffins. These can be used alone or in combination of two or more.
- the content of the plasticizer D in the composition of the present invention is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the copolymer A.
- Examples of the other resin E include (meth) acrylic resins other than the copolymer A, alkyd resins, polyester resins, chlorinated rubber resins, vinyl resins, and the like.
- the other resin E in the composition of the present invention can be contained in an amount of 1 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the copolymer A.
- pigments, dyes, antifoaming agents, anti-sagging agents, dispersants, anti-settling agents, dehydrating agents, organic solvents, and the like can be added to the antifouling coating composition of the present invention as necessary.
- Examples of the pigment include zinc oxide, bengara, talc, titanium oxide, silica, calcium carbonate, barium sulfate, calcium oxide, and magnesium oxide. These can be used alone or in combination of two or more.
- Examples of the dye include various organic dyes that are soluble in an organic solvent.
- Examples of antifoaming agents include silicone resin-based antifoaming agents and acrylic resin-based antifoaming agents.
- Examples of the anti-sagging agent, the dispersing agent or the anti-settling agent include fatty acid amide wax and polyethylene oxide.
- the dehydrating agent examples include anhydrous gypsum, synthetic zeolite-based adsorbent, orthoesters, silicates such as tetraethoxysilane, isocyanates, and the like. These can be used alone or in combination of two or more.
- an organic solvent what is normally mix
- the antifouling coating composition of the present invention can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer A or the like using a disperser. What is necessary is just to adjust suitably content of copolymer A etc. in the said liquid mixture so that it may become content of copolymer A etc. in the said antifouling coating composition, respectively.
- the mixed solution is preferably one in which various materials such as copolymer A are dissolved or dispersed 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.
- 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 coating film is formed on the surface of the coating 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 antifouling effect can be exhibited continuously by overcoating the said composition.
- Examples of the coating film formation include ships (particularly ship bottom), fishing equipment, underwater structures, and the like.
- Examples of the fishery tools include aquaculture or stationary fishing nets, fishing net accessories such as floats and ropes used in the fishing nets, and the like.
- Examples of the underwater structure include a power plant conduit, a bridge, a port facility, and the like.
- the antifouling coating film can be formed by applying the antifouling coating composition to the surface (entirely or partly) of the coating film forming object.
- Examples of the application method include brush coating, spraying, dipping, flow coating, and spin coating. These may be used alone or in combination of two or more. After application, dry.
- the drying temperature may be room temperature. What is necessary is just to set drying time suitably according to the thickness etc. of a coating film.
- the antifouling coating film of the present invention formed using the antifouling coating composition has a long-term balance between the dissolution rate of the coating film in seawater and the water permeability to the coating film. Stable surface renewability is maintained, and further, there is an advantage that recoatability is excellent.
- the thickness of the antifouling coating film may be set as appropriate according to the type of coating film formation, the navigation speed of the ship, the seawater temperature, and the like. For example, when the coating film forming object is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 500 ⁇ m, preferably 100 to 400 ⁇ m.
- the antifouling coating film of the present invention has an appropriate hardness. That is, the antifouling coating film of the present invention has a hardness that does not cause coating film abnormality such as cold flow.
- the coated article of the present invention has the antifouling coating film on the surface.
- the coated product of the present invention may have the antifouling coating film on the entire surface or a part thereof.
- the coated product of the present invention has a coating film excellent in long-term stable surface renewability and recoatability by improving the balance between the dissolution rate of the coating film in seawater and the water permeability to the coating film. Therefore, it can be suitably used as the above-mentioned ship (especially ship bottom), fishing equipment, underwater structure and the like.
- the antifouling coating film when the antifouling coating film is formed on the ship bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, and the coating film surface is constantly renewed, thereby preventing adhesion of waterpox fouling organisms. it can. Moreover, the hydrolysis rate of the antifouling coating film is suitably suppressed. Therefore, the ship can maintain antifouling performance for a long period of time. For example, even in a stationary state such as during berthing or during outfitting, there is little adhesion and accumulation of Minamata fouling organisms, and the antifouling effect can be exhibited for a long period of time.
- the antifouling coating on the surface is basically free from cracks or peeling. Therefore, it is not necessary to perform another operation such as forming a coating film after the coating film is completely removed. Therefore, an antifouling coating film can be suitably formed by directly overcoating the antifouling coating film composition. Thereby, it is possible to easily and continuously maintain the antifouling performance at a low cost.
- % 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.
- the heating residue is a value obtained by heating at 125 ° C. for 1 hour.
- the unit of the blending amount of each component in Tables 1 and 2 is g.
- Production Examples 1 to 4 are production examples of the monomer (b) -containing solution.
- the mixture was cooled and 160 g of PGM was added to obtain a monomer (b) -2 containing solution.
- the solid content of this solution was 50.5%.
- the composition of the solid content in the monomer (b) -2 containing solution is 60% by mass of the total of Versatic acid zinc methacrylate and zinc dimethacrylate (monomer (b) -2).
- Zinc (organic acid metal salt) was 40% by mass.
- the mixture was cooled and 186 g of PGM was added to obtain a monomer (b) -3 containing solution.
- the solid content of this solution was 50.2%.
- the composition of the solid content in the monomer (b) -3 containing solution is 60% by mass of the total of the versatic acid copper acrylate and copper diacrylate (monomer (b) -3), and the by-product versatic acid. Copper (organic acid metal salt) was 40% by mass.
- the mixture was cooled and 165 g of PGM was added to obtain a monomer (b) -4 containing solution.
- the solid content of this solution was 50.5%.
- the composition of the solid content in the monomer (b) -4 containing solution is 50% by mass of the total of naphthenic zinc acrylate and zinc diacrylate (monomer (b) -4), and naphthenic acid by-produced.
- Zinc (organic acid metal salt) was 50 mass%.
- the mixture was cooled, and 130 g of PGM was added to obtain a monomer (b) -5-containing solution.
- the solid content of this solution was 50.0%.
- the composition of the solid content in the monomer (b) -5-containing solution is 50% by mass of the total amount of rosin zinc acrylate and zinc diacrylate (monomer (b) -5).
- the organic acid metal salt) was 50% by mass.
- ⁇ Method for specifying composition of solid content of monomer (b) -containing solution The mass% of the monomer (b) and the mass% of the organic acid metal salt by-produced in the solid content of the monomer (b) -containing solution were determined by the following method. First, the copolymer obtained using the target monomer (b) -containing solution is reprecipitated in a large amount of n-hexane. In the monomer (b) -containing solution, there is an organic acid metal salt by-produced in the production process, but it remains in the copolymer solution as it is because it does not participate in the polymerization. These organic acid metal salts are generally soluble in n-hexane.
- the organic acid metal salt is extracted into n-hexane and separated from the copolymer solution.
- the mass% of the organic acid metal salt can be obtained. From there, back calculation is performed, and the mass% of the monomer (b) represented by the remaining general formula (II) or (III) is calculated.
- the mass of the monomer (b) -containing solution in Tables 1 and 2 the mass of the monomer (b) obtained from the composition determined here and the preparation as the monomer (b) -containing solution
- the amount charged as the monomer (b) -containing solution is shown in parentheses. For example, in Production Example 6 in Table 1, the mass of the monomer (b) -1 is 5 g, and the charged amount of the monomer (b) -containing solution is 16.7 g.
- copolymer A-13 when rosin is used as the organic acid as in copolymer A-13, the polarity changes greatly from the above, and the rosin metal salt becomes insoluble in n-hexane and does not contain the rosin metal salt. The polymer is more soluble. Therefore, the composition of copolymer A-13 was analyzed as follows.
- copolymer A-13 50 g as a solid content
- reprecipitation operation is performed in a large amount of n-hexane.
- a copolymer containing no rosin metal salt is selectively extracted into n-hexane.
- 10 g of a solid content was obtained. This was redissolved with THF, and 100 g of 2% NaOH aqueous solution was added thereto for hydrolysis treatment. Thereafter, 4% hydrochloric acid was added to adjust the liquidity to the acidic side, followed by extraction with toluene.
- Triisopropylsilanol and rosin were distributed on the organic layer side, and 7.97 g of the hydrolyzed resin was separated as a precipitate on the aqueous layer side. When this resin was dissolved in ethanol and the acid value was measured, the solid content acid value was 70 mgKOH / g. On the other hand, 1.36 g (7.80 mmol) of triisopropylsilanol was distilled and separated from the organic layer, and 0.22 g of rosin (0.73 mmol in terms of abieticin) was obtained as a residue.
- the amount of monomer represented by general formula (II) can be determined from the amount of rosin obtained by this operation, and the amount of monomer represented by general formula (III) can also be determined from the obtained acid value and silanol amount. As a result, the mass% of monomer (b) -5 was calculated to be 50%.
- Production Examples 6 to 18 and Comparative Production Examples 1 to 10 are production examples of the copolymer solutions A-1 to A-13 and B-1 to B-10.
- Examples 1 to 22 and Comparative Examples 1 to 10 (Production of Coating Composition)> The components shown in Tables 3 to 5 were blended in the proportions (mass%) shown in Tables 3 to 5 and mixed with glass beads having a diameter of 1.5 to 2.5 mm to produce coating compositions.
- Example 1 (Paint Stability Test) >> The coating compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 10 were sealed in 100 mL wide-mouth tin cans and stored in a thermostat at 45 ° C. for 3 months. Measured with a viscometer. Evaluation was performed by the following method.
- ⁇ Viscosity change of paint is 500 to 5,000 mPa ⁇ s / 25 ° C (thickened slightly)
- ⁇ Viscosity change of paint is over 5,000 mPa ⁇ s / 25 ° C. to 100,000 mPa ⁇ s / 25 ° C. (thickly thickened)
- ⁇ Test Example 2 (Coating adhesion test) >> The adhesion test of the coating film was conducted in accordance with JIS K-5600-5-6. Specifically, the coating compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 10 are about 100 ⁇ m thick on a blasted tin plate (75 ⁇ 150 ⁇ 2 mm) as a dry coating film. After being applied and dried at 40 ° C. for 1 day, an adhesion test was conducted. Evaluation was performed by the following method. The dried coating film was cut with a cutter with 11 vertical and horizontal flaws reaching the base (tinplate) in a goblet shape to make 100 squares of 2 mm square. A cellophane tape (24 mm width, manufactured by Nichiban Co., Ltd.) is applied to the 100 squares so that no air bubbles enter, and one end of this tape is held in hand and quickly peeled off. Examined.
- Example 3 Coating Flexibility Test
- the coating compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 10 were applied to a blasted tin plate (75 ⁇ 150 ⁇ 2 mm) so that the thickness as a dry coating film was about 100 ⁇ m. After drying at 0 ° C. for 1 day, the state of the folded coating film was confirmed by visual observation at 90 degrees.
- Test Example 4 (Rotary test) >> A rotating drum having a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and an automatic pH controller for keeping the pH of the seawater constant were attached. Two test plates were prepared according to the following method. First, a rust-preventing coating film was formed by applying and drying a rust-preventive paint (vinyl A / C) on a hard PVC plate (75 ⁇ 150 ⁇ 1 mm) so that the thickness after drying was about 50 ⁇ m.
- a rust-preventive paint (vinyl A / C)
- the coating compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 10 were applied on the anticorrosive coating film so that the thickness after drying was about 300 ⁇ 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 300 ⁇ 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 kept at 25 ° C. and the pH was kept at 8.0 to 8.2, and the seawater was changed every week.
- the residual film thickness at the beginning of each test plate and every 3 months after the start of the test is measured with a laser focus displacement meter, and the dissolved film thickness is calculated from the difference ( ⁇ m / month )
- the said measurement was performed for 24 months and the said coating-film melt
- dissolution amount was computed every 12 months progress.
- the surface of each coating film was visually observed to evaluate the state of the coating film.
- Test Example 5 (Anti-fouling test) >> The coating compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 10 were applied on both sides of a hard PVC plate (100 ⁇ 200 ⁇ 2 mm) so that the thickness as a dry coating film was about 200 ⁇ m. The obtained coated material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 200 ⁇ m. The test plate was immersed in 1.5 m below the sea surface in Owase City, Mie Prefecture, and the test plate was observed for fouling due to deposits for 24 months.
- the coating compositions of the present invention (Examples 1 to 22) have good storage stability. Moreover, it turns out that the coating film formed using the coating composition of this invention adhere
- the coating film formed using the coating composition of the present invention has excellent water resistance and does not generate cracks or hair cracks, and therefore can maintain antifouling performance for a long period of time. Furthermore, it can be seen that the coating film formed using the coating composition of the present invention has no adhesion of fouling organisms such as shellfish and algae, and almost no slime. Thereby, since the balance of the solubility and water permeability of a coating film is designed suitably, it turns out that favorable surface renewability is maintained for a long period of time.
- the coating film formed using the coating composition of Comparative Examples 1 and 2 has a high hydrolyzable group content, the dissolution rate is too high from the beginning, and the coating film disappears after 24 months. . In this case, it is difficult to design the coating film thickness. In addition, fouling organisms such as shellfish and algae adhere to the coating film after being immersed for 24 months.
- the coating film formed using the coating composition of Comparative Example 3 does not have a good balance between water permeability and coating film dissolution, and in the latter half, dissolution is greatly reduced and hair cracks are generated. Further, it can be seen that the slime started to adhere firmly to the coating film from the beginning, and after 24 months it was thicker and more firmly attached.
- Comparative Example 4 since the content of the hydrolyzable group is too low, the original film dissolution hardly occurs. Although the state of the coating is good, the antifouling property is inferior because there is no dissolution of the coating. In the antifouling test, the coating film of Comparative Example 4 is gradually fouled, and biofouling is observed after 24 months.
- Comparative Examples 5 and 6 consist of a simple mixture of a triorganosilyl group-containing copolymer and a metal-containing copolymer, and it is difficult to balance water permeability and coating film dissolution. It cannot be maintained. Moreover, since compatibility is bad, the crack has arisen. In addition, this coating film has poor antifouling properties as the coating film dissolves in the latter half, and extensive biological adhesion is observed.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
すなわち、本発明は、(a)後述の一般式(I)で表されるトリオルガノシリル基含有単量体10~25質量%、(b)後述の一般式(II)又は(III)で表される金属含有重合性単量体の1種以上を2~10質量%、並びに(c)前記単量体(a)及び(b)以外のエチレン性不飽和単量体65~88質量%を共重合してなる共重合体からなる、防汚塗料組成物用共重合体を提供するものである。
本発明の防汚塗料組成物用共重合体Aは、
(a)下記一般式(I)で表されるトリオルガノシリル基含有単量体10~25質量%、
(b)下記一般式(II)又は(III)で表される金属含有重合性単量体の1種以上を2~10質量%、並びに
(c)前記単量体(a)及び(b)以外のエチレン性不飽和単量体65~88質量%
を共重合してなる共重合体からなる、防汚塗料組成物用共重合体。
さらに、単量体(a)は、好ましくは、15~20質量%である。単量体(b)は、好ましくは、4~7質量%であり、単量体(a)/単量体(b)で表される質量比は、好ましくは、2以上である。
共重合体Aは、単量体(a)10~25質量%と、単量体(b)2~10質量%と、前記単量体(a)および(b)以外のエチレン性不飽和単量体(c)65~88質量%とを共重合してなるものである。共重合体Aを用いることにより、海水中での塗膜の溶解速度と塗膜への透水性のバランスがとれ、膨潤層の形成を抑えることができ、長期間の安定した表面更新性が維持でき、所望の防汚効果を有効に発揮することができる。また、塗膜の優れたリコート性能を発揮することができる。
R2~R4で示されるアルキル基またはアリール基の炭素数は、例えば1~10であり、好ましくは1~6である。アルキル基またはアリール基としては、例えば、メチル基、n-プロピル基、イソプロピル基、n-ブチル基、s-ブチル基、シクロヘキシル基、フェニル基等が挙げられる。これらの中で好ましいものは、製造コスト、原料入手容易性の観点/理由から、トリイソプロピル基、トリn-ブチル基、トリフェニル基であり、特に好ましいものは、トリイソプロピル基である。
これらの単量体(a)は、単独で又は2種以上を組み合わせて使用できる。
単量体(b)は、一般式(II)または(III)で表される単量体1種以上からなる。
式(II)中、R6で示される有機酸残基の炭素数は、例えば6~20であり、好ましくは7~15であり、さらに好ましくは7~12である。有機酸としては、例えば、バーサチック酸、オクチル酸、ラウリン酸、ステアリン酸、ナフテン酸等が挙げられ、原料入手容易性や塗膜物性の観点から、バーサチック酸が好ましい。
これらは、単独でも使用でき、又2種以上を組み合わせて使用することもできる。
単量体(c)としては、例えば、(メタ)アクリレート化合物、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。
これら単量体(c)は単独又は二種以上で用いることができる。
防汚薬剤Bとしては、海棲汚損生物に対して殺傷又は忌避作用を有する物質であればよく、特に限定されない。例えば無機薬剤及び有機薬剤が挙げられる。
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。
前記溶出調整剤Cとしては、例えば、ロジン、ロジン誘導体およびこれらの金属塩、モノカルボン酸およびその塩または脂環式炭化水素樹脂等が挙げられる。溶出調整剤Cは、1種又は2種以上併用して使用できる。
耐クラック性・耐水性の向上の点で、ロジンまたはロジン誘導体の銅塩または亜鉛塩を含有することが特に好ましい。
本発明の防汚塗料組成物に可塑剤Dを含有させることにより、前記組成物の可塑性を向上させることができ、その結果、強靱な塗膜を好適に形成できる。
本発明の防汚塗料組成物に他の樹脂Eを含有させることにより、本発明の効果を損なうことなく、コストダウンが可能であり、また、樹脂Eの持つ物性との相乗効果を得ることができる。
さらに、本発明の防汚塗料組成物には、必要に応じて、顔料、染料、消泡剤、タレ止め剤、分散剤、沈降防止剤、脱水剤、有機溶媒等を添加することができる。
染料として、有機溶剤可溶の各種有機染料等が挙げられる。
消泡剤として、シリコーン樹脂系消泡剤、アクリル樹脂系消泡剤等が挙げられる。
タレ止め剤、分散剤または沈降防止剤として、脂肪酸アマイドワックス、酸化ポリエチレン等が挙げられる。
脱水剤としては、例えば、無水石膏、合成ゼオライト系吸着剤、オルソエステル類、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。
有機溶媒としては、例えば、脂肪族系溶剤、芳香族系溶剤、ケトン系溶剤、エステル系溶剤、エーテル系溶剤等の通常、防汚塗料に配合されるものが挙げられる。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、共重合体A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。
前記混合液中における共重合体A等の含有量は、それぞれ上記防汚塗料組成物中の共重合体A等の含有量となるように適宜調整すればよい。
前記混合液としては、共重合体A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。また、塗膜を溶解させた後、上記組成物を上塗りすることにより、継続的に防汚効果を発揮することができる。
ガードカラム・・・TSKguardcolumn α(東ソー株式会社製)
カラム・・・ TSKgel αタイプ(α-M)7.8mmI.D.30cm(東ソー株式会社製)2本直列接続
流量・・・ 1.0 mL/min
検出器・・・ RI
カラム恒温槽温度・・・ 40℃
展開溶媒・・・ 20mM LiBr/DMF溶液
試料濃度・・・10g/L
注入量・・・50μL
また、表1~表2中の各成分の配合量の単位はgである。
製造例1~4は、単量体(b)含有溶液の製造例である。
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、プロピレングリコールモノメチルエーテル(PGM)350g、酸化亜鉛144g、水3gを仕込み、窒素雰囲気下、75℃まで加温した。その後アクリル酸127gとバーサチック酸(酸価330mgKOH/g)300gの混合液を3時間かけて滴下した。滴下終了後、さらに2時間熟成すると、淡黄色透明液体となった。その後冷却し、PGM 160gを添加して、単量体(b)-1含有溶液を得た。この溶液の固形分は50.1%であった。単量体(b)-1含有溶液中の固形分の組成は、後述する方法で算出したところ、バーサチック酸亜鉛アクリレート及び亜鉛ジアクリレートの合計(単量体(b)-1)が60質量%であり、副生するバーサチック酸亜鉛(有機酸金属塩)が40質量%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、プロピレングリコールモノメチルエーテル(PGM)353g、酸化亜鉛144g、水3gを仕込み、窒素雰囲気下、75℃まで加温した。その後メタクリル酸152gとバーサチック酸(酸価330mgKOH/g)300gの混合液を3時間かけて滴下した。滴下終了後、さらに2時間熟成すると、淡黄色透明液体となった。その後冷却し、PGM 160gを添加して、単量体(b)-2含有溶液を得た。この溶液の固形分は50.5%であった。単量体(b)-2含有溶液中の固形分の組成は、バーサチック酸亜鉛メタクリレート及び亜鉛ジメタクリレートの合計(単量体(b)-2)が60質量%であり、副生するバーサチック酸亜鉛(有機酸金属塩)が40質量%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、プロピレングリコールモノメチルエーテル(PGM)353g、水酸化銅172g、水3gを仕込み、窒素雰囲気下、75℃まで加温した。その後アクリル酸127gとバーサチック酸(酸価330mgKOH/g)300gの混合液を3時間かけて滴下した。滴下終了後、さらに2時間熟成すると、濃緑色透明液体となった。その後冷却し、PGM 186gを添加して、単量体(b)-3含有溶液を得た。この溶液の固形分は50.2%であった。単量体(b)-3含有溶液中の固形分の組成は、バーサチック酸銅アクリレート及び銅ジアクリレートの合計(単量体(b)-3)が60質量%であり、副生するバーサチック酸銅(有機酸金属塩)が40質量%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、プロピレングリコールモノメチルエーテル(PGM)270g、酸化亜鉛96g、水3gを仕込み、窒素雰囲気下、75℃まで加温した。その後アクリル酸85gとナフテン酸(酸価220mgKOH/g)300gの混合液を3時間かけて滴下した。滴下終了後、さらに2時間熟成すると、淡黄色透明液体となった。その後冷却し、PGM 165gを添加して、単量体(b)-4含有溶液を得た。この溶液の固形分は50.5%であった。単量体(b)-4含有溶液中の固形分の組成は、ナフテン酸亜鉛アクリレート及び亜鉛ジアクリレートの合計(単量体(b)-4)が50質量%であり、副生するナフテン酸亜鉛(有機酸金属塩)が50質量%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、プロピレングリコールモノメチルエーテル(PGM)270g、酸化亜鉛72g、水3gを仕込み、窒素雰囲気下、75℃まで加温した。その後アクリル酸64gとロジン(酸価167mgKOH/g)300gの混合液を3時間かけて滴下した。滴下終了後、さらに2時間熟成すると、淡黄色透明液体となった。その後冷却し、PGM 130gを添加して、単量体(b)-5含有溶液を得た。この溶液の固形分は50.0%であった。単量体(b)-5含有溶液中の固形分の組成は、ロジン亜鉛アクリレート及び亜鉛ジアクリレートの合計(単量体(b)-5)が50質量%であり、副生するロジン亜鉛(有機酸金属塩)が50質量%であった。
上記単量体(b)含有溶液の固形分中の単量体(b)の質量%および、副生する有機酸金属塩の質量%は、下記方法によって決定した。
まず、対象の単量体(b)含有溶液を用いて得られた共重合体を、多量のn-ヘキサン中で再沈殿操作する。単量体(b)含有溶液には、その製造過程において副生する有機酸金属塩が存在するが、重合には関与しないため、共重合体溶液中にそのまま残存する。また、これら有機酸金属塩は一般的にn-ヘキサンに可溶である。よって、上記再沈殿操作により、有機酸金属塩は、n-ヘキサン中に抽出され、共重合体溶液から分離される。抽出量が恒量になった時のその抽出量を測定し、添加した共重合体の固形分値で割ることで、有機酸金属塩の質量%がわかる。そこから逆算し、残りの一般式(II)または(III)で表される単量体(b)の質量%が算出される。表1~表2中の単量体(b)含有溶液の行には、ここで決定された組成から求めた単量体(b)の質量と、単量体(b)含有溶液としての仕込み量を示し、単量体(b)含有溶液としての仕込み量は括弧内に示した。例えば表1の製造例6では、単量体(b)-1の質量が5gであり、単量体(b)含有溶液の仕込み量が16.7gである。
この操作で得られたロジン量により、一般式(II)で表される単量体量がわかり、さらに得られた酸価及びシラノール量から一般式(III)で表される単量体量も算出され、結果として単量体(b)-5の質量%が50%と算出された。
製造例6~18及び比較製造例1~10は、共重合体溶液A-1~A-13、B-1~B-10の製造例である。
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30g、プロピレングリコールモノメチルエーテル(PGM) 30gを仕込み、窒素雰囲気下、85±5℃で攪拌しながら、トリイソプロピルシリルアクリレート15g、単量体(b)-1含有溶液を16.7g(このうち、単量体(b)-1は5g)、メチルメタクリレート50g、n-ブチルアクリレート20g、2-メトキシエチルアクリレート5g、2-メトキシエチルメタクリレート5g、及び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4g(初期添加)の混合液を3時間かけて滴下した。その後同温度で2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1g(後添加)を1時間毎に3回添加して重合反応を完結した後、キシレン38g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。A-1の加熱残分、重量平均分子量Mwを表1に示す。なお、共重合体の重量平均分子量Mwは、共重合体からn-ヘキサンにて非重合性の有機酸金属塩を除去した後の共重合体を、前記GPCにより求めた値である。
表1~表2に示す有機溶剤、単量体及び重合開始剤を用いて、製造例6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A-2~A-10を得た。得られた各共重合体溶液の粘度、加熱残分、Mwを表1~表2に示す。
表3~表5に示す成分を表3~表5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。
ガムロジン亜鉛塩溶液: 固形分約50%キシレン溶液
水添ロジン亜鉛塩溶液: 固形分約50%キシレン溶液
ガムロジン銅塩溶液: 固形分約50%キシレン溶液
水添ロジン銅塩溶液: 固形分約50%キシレン溶液
ガムロジン溶液: 固形分約50%キシレン溶液
クイントン1500: 日本ゼオン社製の脂環族系炭化水素樹脂、50%キシレン溶液
亜酸化銅: 日進ケムコ社製、NC-301 平均粒径3μm
カッパーピリチオン: アーチケミカルス社製、カッパーオマジン
シーナイン211: R&H社製、有効成分30%キシレン溶液
ベンガラ: 戸田ピグメント製、TODA COLOR EP-13D
タルク: 松村産業製、クラウンタルク3S
マイカ:脇元雲母有限会社製、マイカ白玉
酸化亜鉛: 正同化学製、酸化亜鉛2種(商品名)
酸化チタン: 古河機械金属製、FR-41
有機赤色顔料: 山陽色素製、スカーレットTR
テトラエトキシシラン: キシダ化学製、試薬特級
ディスパロンA603-20X: 楠本化成製、 脂肪酸アマイド系揺変剤、有効成分30%キシレンペースト
塩素化パラフィン:東ソー社製、トヨパラックス150
サンソサイザー E-2000H:新日本理化社製
実施例1~22及び比較例1~10で得られた塗料組成物を、100mLの広口ブリキ缶に入れ密封し45℃の恒温器に3ヶ月間保存した後、該塗料組成物の粘度をB形粘度計で測定した。
評価は以下の方法で行った。
◎:塗料の粘度変化が500mPa・s/25℃未満のもの(塗料状態が殆ど変化しなかったもの)
○:塗料の粘度変化が500~5,000mPa・s/25℃のものを(わずかに増粘したもの)
△:塗料の粘度変化が5,000mPa・s/25℃超~100,000mPa・s/25℃のもの(大きく増粘したもの)
×:塗料粘度が測定不能まで変化したもの(ゲル状になったもの又は固化したもの)
JIS K-5600-5-6の規定に従って、塗膜の付着性試験を行った。具体的には、実施例1~22及び比較例1~10で得られた塗料組成物を、ブラスト仕上げをしたブリキ板(75×150×2mm)上に、乾燥塗膜としての厚みが約100μmとなるように塗布し40℃で1日乾燥させた後、付着性試験を行った。
評価は以下の方法で行った。
乾燥後の塗膜にカッターで、下地(ブリキ板)に達する縦横各11本の傷をごばん目状に入れて2mm角のマス目を100個作製した。前記100個のマス目にセロハンテープ(ニチバン(株)製 テープ幅24mm)を気泡の入らないように張りつけ、このテープの一端を手に持って急速にはがして、塗膜の付着状態を目視で調べた。
○:剥離しなかったごばん目の数が40~69個の場合
△:剥離しなかったごばん目の数が20~39個の場合
×:剥離しなかったごばん目の数が0~19個の場合
実施例1~22及び比較例1~10で得られた塗料組成物を、ブラスト仕上げをしたブリキ板(75×150×2mm)に、乾燥塗膜としての厚みが約100μmとなるよう塗布し40℃で1日間乾燥させた後、90度に折り曲げ塗膜の状態を肉眼観察により確認した。
◎:殆どクラックが生じなかったもの
○:微細なクラックが生じたもの
△:大きなクラックが生じたもの
×:塗膜の一部が容易に剥離したもの
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2つ作製した。
まず、硬質塩ビ板(75×150×1mm)上に、防錆塗料(ビニル系A/C)を乾燥後の厚みが約50μm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1~22及び比較例1~10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300μm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300μm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25℃、pHを8.0~8.2に保ち、一週間毎に海水を入れ換えた。
各試験板の初期と試験開始後3ヶ月毎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1ヶ月あたりの塗膜溶解量(μm/月)を得た。なお、前記測定は24ヶ月間行われ、前記塗膜溶解量を12ヶ月経過ごとに算出した。
また、ロータリー試験終了後(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。
◎:全く異常のない場合
○:僅かにヘアークラックが見られるもの
△:塗膜全面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などの塗膜に異常が見られるもの
実施例1~22及び比較例1~10で得られた塗料組成物を、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となるよう塗布した。得られた塗布物を室温(25℃)で3日間乾燥させることにより、厚みが約200μmの乾燥塗膜を有する試験板を作製した。この試験板を三重県尾鷲市の海面下1.5mに浸漬して付着物による試験板の汚損を24ヶ月観察した。
◎:貝類や藻類などの汚損生物の付着がなく、かつ、スライムも殆ど付着していないレベル
○:貝類や藻類などの汚損生物の付着がなく、かつ、スライムが薄く(塗膜面が見える程度)付着して
いるものの刷毛で軽く拭いて取れるレベル
△:貝類や藻類などの汚損生物の付着はないが、スライムが薄く(塗膜面が見える程度)付着しており
刷毛で強く拭いて取れないレベル
×:貝類や藻類などの汚損生物の付着はないが、スライムが塗膜面が見えない程度に厚く付着して
おり刷毛で強く拭いても取れないレベル
××:貝類や藻類などの汚損生物が付着しているレベル
表6から、本発明の塗料組成物(実施例1~22)は、保存安定性が良好であることが分かる。また、本発明の塗料組成物を用いて形成された塗膜は、ブリキ板に対して強固に接着し、屈曲されてもクラックが生じにくいことが分かる。この塗膜は、海水中での溶解量が、1ヶ月当たり2~10μm程度(年平均)であり、24ヶ月経過後も安定した溶解量を維持していることが分かる。これは、本発明の効果である塗膜溶解速度と透水性とのバランスが取れていることを表しており、膨潤層の形成が抑えられていると考えられる。この結果、本発明の塗料組成物を用いて形成された塗膜は、耐水性に優れクラックやヘヤークラック等を生じないため、長期間防汚性能を維持することができる。さらに、本発明の塗料組成物を用いて形成された塗膜には、貝類や藻類などの汚損生物の付着がなく、かつスライムの付着も殆どないことが分かる。これにより、塗膜の溶解性と透水性のバランスが好適に設計されているため、良好な表面更新性を長期に維持していることが分かる。
Claims (4)
- (a)下記一般式(I)で表されるトリオルガノシリル基含有単量体10~25質量%、
(b)下記一般式(II)又は(III)で表される金属含有重合性単量体の1種以上を2~10質量%、並びに
(c)前記単量体(a)及び(b)以外のエチレン性不飽和単量体65~88質量%
を共重合してなる共重合体からなる、防汚塗料組成物用共重合体。
一般式(I):
一般式(II):
一般式(III):
- 前記単量体(b)のR6がバーサチック酸の残基である請求項1に記載の防汚塗料組成物用共重合体。
- 請求項1に記載の共重合体を含有する防汚塗料組成物。
- 請求項3に記載の防汚塗料組成物を用いて形成される防汚塗膜。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020177013392A KR20170074925A (ko) | 2014-10-22 | 2015-10-15 | 방오도료 조성물용 공중합체, 방오도료 조성물, 방오도막 |
EP15852068.4A EP3211014A4 (en) | 2014-10-22 | 2015-10-15 | Copolymer for antifouling coating composition, antifouling coating composition, antifouling coating film |
CN201580054381.4A CN106795248B (zh) | 2014-10-22 | 2015-10-15 | 防污涂料组合物用共聚物、防污涂料组合物、防污涂膜 |
JP2016555195A JP6595494B2 (ja) | 2014-10-22 | 2015-10-15 | 防汚塗料組成物用共重合体、防汚塗料組成物、防汚塗膜 |
SG11201702664YA SG11201702664YA (en) | 2014-10-22 | 2015-10-15 | Copolymer for antifouling coating composition, antifouling coating composition, antifouling coating film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-215414 | 2014-10-22 | ||
JP2014215414 | 2014-10-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016063789A1 true WO2016063789A1 (ja) | 2016-04-28 |
Family
ID=55760830
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/079173 WO2016063789A1 (ja) | 2014-10-22 | 2015-10-15 | 防汚塗料組成物用共重合体、防汚塗料組成物、防汚塗膜 |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP3211014A4 (ja) |
JP (1) | JP6595494B2 (ja) |
KR (1) | KR20170074925A (ja) |
CN (1) | CN106795248B (ja) |
MY (1) | MY181589A (ja) |
SG (2) | SG10201903432QA (ja) |
WO (1) | WO2016063789A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018040863A1 (zh) * | 2016-08-30 | 2018-03-08 | 厦门双瑞船舶涂料有限公司 | 自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物及其制备方法 |
JP2018070685A (ja) * | 2016-10-25 | 2018-05-10 | 中国塗料株式会社 | 防汚塗料組成物、防汚塗膜、防汚塗膜付き基材及びその製造方法、並びに防汚方法 |
JP6490277B1 (ja) * | 2018-04-13 | 2019-03-27 | 関西ペイント株式会社 | 防汚塗料組成物、及びその塗膜を有する塗装物品 |
JPWO2019069777A1 (ja) * | 2017-10-04 | 2020-11-05 | 日東化成株式会社 | 防汚塗料組成物、該組成物を用いて形成される防汚塗膜を表面に有する塗装物 |
GB202107159D0 (en) | 2021-03-23 | 2021-06-30 | Jotun As | Monitoring a vessel |
WO2021180588A2 (en) | 2020-03-09 | 2021-09-16 | Jotun A/S | Hull cleaning robot |
WO2021191388A1 (en) | 2020-03-27 | 2021-09-30 | Jotun A/S | Antifouling coating composition |
WO2022191100A1 (ja) * | 2021-03-12 | 2022-09-15 | 日東化成株式会社 | 防汚塗料組成物 |
WO2022200430A1 (en) | 2021-03-23 | 2022-09-29 | Jotun A/S | Monitoring the cleanliness of an underwater surface of a stationary object |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107649069B (zh) * | 2017-09-22 | 2019-11-05 | 永嘉俊腾机械科技有限公司 | 一种磷酸盐型三元嵌段共聚物分散剂及其制备方法 |
KR20190057650A (ko) | 2017-11-20 | 2019-05-29 | 주식회사 에코웨이브 | 방오도료용 중합체 |
CN111886304B (zh) * | 2018-04-20 | 2022-02-01 | 日东化成株式会社 | 防污涂料组合物 |
JP7295694B2 (ja) * | 2018-05-10 | 2023-06-21 | 中国塗料株式会社 | 防汚塗料組成物 |
JP7287648B2 (ja) * | 2019-03-15 | 2023-06-06 | 日東化成株式会社 | 防汚塗料組成物 |
CN111171678A (zh) * | 2020-02-24 | 2020-05-19 | 中环海化(厦门)船舶智能涂料有限公司 | 一种含铜及铜合金粉的铜粉基接触型防污涂料及制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1030071A (ja) * | 1996-04-17 | 1998-02-03 | Nof Corp | 塗料組成物 |
JPH10168350A (ja) * | 1996-12-10 | 1998-06-23 | Mitsubishi Rayon Co Ltd | 防汚性塗料組成物 |
JP2004002819A (ja) * | 2002-04-19 | 2004-01-08 | Nippon Paint Co Ltd | 防汚塗料 |
JP2004307816A (ja) * | 2003-03-27 | 2004-11-04 | Mitsubishi Rayon Co Ltd | 塗料組成物及び共重合体 |
JP2006265560A (ja) * | 2001-12-26 | 2006-10-05 | Nippon Paint Co Ltd | アクリル樹脂及び防汚塗料 |
WO2010038692A1 (ja) * | 2008-09-30 | 2010-04-08 | 日本ペイント株式会社 | 塗料組成物およびその製造方法、塗膜、ならびに水中構造物 |
WO2011118526A1 (ja) * | 2010-03-23 | 2011-09-29 | 中国塗料株式会社 | 防汚塗料組成物およびその用途 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NO328137B1 (no) * | 2001-12-26 | 2009-12-14 | Nippon Paint Co Ltd | Akrylharpiks og antibegroingsbelegg |
JP5415551B2 (ja) * | 2009-10-13 | 2014-02-12 | 日本ペイントマリン株式会社 | 防汚塗料組成物、ならびに防汚塗膜、複合塗膜および水中構造物 |
-
2015
- 2015-10-15 SG SG10201903432QA patent/SG10201903432QA/en unknown
- 2015-10-15 JP JP2016555195A patent/JP6595494B2/ja not_active Expired - Fee Related
- 2015-10-15 EP EP15852068.4A patent/EP3211014A4/en not_active Withdrawn
- 2015-10-15 KR KR1020177013392A patent/KR20170074925A/ko unknown
- 2015-10-15 WO PCT/JP2015/079173 patent/WO2016063789A1/ja active Application Filing
- 2015-10-15 MY MYPI2017701141A patent/MY181589A/en unknown
- 2015-10-15 CN CN201580054381.4A patent/CN106795248B/zh not_active Expired - Fee Related
- 2015-10-15 SG SG11201702664YA patent/SG11201702664YA/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1030071A (ja) * | 1996-04-17 | 1998-02-03 | Nof Corp | 塗料組成物 |
JPH10168350A (ja) * | 1996-12-10 | 1998-06-23 | Mitsubishi Rayon Co Ltd | 防汚性塗料組成物 |
JP2006265560A (ja) * | 2001-12-26 | 2006-10-05 | Nippon Paint Co Ltd | アクリル樹脂及び防汚塗料 |
JP2004002819A (ja) * | 2002-04-19 | 2004-01-08 | Nippon Paint Co Ltd | 防汚塗料 |
JP2004307816A (ja) * | 2003-03-27 | 2004-11-04 | Mitsubishi Rayon Co Ltd | 塗料組成物及び共重合体 |
WO2010038692A1 (ja) * | 2008-09-30 | 2010-04-08 | 日本ペイント株式会社 | 塗料組成物およびその製造方法、塗膜、ならびに水中構造物 |
WO2011118526A1 (ja) * | 2010-03-23 | 2011-09-29 | 中国塗料株式会社 | 防汚塗料組成物およびその用途 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3211014A4 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018040863A1 (zh) * | 2016-08-30 | 2018-03-08 | 厦门双瑞船舶涂料有限公司 | 自抛光防污漆用的(甲基)丙烯酸锌-硅共聚物及其制备方法 |
JP2018070685A (ja) * | 2016-10-25 | 2018-05-10 | 中国塗料株式会社 | 防汚塗料組成物、防汚塗膜、防汚塗膜付き基材及びその製造方法、並びに防汚方法 |
JPWO2019069777A1 (ja) * | 2017-10-04 | 2020-11-05 | 日東化成株式会社 | 防汚塗料組成物、該組成物を用いて形成される防汚塗膜を表面に有する塗装物 |
JP7213554B2 (ja) | 2017-10-04 | 2023-01-27 | 日東化成株式会社 | 防汚塗料組成物、該組成物を用いて形成される防汚塗膜を表面に有する塗装物 |
JP6490277B1 (ja) * | 2018-04-13 | 2019-03-27 | 関西ペイント株式会社 | 防汚塗料組成物、及びその塗膜を有する塗装物品 |
JP2019183050A (ja) * | 2018-04-13 | 2019-10-24 | 関西ペイント株式会社 | 防汚塗料組成物、及びその塗膜を有する塗装物品 |
WO2021180588A2 (en) | 2020-03-09 | 2021-09-16 | Jotun A/S | Hull cleaning robot |
WO2021191388A1 (en) | 2020-03-27 | 2021-09-30 | Jotun A/S | Antifouling coating composition |
WO2022191100A1 (ja) * | 2021-03-12 | 2022-09-15 | 日東化成株式会社 | 防汚塗料組成物 |
GB202107159D0 (en) | 2021-03-23 | 2021-06-30 | Jotun As | Monitoring a vessel |
WO2022200427A1 (en) | 2021-03-23 | 2022-09-29 | Jotun A/S | Monitoring a vessel |
WO2022200430A1 (en) | 2021-03-23 | 2022-09-29 | Jotun A/S | Monitoring the cleanliness of an underwater surface of a stationary object |
Also Published As
Publication number | Publication date |
---|---|
EP3211014A4 (en) | 2017-10-25 |
JP6595494B2 (ja) | 2019-10-23 |
EP3211014A1 (en) | 2017-08-30 |
JPWO2016063789A1 (ja) | 2017-08-31 |
KR20170074925A (ko) | 2017-06-30 |
CN106795248B (zh) | 2019-06-07 |
SG10201903432QA (en) | 2019-05-30 |
SG11201702664YA (en) | 2017-05-30 |
CN106795248A (zh) | 2017-05-31 |
MY181589A (en) | 2020-12-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6595494B2 (ja) | 防汚塗料組成物用共重合体、防汚塗料組成物、防汚塗膜 | |
JP5632566B1 (ja) | 防汚塗料組成物、該組成物を用いて形成される防汚塗膜を表面に有する塗装物 | |
JP5747198B2 (ja) | 防汚塗料組成物、防汚塗料組成物用共重合体の製造方法、該組成物を用いて形成される防汚塗膜を表面に有する塗装物 | |
JP4228107B2 (ja) | 防汚塗料組成物、該組成物の製造方法、該組成物を用いて形成される防汚塗膜、該塗膜を表面に有する塗装物、及び該塗膜を形成する防汚処理方法 | |
JP4769331B1 (ja) | 防汚塗料組成物、防汚塗料組成物用共重合体、該組成物を用いて形成される防汚塗膜を表面に有する塗装物 | |
US7977407B1 (en) | Antifouling coating composition, antifouling coating film formed from the composition, coated object having the coating film on surface, and method of antifouling by forming the coating film | |
JP4340777B2 (ja) | 防汚塗料組成物、該組成物の製造方法、該組成物を用いて形成される防汚塗膜、該塗膜を表面に有する塗装物、及び該塗膜を形成する防汚処理方法 | |
JP2011026357A (ja) | 防汚塗料組成物、該組成物の製造方法、該組成物を用いて形成される防汚塗膜、該塗膜を表面に有する塗装物、及び該塗膜を形成する防汚処理方法 | |
JP6621121B2 (ja) | 防汚塗料組成物用共重合体、防汚塗料組成物、該組成物を用いて形成される防汚塗膜、該塗膜を表面に有する塗装物、及び該塗膜を形成する防汚処理方法 | |
JP2012251158A (ja) | 防汚塗料組成物、防汚塗膜、該防汚塗膜で被覆された船舶または水中構造物、並びに船舶外板または水中構造物の防汚方法 | |
JP6624665B1 (ja) | 防汚塗料組成物用共重合体、該共重合体を含む防汚塗料組成物 | |
JP6954649B2 (ja) | 防汚塗料組成物、該組成物を用いて形成される防汚塗膜を表面に有する塗装物 | |
KR20200062269A (ko) | 방오 도료 조성물, 이 조성물을 이용하여 형성되는 방오 도막을 표면에 갖는 도장물 | |
JP2007186705A (ja) | 防汚塗料組成物、防汚塗膜、該防汚塗膜で被覆された船舶または水中構造物、並びに船舶外板または水中構造物の防汚方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15852068 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016555195 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015852068 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11201702664Y Country of ref document: SG |
|
ENP | Entry into the national phase |
Ref document number: 20177013392 Country of ref document: KR Kind code of ref document: A |