WO2019069778A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2019069778A1 WO2019069778A1 PCT/JP2018/035888 JP2018035888W WO2019069778A1 WO 2019069778 A1 WO2019069778 A1 WO 2019069778A1 JP 2018035888 W JP2018035888 W JP 2018035888W WO 2019069778 A1 WO2019069778 A1 WO 2019069778A1
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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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
Definitions
- the present invention relates to an antifouling coating composition and a coated article having an antifouling coating film formed using the composition on the surface.
- Waterborne fouling organisms such as barnacles, celpras, blue mussels, scabs, sea squirts, sea squirts, sea bream, sea bream, seaweed, slime etc., underwater structures such as fishing tools such as ships (especially ship bottom), fishing nets, fishing net accessories etc.
- fishing tools such as ships (especially ship bottom), fishing nets, fishing net accessories etc.
- the antifouling coating composition is applied to a ship or the like to form an antifouling coating film, and the antifouling agent is released from the antifouling coating film to release the antifouling agent for a long period of time.
- Patent Document 1 a technology for exhibiting performance
- the present invention has been made in view of such circumstances, maintains stable coating film dissolution rate in seawater for a long period of time, and has stable antifouling performance without causing coating film abnormality such as cracks.
- An antifouling coating composition capable of maintaining
- the copolymer (A), the ester compound (B) and the copper suboxide (C) are contained, and the copolymer (A) is a triorganosilyl group-containing monomer (a) And a triorganosilyl ester-containing copolymer obtained from a mixture of an oxygen atom-containing monomer (b) and an ethylenically unsaturated monomer (c), and the monomer (a) has a chemical formula (C) 1), the monomer (b) is represented by the chemical formula (2), and the monomer (c) is a monomer other than the monomer (a) and the monomer (b).
- a monomer, and copolymerizable with the monomer (a) and the monomer (b), and the ester compound (B) is at least represented by the chemical formulas (3) to (9)
- An antifouling paint composition is provided, which comprises one ester compound.
- the inventors of the present invention conducted intensive studies and found that by adding a specific ester compound (B) to the copolymer (A) and copper suboxide (C) having a specific configuration, copper suboxide on the coating film surface
- the present inventors have found that the antifouling property is maintained over a long period of time by adjusting the dissolution rate of H.sub.2 and adjusting the dissolution rate of H.sub.2 to adjust the dissolution rate of the resin, resulting in the completion of the present invention.
- the antifouling-paint composition which can form the antifouling coating film in which high antifouling performance is maintained over a long period of time is provided.
- FIG. 1 It is an image (SEM image and elemental mapping of Cu, Fe, Ti by EDS) of SEM-EDS of Example 1.
- FIG. 2 It is an image (SEM image and elemental mapping of Cu, Fe, Ti by EDS) of the SEM-EDS of the comparative example 1.
- FIG. 1 It is an image (SEM image and elemental mapping of Cu, Fe, Ti by EDS) of the SEM-EDS of the comparative example 1.
- the antifouling coating composition of the present invention contains a copolymer (A), an ester compound (B), and copper suboxide (C).
- Copolymer (A) The copolymer (A) is a triorganosilyl obtained from a mixture of a triorganosilyl group-containing monomer (a), an oxygen atom-containing monomer (b) and an ethylenically unsaturated monomer (c). It is an ester containing copolymer.
- a triorganosilyl group-containing monomer
- b oxygen atom-containing monomer
- c ethylenically unsaturated monomer
- It is an ester containing copolymer.
- the synthesis method of the monomer (a), the monomer (b), the monomer (c), and the copolymer (A) will be specifically described.
- the monomer (a) has a structure represented by the chemical formula (1).
- X represents an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group.
- the hydrocarbon group having a carbon number of 3 to 8 and branched at the ⁇ -position is, for example, isopropyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1,1-Dimethylpropyl, 1,1-Dimethylbutyl, Texyl, cyclohexyl, 1,1-Dimethylpentyl, 1-Methylhexyl, 1,1-Dimethylhexyl, 1-Methylheptyl, etc. It can be mentioned.
- hydrocarbon group whose ⁇ -position is branched examples include a 2,2-dimethylpropyl group, a cyclohexylmethyl group, a 2-ethylhexyl group, a 2-propylpentyl group and the like.
- R is preferably the same or different and is an isopropyl group, an s-butyl group, a t-butyl group, a phenyl group or a 2-ethylhexyl group, more preferably an isopropyl group preferable.
- the monomer (a) for example, triisopropylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, diisopropyl s-butylsilyl (meth) acrylate, (Meth) acrylic acid diisopropyl t-butylsilyl, (meth) acrylic acid diisopropyl texylsilyl, (meth) acrylic acid diisopropylphenylsilyl, (meth) acrylic acid isopropyl di-s-butylsilyl, (meth) acrylic acid isopropyldiphenylsilyl, ( (Meth) acrylic acid diphenyltexylsilyl, (meth) acrylic acid t-butyldiphenylsilyl, (meth) acrylic acid diisopropylcyclohexylsilane, (meth) acrylic acid tricyclohex
- triisopropylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, and (meth) acrylic acid are preferred because they are less likely to cause coating film abnormalities and can form an antifouling coating excellent in water resistance.
- t-Butyldiphenylsilyl and tri (2-) ethylhexylsilyl (meth) acrylate are preferred, and triisopropyl (meth) acrylate is more preferred.
- These (meth) acrylic acid triorganosilyl ester monomers are used alone or in combination of two or more.
- the monomer (b) has a structure represented by the chemical formula (2).
- Y-R ... (2) (Wherein R represents an alkyl or aryl group having an oxygen atom of 2 to 10 carbon atoms, and Y represents an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group).
- the monomer (b) is an oxygen atom-containing ethylenic unsaturated monomer copolymerizable with the monomer (a), for example, 2-methoxyethyl (meth) acrylate, (meth) acrylic acid 2 -Methoxypropyl, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, diethylene glycol monomethyl (meth) acrylate, (meth) Propylene glycol monomethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc.
- 2-methoxyethyl (meth) acrylate for example, 2-methoxyeth
- the monomer (b) of the said illustration can be used individually or as 2 or more types as a monomer component of the said copolymer (A).
- the monomer (c) is a monomer other than the monomer (a) and the monomer (b), and can be copolymerized with the monomer (a) and the monomer (b) Ethylenic unsaturated monomer.
- Monomer (c) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate ( (Meth) acrylate zinc, (meth) acrylate copper, (meth) acrylate zinc versatate, (meth) acrylate copper versatate, (meth) acrylate zinc naphthenate, (meth) acrylate copper naphthenate, ( (Meth) acrylic acid esters of (meth) acrylic acid stearate, zinc
- (meth) acrylic acid esters are particularly preferable, and methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylate 2-ethylhexyl, zinc (meth) acrylate, zinc naphthenate (meth) acrylate, copper abietic acid (meth) acrylate, zinc zinc (meth) acid, zinc zinc (meth) acid, copper More preferable.
- the monomer (c) of the said illustration can be used individually or as 2 or more types as a monomer component of the said copolymer (A).
- the copolymer (A) is obtained by polymerizing a mixture of the monomer (a), the monomer (b) and the monomer (c).
- the content of the monomer (a) in the mixture is preferably about 20 to 70% by mass, and more preferably about 30 to 60% by mass.
- the weight average molecular weight (Mw) of the copolymer (A) is preferably 10,000 to 100,000, and particularly preferably 20,000 to 70,000.
- the coating does not become brittle and the dissolution of the coating is appropriate, so that the desired antifouling effect can be exhibited effectively.
- GPC gel permeation chromatography
- the copolymer (A) is a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer of the monomer (a), the monomer (b) and the monomer (c). It may be any copolymer of unity.
- 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.
- polymerization initiator used in the polymerization reaction examples include, for example, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, dimethyl-2,2 ' -Azo compounds such as azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate, tert-butylperoxy 2-ethylhexanoate, Peroxides such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and 1,1,3,3-tetramethylbutylperoxyneodecanoate can be mentioned.
- AIBN 2,2'-azobisisobutyronitrile
- 2,2'-azobis-2-methylbutyronitrile dimethyl-2,2 ' -Azo compounds
- polymerization initiators can be used alone or in combination of two or more.
- the polymerization initiator in particular, AIBN, tert-butylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate or 1,1,3 Preferred is 3,3-tetramethylbutyl peroxy neodecanoate.
- the molecular weight of the copolymer (A) can be adjusted by appropriately setting the amount of the polymerization initiator used.
- a chain transfer agent such as mercaptan or ⁇ -methylstyrene dimer can also be used.
- polymerization method examples include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like.
- solution polymerization is preferable in that the copolymer (A) can be obtained easily and precisely.
- an organic solvent may be used if 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 Alcohol solvents such as alcohol, butyl alcohol and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether and dibutyl ether; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
- ester solvents ester solvents, alcohol solvents and aromatic hydrocarbon solvents are preferable, and butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, toluene and xylene are more preferable.
- These solvents may be used alone or in combination of two or more.
- the reaction temperature in the polymerization reaction may be appropriately set according to the type 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 carried out under an inert gas atmosphere such as nitrogen gas or argon gas.
- the content of the copolymer (A) in the composition of the present invention is not particularly limited, but is usually 2 to 50% by mass, preferably 4 to 25% by mass in the solid content of the composition of the present invention.
- the content of the copolymer (A) is 4% by mass to 25% by mass, an appropriate coating film dissolution rate and coating film physical property in seawater can be obtained, and stable surface renewal property can be maintained for a long time, A desired antifouling effect can be exhibited effectively. Moreover, the outstanding recoat performance of a coating film can be exhibited.
- ester compound (B) The ester compound (B) of the present invention contains at least one ester compound (3) to (9) represented by the chemical formulas (3) to (9).
- the ester compound (3) has a structure represented by the chemical formula (3).
- the ester compound (3) is, for example, an aliphatic chain ester or an aromatic ester, and is, for example, an ester compound in which a monocarboxylic acid and a monoalcohol are ester-bonded.
- R 1 is an aliphatic hydrocarbon group which may contain a hetero atom.
- R 1 has an aromatic ring. The aromatic ring is preferably directly bonded to the carbon atom of the carbonyl group.
- R 1 and R 2 are each a hydrocarbon group having 1 to 22 carbon atoms which may contain a hetero atom, and the hydrocarbon group is aliphatic or aromatic and is linear or branched. It has a chain or cyclic structure.
- the carbon number of the hydrocarbon group of R 1 and R 2 is preferably 2 to 18, and specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 and may be in the range between any two of the numerical values exemplified here.
- Examples of the hetero atom of R 1 and R 2 include an oxygen atom, a sulfur atom, and a nitrogen atom.
- ester compound (3) examples include aliphatic esters such as decyl decanoate, geranyl acetate, isopropyl myristate, isopropyl palmitate, benzyl isovalerate, benzyl acetoacetate, p-tolyl n-octanoic acid, 7, Examples thereof include benzyl 8-epoxystearate, octyl 9,10-epoxystearate, cetyl stearate and the like.
- aliphatic esters such as decyl decanoate, geranyl acetate, isopropyl myristate, isopropyl palmitate, benzyl isovalerate, benzyl acetoacetate, p-tolyl n-octanoic acid, 7, Examples thereof include benzyl 8-epoxystearate, octyl 9,10-epoxystearate, cetyl stearate and the like.
- ester compound (3) examples include, for aromatic esters, isoamyl phenylacetate, 2-ethylhexyl benzoate, hexyl 4-hydroxybenzoate and the like.
- the ester compound (4) has a structure represented by the chemical formula (4).
- the ester compound (4) is, for example, an aliphatic chain ester, and is, for example, an ester compound in which a dicarboxylic acid and two monoalcohols are ester-bonded.
- X and R each represents a hydrocarbon group having 1 to 22 carbon atoms which may contain a hetero atom, and the hydrocarbon group is aliphatic or aromatic, and is linear, branched, or It has a cyclic structure, and two R's are the same or different.
- the carbon number of the hydrocarbon group of X and R is preferably 2 to 18, and specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12. , 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 and may be in the range between any two of the numerical values exemplified here.
- a hetero atom of X and R an oxygen atom, a sulfur atom, a nitrogen atom etc. are mentioned.
- X is an alkylene group having 2 to 16 carbon atoms.
- ester compound (4) examples include di 2-ethylhexyl succinate, di 2-butoxyethyl adipate, di 2-ethyl hexyl adipate, diisononyl adipate, di 2-ethyl hexyl azelate, di 2-ethyl hexyl sebacate Etc.
- the ester compound (5) has a structure represented by the chemical formula (5).
- the ester compound (5) is, for example, an ethylene glycol ester, and is, for example, an ester compound in which two monocarboxylic acids and a dialcohol are ester-bonded.
- X is an oxygen atom or a hydrocarbon group having 1 to 22 carbon atoms containing an oxygen atom, and the hydrocarbon group is aliphatic or aromatic and is linear or branched.
- R 1 and R 2 each is a hydrocarbon group having 1 to 22 carbon atoms which may contain a hetero atom, and the hydrocarbon group is aliphatic or aromatic, and R 3 and R 4 are each a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms which may contain a hetero atom, and this hydrocarbon group Is aliphatic or aromatic and has a linear, branched or cyclic structure, m is an integer of 1 to 20, and two R 3 's are the same or different, and two R 4' s are , Identical or different, m is an integer of 1 to 20.)
- the ester compound (5) preferably contains an ester compound represented by the chemical formula (15). That is, in the chemical formula (5), it is preferable that X be an oxygen atom and R 3 and R 4 be a hydrogen atom.
- the carbon number of the hydrocarbon group of X and R 1 to R 4 is preferably 2 to 18, and specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 , 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 and may be in the range between any two of the numerical values exemplified here.
- Examples of the hetero atom of R 1 to R 4 include an oxygen atom, a sulfur atom, and a nitrogen atom.
- m is preferably 1 to 10, and specifically, for example, specifically, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 , 16, 17, 18, 19, 20, and may be in the range between any two of the numerical values exemplified here.
- ester compound (5) examples include diethylene glycol dibenzoate, triethylene glycol di (2-ethylhexanoate), propylene glycol dilaurate and the like.
- the ester compound (6) has a structure represented by the chemical formula (6).
- the ester compound (6) is, for example, an aromatic ester, and is, for example, an ester compound in which an aromatic dicarboxylic acid and two monoalcohols are ester-bonded.
- two R 1 s are the same or different and each is a hydrocarbon group having 1 to 22 carbon atoms which may contain a hetero atom, and the hydrocarbon group is aliphatic or aromatic and is linear
- Each of R 2 to R 4 is a hydrocarbon group having 1 to 22 carbon atoms which may be a hydrogen atom or may contain a hetero atom, and the hydrocarbon group is a branched or cyclic structure.
- Aliphatic or aromatic, having a linear, branched or cyclic structure, and two R 3 's may be the same or different
- the carbon number of the hydrocarbon group of R 1 to R 4 is preferably 2 to 18, and specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 and may be in the range between any two of the numerical values exemplified here.
- Examples of the hetero atom of R 1 to R 4 include an oxygen atom, a sulfur atom, and a nitrogen atom.
- R 2 to R 4 are preferably hydrogen atoms.
- ester compound (6) examples include diethyl isophthalate, cyclohexyl isophthalate, di-2-ethylhexyl isophthalate, di n-octyl isophthalate, and diisononyl isophthalate.
- the ester compound (7) has a structure represented by the chemical formula (7).
- the ester compound (7) is, for example, an aromatic ester, and is, for example, an ester compound in which an aromatic dicarboxylic acid and two monoalcohols are ester-bonded.
- two R 1 s are the same or different and each is a hydrocarbon group having 1 to 22 carbon atoms which may contain a hetero atom, and the hydrocarbon group is aliphatic or aromatic and is linear
- the four R 2 s are hydrocarbon groups having 1 to 22 carbon atoms which may be the same or different and each may be a hydrogen atom or may contain a hetero atom, and this hydrocarbon group is a branched or cyclic structure. Is aliphatic or aromatic and has a linear, branched or cyclic structure.
- the carbon number of the hydrocarbon group of R 1 to R 2 is preferably 2 to 18, and specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 and may be in the range between any two of the numerical values exemplified here.
- Examples of the hetero atom of R 1 to R 2 include an oxygen atom, a sulfur atom and a nitrogen atom.
- R 2 is preferably a hydrogen atom.
- ester compound (7) examples include diethyl terephthalate, cyclohexyl terephthalate, di 2-ethylhexyl terephthalate, di n-octyl terephthalate, and diisononyl terephthalate.
- the ester compound (8) has a structure represented by the chemical formula (8).
- the ester compound (8) is, for example, an aromatic ester, and is, for example, an ester compound in which an aromatic tricarboxylic acid and three monoalcohols are ester-bonded.
- R 1 to R 3 are each a hydrocarbon group having 1 to 22 carbon atoms which may contain a hetero atom, and this hydrocarbon group is aliphatic or aromatic, and is linear or branched.
- Each of R 4 to R 6 is a hydrocarbon group having 1 to 22 carbon atoms which may be a hydrogen atom or may contain a hetero atom, and the hydrocarbon group is an aliphatic group. Or aromatic, having a linear, branched or cyclic structure
- the carbon number of the hydrocarbon group of R 1 to R 6 is preferably 2 to 18, and specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 and may be in the range between any two of the numerical values exemplified here.
- Examples of the hetero atom of R 1 to R 6 include an oxygen atom, a sulfur atom, and a nitrogen atom.
- R 4 to R 6 are preferably hydrogen atoms.
- ester compound (8) examples include trimethyl trimellitate, tri 2-ethylhexyl trimellitate, tri n-octyl trimellitate, triisononyl trimellitate and the like.
- the ester compound (9) has a structure represented by the chemical formula (9).
- the ester compound (9) is, for example, an aromatic ester, and is, for example, an ester compound in which a tetracarboxylic acid and four monoalcohols are ester-bonded.
- R 1 s are the same or different and each is a hydrocarbon group having 1 to 22 carbon atoms which may contain a hetero atom, this hydrocarbon group is aliphatic or aromatic, and is linear
- the two R 2 s are the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms which may contain a hetero atom, and this hydrocarbon group is a branched or cyclic structure. Is aliphatic or aromatic and has a linear, branched or cyclic structure.
- the carbon number of the hydrocarbon group of R 1 to R 2 is preferably 2 to 18, and specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 and may be in the range between any two of the numerical values exemplified here.
- Examples of the hetero atom of R 1 to R 2 include an oxygen atom, a sulfur atom and a nitrogen atom.
- R 2 is preferably a hydrogen atom.
- ester compound (8) examples include tetramethyl pyromellitic acid, tetra 2-ethylhexyl pyromellitic acid, tetra n-octyl pyromellitic acid, tetraisononyl pyromellitic acid, and the like.
- ester compound (B) is not particularly limited, and those produced by known methods, those commercially available, those available as reagents, and the like can be used.
- Examples of known production methods include dehydration condensation reaction with carboxylic acids and alcohols, transesterification reaction with esters and alcohols, and ester synthesis reaction of carboxylic acid chlorides with alcohols. Also, for some ester compounds, partial conversion of commercially available products such as epoxidation or hydrogenation of unsaturated moieties of similar compounds available as commercially available products, or substitution reactions of commercially available ester compounds, coupling reactions, etc. It can be manufactured by
- pyromellitic acid tetra 2-ethylhexyl ester is "UL-80 (trade name)” manufactured by ADEKA Co., Ltd.
- di 2-ethylhexyl terephthalate is And triethylene glycol bis (2-ethylhexanoate) include Sanko Co., Ltd. “Proviplast 1783”).
- the ester compound (B) of the present invention is contained in an amount of 0.1 to 15% by mass, preferably 0.4 to 10% by mass, based on the solid content of the composition of the present invention, particularly preferably 0.5 to 8 % Mass% is contained.
- the content of the ester compound (B) is within the above range, the dissolution rate of cuprous oxide and the dissolution rate of the resin are matched, and long-term antifouling properties are maintained.
- no coating abnormality (such as cracks) occurs in the antifouling coating after being immersed in seawater for a certain period of time.
- Copper suboxide (C) The content of copper suboxide (C) in the composition of the present invention is not particularly limited, but the content ratio with the ester compound (B) is, in terms of solid content, the mass ratio (copper suboxide (C) / the above The ester compound (B)) is usually 0.5 to 120, preferably 1 to 90, more preferably 3 to 60. When the content of the antifouling agent (G) is within the above range, the long-term antifouling property is maintained.
- the long-term antifouling property is more remarkably maintained. It is preferable from the viewpoint of long-term stability during storage that the above cuprous oxide (C) is surface-treated with glycerin, sucrose, stearic acid, lauric acid, licistine, mineral oil and the like, glycerin, sucrose, When coated with any of stearic acid, the above-mentioned long-term antifouling property is more remarkably maintained.
- the antifouling coating composition according to the present invention may contain, in addition to the copolymer (A), the ester compound (B) and the copper suboxide (C), if necessary, a thermoplastic resin (D), others Resin (E), other additives (F), other antifouling agents (G), etc. can be blended. Thereby, the further outstanding antifouling effect can be exhibited.
- thermoplastic resin (D) examples include rosin, rosin derivatives and metal salts thereof, monocarboxylic acids and salts thereof, and alicyclic hydrocarbon resins.
- Examples of the rosin include tall oil rosin, gum rosin, wood rosin and the like.
- Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleinized rosin, formylated rosin, polymerized rosin and the like.
- a metal salt of rosin and a metal salt of a rosin derivative a reaction product of a metal compound and rosin can be used.
- As a metal salt of rosin for example, gum rosin zinc (or copper) salt, wood rosin zinc (or copper) salt, Tall oil rosin zinc (or copper) salt etc. are mentioned.
- metal salts of rosin derivatives hydrogenated rosin zinc (or copper) salts, disproportionated rosin zinc (or copper) salts, maleated rosin zinc (or copper) salts, formylated rosin zinc (or copper) salts, polymerization Examples include rosin zinc (or copper) salts and the like.
- Examples of the monocarboxylic acid include fatty acids having about 5 to 30 carbon atoms, synthetic fatty acids, and naphthenic acids.
- As salts of monocarboxylic acids copper salts, zinc salts, magnesium salts, calcium salts and the like can be mentioned.
- Quintone 1500, 1525L, 1700 (a brand name, Nippon Zeon company make) etc. are mentioned as a commercial item, for example.
- the composition of the present invention is a thermoplastic resin (D) from the group consisting of rosin, rosin derivatives and metal salts thereof in that appropriate coating hardness and water resistance can be imparted to the composition of the present invention. It is preferable to contain at least one selected, and it is particularly preferable to contain a rosin or a copper salt or zinc salt of a rosin derivative from the viewpoint of improvement in crack resistance and water resistance.
- the content of the thermoplastic resin (D) 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 thermoplastic resin (D) is less than 1 part by mass, the effect of preventing the adhesion of aquatic fouling organisms, in particular, the effect of preventing the adhesion of aquatic fouling organisms during the period of covering can not be expected.
- the content of the thermoplastic resin (D) exceeds 80 parts by mass, defects such as cracks and peeling easily occur in the coating film, and there is a possibility that the effect of preventing adhesion of aquatic fouling organisms can not be sufficiently exhibited.
- the content of the thermoplastic resin (D) is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 with respect to 100 parts by mass of the copolymer (A). , 60, 65, 70, 75, 80 parts by mass, and may be within the range of any two numerical values exemplified here.
- ⁇ Other resin (E)> By including another resin (E) in the antifouling coating composition of the present invention, cost reduction is possible without impairing the effects of the present invention, and a synergistic effect with physical properties of the resin (E) You can get As another resin (E), for example, (meth) acrylic resin, alkyd resin, polyester resin, chlorinated rubber resin, vinyl resin, petroleum resin, (modified) terpene phenol resin, cellulose resin, vinyl ether resin, epoxy resin, urethane Resin, metal-containing resin, zwitterionic compound-containing resin, silicone resin, etc. may be mentioned.
- another resin (E) for example, (meth) acrylic resin, alkyd resin, polyester resin, chlorinated rubber resin, vinyl resin, petroleum resin, (modified) terpene phenol resin, cellulose resin, vinyl ether resin, epoxy resin, urethane Resin, metal-containing resin, zwitterionic compound-containing resin, silicone resin, etc. may be mentioned.
- the other resin (E) in the composition of the present invention can be contained in a range in which the appropriate coating film dissolution rate in seawater and the physical properties of the coating film are not impaired, and the content thereof is A)
- the amount is 1 to 200 parts by mass, preferably 20 to 100 parts by mass with respect to 100 parts by mass.
- the other antifouling agent (G) is not particularly limited as long as it is a substance having a killing or repellent action on marine fouling organisms.
- inorganic drugs and organic drugs can be mentioned.
- the inorganic agent examples include copper thiocyanate (general name: copper of rhodan), cupronickel, copper powder, zinc oxide and the like. Among these, rodane copper is particularly preferable.
- organic agents include organic copper compounds such as 2-mercaptopyridine-N-oxide copper (general name: kappa pyrithione), 2-mercaptopyridine-N-oxide zinc (general name: zinc pyrithione), zinc ethylene bis dithiocarbamate
- Organic zinc compounds such as (general name: zineb), bis (dimethyldithiocarbamic acid) zinc (general name: dirham), bis (dimethyldithiocarbamate) ethylenebis (dithiocarbamate) dizinc (general name: polycarbamate);
- Organic boron compounds such as triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, 4-phenylpyridyl-diphenylborane, triphenylboron-n-octadecylamine, triphenyl [3- (2-ethylhexyloxy) propylamine] boron Maleimide compounds such as 2,4,6-
- zinc pyrithione, kappa pyrithione, pyridine triphenylborane, 4-isopropyl pyridyl-diphenylmethyl borane, betoxazine, dineb, seane 211 and irugalol 1051 are preferable, and kappa pyrithione, zinc pyrithione, seanee 211, pyridine triphenylborane and More preferred is betoxazine.
- These antifouling agents can be used alone or in combination of two or more.
- the content of the antifouling agent (G) in the composition of the present invention is not particularly limited, but it 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 is there.
- the content of the antifouling agent (G) exceeds 75% by mass, the coating film to be formed is fragile, and further, the adhesion to a coating film formed article is weak, and the function as the antifouling coating film is sufficiently I can not finish it.
- the antifouling coating composition of the present invention is, for example, a mixture containing the above-mentioned copolymer (A), ester compound (B), copper suboxide (C) and other additives and the like.
- the liquid can be produced by mixing and dispersing using a disperser.
- the content of the copolymer, the antifouling agent and the like in the mixed solution may be appropriately adjusted to be the content of the copolymer, the antifouling agent and the like in the antifouling coating composition, respectively.
- the liquid mixture is preferably one obtained by dissolving or dispersing various materials such as a copolymer and an antifouling agent in a solvent.
- the thing similar to the said organic solvent can be used.
- the disperser what can be used as a pulverizer can be used suitably, for example.
- commercially available homomixers, sand mills, bead mills and the like can be used.
- the mixture may be mixed and dispersed by using a container provided with a stirrer and glass beads for mixing and dispersing added thereto.
- the antifouling treatment method of the present invention forms an antifouling coating film on the surface of a to-be-coated film formed article using the above antifouling coating composition.
- the anti-soiling coating is gradually dissolved from the surface and the coating surface is constantly renewed, so that the adhesion of the water-borne fouling organism can be prevented.
- the antifouling effect can be exhibited continuously by applying the above composition.
- the antifouling coating film can be formed by applying the above antifouling coating composition to the surface (in whole or in part) of the article to be coated.
- the coating method include a brush coating method, a spray method, a dipping method, a flow coating method, and a spin coating method. These may be used alone or in combination of two or more. After application, let it dry.
- the drying temperature may be room temperature.
- the drying time may be appropriately set according to the thickness of the coating film and the like.
- the antifouling coating film of the present invention formed by using the above antifouling coating composition exhibits appropriate coating film dissolution rate and coating film properties in seawater, and can maintain stable surface renewal property over a long period of time The desired antifouling effect can be exhibited effectively. Moreover, it has the advantage that the outstanding recoat performance of a coating film can be exhibited.
- the thickness of the antifouling coating film may be appropriately set according to the type of the coating film formed article, the traveling speed of the ship, the temperature of seawater, and the like.
- the thickness of the antifouling coating is usually 50 to 700 ⁇ m, preferably 100 to 600 ⁇ 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 on the surface.
- the coated article of the present invention may have the antifouling coating on the entire surface, or may have on a part thereof.
- the coated article of the present invention is provided with a coating film excellent in long-term stable surface renewal and recoatability by improving the appropriate coating film dissolution rate and coating film properties in seawater, so In particular, it can be suitably used as a ship's bottom, fishery tools, underwater structures and the like.
- a coating film excellent in long-term stable surface renewal and recoatability by improving the appropriate coating film dissolution rate and coating film properties in seawater, so
- it can be suitably used as a ship's bottom, fishery tools, underwater structures and the like.
- the antifouling coating film is formed on the bottom surface of a ship, the antifouling coating film is gradually dissolved from the surface and the coating film surface is constantly updated, thereby preventing adhesion of water-borne fouling organisms. it can.
- the antifouling coating film is suitably suppressed in hydrolysis rate. Therefore, the ship can maintain the antifouling performance for a long period of time, and for example, it can exert antifouling effect for a long time with little adhesion / accumulation of a water fouling organism even in a stationary state such as during berthing or during installation period.
- an antifouling coating film can be suitably formed by directly applying the above antifouling coating film composition. This makes it possible to maintain the antifouling performance simply and at low cost.
- % In each production example, an example, and a comparative example shows 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. Device: Tosoh Corporation HLC-8220GPC Column ⁇ TSKgel Super HZM-M (made by Tosoh Corp.) 2 Flow ⁇ ⁇ ⁇ 0.35 mL / min Detector ... RI Column thermostat temperature ...
- the heating residue is a value measured in accordance with JIS K 5601-1-2: 1999 (ISO 3251: 1993) "paint component test method-heating residue".
- the solid content is a value calculated by rounding off the first place after the decimal point of the heating residue value obtained by the above method.
- the unit of the compounding quantity of each component in Table 1 is g.
- Coating compositions were prepared by blending the components shown in Tables 2 to 4 at the proportions (mass%) shown in these tables and mixing and dispersing them with glass beads having a diameter of 1.5 to 2.5 mm.
- Test examples 1 and 2 (rotary test and antifouling test) The test shown below was done about the paint composition of an Example and a comparative example.
- Test Example 1 (rotary test) A rotating drum of 515 mm in diameter and 440 mm in height was mounted at the center of the water tank, which was made to be rotatable by a motor. In addition, a cooling device for keeping the temperature of seawater constant and a pH automatic controller for keeping the pH of seawater constant were attached.
- the test plate was produced according to the following method. First, an anticorrosive paint (epoxy vinyl A / C) is applied on a hard polyvinyl chloride board (71 x 100 x 1 mm) so that the thickness after drying becomes about 50 to 250 ⁇ m, and dried. It formed.
- an anticorrosive paint epoxy vinyl A / C
- the paint compositions obtained in the examples and comparative examples are each coated on the anticorrosion coating film so that the thickness after drying is about 300 to 550 ⁇ m, and the obtained coated products are heated at 40 ° C.
- a test plate having an antifouling coating was produced.
- One of the prepared test plates was fixed to the rotating drum of the rotating device of the above apparatus so as to be in contact with seawater, and the rotating drum was rotated at a speed of 20 knots. Meanwhile, the temperature of seawater was kept at 25 ° C., the pH was kept at 8.0 to 8.2, and seawater was replaced weekly.
- the initial film thickness of each test plate and the remaining film thickness every three months after the test start are measured with a laser focus displacement meter, and the film thickness dissolved is calculated from the difference to calculate the amount of film dissolution per month ( ⁇ m / month Got). The measurement was performed for 24 months, and the coating film dissolution amount was calculated every 12 months.
- ⁇ Test Example 2 (Antifouling test)> The paint compositions obtained in the examples and comparative examples were applied to both sides of a hard polyvinyl chloride plate (100 ⁇ 200 ⁇ 2 mm) so that the thickness as a dried coating film was about 200 ⁇ m.
- the obtained coated product was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dried coating of about 200 ⁇ m in thickness.
- This test plate was immersed 1.5 m below the sea surface in Owase City, Mie, and fouling of the test plate due to deposits was observed every six months. The evaluation was performed by visually observing the state of the coating film surface, and was judged based on the following criteria.
- ⁇ There is no adhesion of fouling organisms such as shellfish and algae, and almost no slime.
- ⁇ There is no adhesion of fouling organisms such as shellfish and algae, and the level that it can be lightly wiped off with a thin brush of slime (the degree to which the coated surface can be seen) attached.
- ⁇ There is no adhesion of fouling organisms such as shellfish and algae, but slime adheres so thick that the coating film surface can not be seen, and even if it is wiped with a brush strongly, it is a level which can not be removed.
- X Level at which fouling organisms such as shellfish and algae are attached.
- the coating films formed using the coating compositions of the examples of the present invention maintain stable coating film dissolution amount during any period, and water resistance , It is understood that the crack resistance and the adhesion are good.
- AADBE Di 2-butoxyethyl adipate: trade name "Bis (2-butoxyethyl) Adipate” (manufactured by Tokyo Kasei Co., Ltd.)
- AAEH Di-2-ethylhexyl adipate: trade name "Bis (2-ethylhexyl) Adipate” (manufactured by Tokyo Kasei Co., Ltd.)
- AADiN diisononyl adipate: trade name "diisononyl adipate” (Wako Pure Chemical Industries, Ltd.)
- AzAEH Di 2-ethylhexyl azelate: trade name "Bis (2-ethylhexyl) Azelate” (manufactured by Tokyo Kasei Co., Ltd.)
- DOS Di 2-ethylhexyl sebacate: Brand name "Sancizer DOS” (made by Shin Nippon Rika Co., Ltd.)
- TEHTM Tri 2-ethylhexyl trimellitate: trade name "Tris (2-ethylhexyl) Trimellitate” (manufactured by Tokyo Kasei Co., Ltd.)
- Rosin solution about 50% solid solution of gum rosin (WW) solution in China Rosin zinc salt solution: used as prepared in Preparation Example 13 hydrogenated rosin solution: trade name "Hyper CH” (manufactured by Arakawa Chemical Co., Ltd.) 50% solid solution in xylene).
- NT-RMZ hydrogenated rosin zinc salt solution: trade name "NT-RMZ” (manufactured by Nitto Kasei Co., Ltd.) is used. 65% solids.
- MP25 Brand name "Laroflex (registered trademark) MP 25" (manufactured by BASF)
- EVA15 trade name "Novatec TM EVA LV440" (Japan Polyethylene Co., Ltd.)
- TP-217 trade name "Nichigo poly Esther TM TP-217” (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
- TP-290 trade name "Nichigo poly Esther TM TP-290” (Nippon Synthetic Chemical Industry Co., Ltd.)
- DOP Dioctyl phthalate: Brand name "DOP” (Mitsubishi Chemical Corporation)
- DINP diisononyl phthalate: trade name "diisononyl phthalate” (manufactured by Wako Pure Chemical Industries, Ltd.)
- DIDP diisodecyl phthalate: trade name "diisodecyl phthalate” (manufactured by Wako Pure Chemical Industries, Ltd.)
- ESBO Epoxidized soybean oil: Brand name "SANSO CIZER E-2000H” (manufactured by Shin Nippon Rika Co., Ltd.)
- Test example 3 (elemental analysis of the coating layer) After conducting a 18 month rotary test in the same manner as in Test Example 1 (rotary test), the test plate is dried at 25 ° C. for 72 hours, and the white water-based epoxy paint containing titanium oxide is dried on the test plate. Of about 200 to 500 .mu.m and dried at 25.degree. C. for 72 hours. The test plate after the end of the rotary test protected by the above operation was trimmed to an optimum size as a sample for SEM-EDS measurement, and cut out of a cross section and its surface were polished.
- osmium deposition is applied to the measurement sample, and SEM observation of the cross section of the test plate by SEM-EDS (JSM-6335F, JSM-6335F manufactured by JEOL Ltd.) (acceleration voltage: 20 kV, magnification) And element mapping (Cu, Fe, Ti) by EDS analysis were performed to obtain a SEM image and an element mapping image.
- the elemental mapping measurement time of EDS is about 12 minutes.
- the distribution range of Cu, Fe, and Ti is displayed respectively, and each image including the SEM image (the small on the left is four images) is displayed in an overlapping manner (the large one on the right).
- the presence or absence of a layer (skeleton layer) in which Cu derived from copper oxide (C) was eluted was confirmed, and the thickness of the layer was measured in ⁇ m order.
- FIG. 1 shows the result of a paint film made of the paint of Example 1
- FIG. 2 shows the result of a paint film made of the paint of Comparative Example 1.
- the layer having Cu distribution not observed is 11 ⁇ m in the surface layer, whereas in FIG. 2, the layer is formed 24 ⁇ m more than double.
- Fe is distributed to the layer in which distribution of Cu is not recognized, respectively.
- a layer in which the distribution of Cu is not observed in the surface layer of the coating means copper suboxide (C Is assumed to be a layer in which other components such as bengara and resin remained after dissolution from the surface layer, and the result is that after 24 months even if dissolution of the coating continues in the rotary test of Test Example 1,
- C Is assumed to be a layer in which other components such as bengara and resin remained after dissolution from the surface layer and the result is that after 24 months even if dissolution of the coating continues in the rotary test of Test Example 1
- the results of the deterioration of the coating film condition and the results of the reduction of the antifouling property after 18 months in the antifouling test of Test Example 2 are supported.
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Abstract
Description
本発明の防汚塗料組成物は、共重合体(A)、エステル化合物(B)、及び亜酸化銅(C)を含有する。
共重合体(A)は、トリオルガノシリル基含有単量体(a)と、酸素原子含有単量体(b)と、エチレン性不飽和単量体(c)の混合物から得られるトリオルガノシリルエステル含有共重合体である。以下、前記単量体(a)、前記単量体(b)、前期単量体(c)、前記共重合体(A)の合成方法等について具体的に説明する。
単量体(a)は、化学式(1)で表される構造を有する。
単量体(b)は、化学式(2)で表される構造を有する。
Y-R ...(2)
(式中、Rは炭素数2~10の酸素原子を有するアルキル基またはアリール基を示し、Yはアクリロイルオキシ基、メタクリロイルオキシ基、マレイノイルオキシ基、フマロイルオキシ基またはイタコノイルオキシ基を示す。)
単量体(c)は、前記単量体(a)及び前記単量体(b)以外の単量体であって、且つ単量体(a)および単量体(b)と共重合可能なエチレン性不飽和単量体である。単量体(c)は、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸i-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ラウリル、 (メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸ジエチルアミノエチル、(メタ)アクリル酸ベンジル、及び(メタ)アクリル酸フェニル、(メタ)アクリル酸亜鉛、(メタ)アクリル酸銅、(メタ)アクリル酸バーサチック酸亜鉛、(メタ)アクリル酸バーサチック酸銅、(メタ)アクリル酸ナフテン酸亜鉛、(メタ)アクリル酸ナフテン酸銅、(メタ)アクリル酸ステアリン酸亜鉛、(メタ)アクリル酸アビエチン酸銅、等の(メタ)アクリル酸エステル;塩化ビニル、塩化ビニリデン、(メタ)アクリロニトリル、酢酸ビニル、ブチルビニルエーテル、ラウリルビニルエーテル、N-ビニルピロリドン等のビニル化合物;スチレン、ビニルトルエン、α-メチルスチレン等の芳香族化合物等が挙げられる。この中でも特に、(メタ)アクリル酸エステルが好ましく、(メタ)アクリル酸メチル、 (メタ)アクリル酸エチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸i-ブチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸亜鉛、(メタ)アクリル酸ナフテン酸亜鉛、(メタ)アクリル酸アビエチン酸銅、(メタ)アクリル酸水添ロジン亜鉛、(メタ)アクリル酸水添ロジン銅、がより好ましい。前記例示の単量体(c)は、前記共重合体(A)のモノマー成分として単独又は二種以上で使用できる。
共重合体(A)は、前記単量体(a)、前記単量体(b)及び前記単量体(c)との混合物を重合させることにより得られる。前記混合物中における前記単量体(a)の含有量は20~70質量%程度が好ましく、30~60重量%程度がより好ましい。前記単量体(a)の含有量が30~60重量%程度の場合、得られる防汚塗料組成物を用いて形成した塗膜が、安定した塗膜溶解性を示し、長期間、防汚性能を維持できる。
共重合体(A)の重量平均分子量(Mw)は、好ましくは、10,000~100,000であり、特に好ましくは、20,000~70,000である。Mwが10,000~100,000の場合、塗膜が脆くならず、かつ、塗膜の溶解が適度であるため、所望の防汚効果を有効に発揮できる。Mwの測定方法としては、例えばゲル浸透クロマトグラフィー(GPC)が挙げられる。
本発明のエステル化合物(B)は、化学式(3)~(9)で表される少なくとも1種のエステル化合物(3)~(9)を含有する。
エステル化合物(3)は、化学式(3)で表される構造を有する。エステル化合物(3)は、例えば、脂肪族鎖状エステル又は芳香族エステルであり、例えば、モノカルボン酸とモノアルコールがエステル結合したエステル化合物である。エステル化合物(3)が脂肪族鎖状エステルである場合、R1はヘテロ原子を含んでもよい脂肪族炭化水素基である。一方、エステル化合物(3)が芳香族エステルである場合、R1が芳香環を有している。この芳香環は、カルボニル基の炭素原子に直接結合していることが好ましい。
エステル化合物(4)は、化学式(4)で表される構造を有する。エステル化合物(4)は、例えば、脂肪族鎖状エステルであり、例えば、ジカルボン酸と2つのモノアルコールがエステル結合したエステル化合物である。
エステル化合物(5)は、化学式(5)で表される構造を有する。エステル化合物(5)は、例えば、エチレングリコール系エステルであり、例えば、2つのモノカルボン酸とジアルコールがエステル結合したエステル化合物である。
エステル化合物(6)は、化学式(6)で表される構造を有する。エステル化合物(6)は、例えば、芳香族エステルであり、例えば、芳香族ジカルボン酸と2つのモノアルコールがエステル結合したエステル化合物である。
エステル化合物(7)は、化学式(7)で表される構造を有する。エステル化合物(7)は、例えば、芳香族エステルであり、例えば、芳香族ジカルボン酸と2つのモノアルコールがエステル結合したエステル化合物である。
エステル化合物(8)は、化学式(8)で表される構造を有する。エステル化合物(8)は、例えば、芳香族エステルであり、例えば、芳香族トリカルボン酸と3つのモノアルコールがエステル結合したエステル化合物である。
エステル化合物(9)は、化学式(9)で表される構造を有する。エステル化合物(9)は、例えば、芳香族エステルであり、例えば、テトラカルボン酸と4つのモノアルコールがエステル結合したエステル化合物である。
エステル化合物(B)は、特に制限なく、公知の方法で製造したものや、市販品、試薬等で入手できるもの等が使用できる。
本発明の組成物中における亜酸化銅(C)の含有量は、特に制限されないが、エステル化合物(B)との含有割合が、固形分換算で、質量比(亜酸化銅(C)/前記エステル化合物(B))、通常0.5~120であり、好ましくは1~90で、より好ましくは3~60である。防汚薬剤(G)の含有量が前記範囲内にあるとき、長期の防汚性が保たれる。
前記亜酸化銅(C)が、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好ましく、グリセリン、ショ糖、ステアリン酸のいずれかでコーティングされている時、前記、長期防汚性がさらに顕著に保たれる。
本発明における防汚塗料組成物には、共重合体(A)、エステル化合物(B)および亜酸化銅(C)のほかに、必要に応じて、熱可塑性樹脂(D)、他の樹脂(E)、他の添加剤(F)、他の防汚薬剤(G)等を配合することができる。これにより、さらに優れた防汚効果を発揮できる。
熱可塑性樹脂(D)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。
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。
他の樹脂(E)としては、例えば(メタ)アクリル樹脂、アルキド樹脂、ポリエステル樹脂、塩化ゴム樹脂、ビニル樹脂、石油樹脂、(変性)テルペンフェノール樹脂、セルロース系樹脂、ビニルエーテル樹脂、エポキシ樹脂、ウレタン樹脂、金属含有樹脂、双極性イオン化合物含有樹脂、シリコーン樹脂、等が挙げられる。
本発明の組成物中における他の樹脂(E)は、海水中での適度な塗膜溶解速度と塗膜物性が損なわれない範囲で含有することができ、その含有量は、共重合体(A)100質量部に対して1~200質量部、好ましくは20~100質量部である。
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、可塑剤、有機溶媒等を、海水中での適度な塗膜溶解速度と塗膜物性が損なわれない範囲で添加することができる。
他の防汚薬剤(G)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。
本発明の防汚塗料組成物は、例えば、前記共重合体(A)、エステル化合物(B)、亜酸化銅(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。
前記混合液中における前記共重合体及び防汚薬剤等の含有量は、それぞれ防汚塗料組成物中の共重合体及び防汚薬剤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、共重合体及び防汚薬剤等の各種材料を溶媒に溶解または分散させたものであることが好ましい。前記溶媒としては、上記有機溶媒と同様のものを使用できる。
前記分散機としては、例えば、微粉砕機として使用できるものを好適に用いることができる。例えば、市販のホモミキサー、サンドミル、ビーズミル等を使用することができる。また、撹拌機を備えた容器に混合分散用のガラスビーズ等を加えたものを用い、前記混合液を混合分散してもよい。
本発明の防汚処理方法は、上記防汚塗料組成物を用いて被塗膜形成物の表面に防汚塗膜を形成する。本発明の防汚処理方法によれば、前記防汚塗膜が表面から徐々に溶解し塗膜表面が常に更新されることにより、水棲汚損生物の付着防止を図ることができる。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。
防汚塗膜は、上記防汚塗料組成物を被塗膜形成物の表面(全体又は一部)に塗布することにより形成できる。塗布方法としては、例えば、ハケ塗り法、スプレー法、ディッピング法、フローコート法、スピンコート法等が挙げられる。これらは、1種又は2種以上を併用して行ってもよい。
塗布後、乾燥させる。乾燥温度は、室温でよい。乾燥時間は、塗膜の厚み等に応じて適宜設定すればよい。
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(東ソー株式会社製)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。なお、固形分は上記方法で得られた加熱残分値の小数点以下第一位を四捨五入して算出した値である。
また、表1中の各成分の配合量の単位はgである。
<製造例1(単量体(c)-1含有溶液の製造)>
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、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、加熱残分が50%になるようにPGMを添加して、単量体(c)-1含有溶液を得た。この溶液の固形分は50.5%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)350g、水酸化銅96g、水3gを仕込み、75℃まで加温した。その後アクリル酸70gと水添ロジン(ハイペールCH(荒川化学工業(株)製)330gの混合液を3時間かけて滴下した。滴下終了後、さらに5時間熟成すると、濃緑色透明液体となった。その後冷却し、加熱残分が50%になるようにPGMを添加して、単量体(c)-2含有溶液を得た。この溶液の固形分は50.2%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200gを仕込み、窒素雰囲気下、85±5℃で攪拌しながら、アクリル酸トリイソプロピルシリル270g、メタクリル酸メチル200g、アクリル酸2-メトキシエチル30g、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2.4g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0.3gを1時間毎に5回添加して重合反応を完結した後、加熱残分が50%になるようにキシレンを添加し溶解させることにより、トリオルガノシリルエステル含有共重合体溶液A-1を得た。得られた共重合体溶液の粘度は300mPa・s(25℃)、加熱残分は49.5%、Mwは47,700であった。
表1に示す有機溶剤、単量体及び重合開始剤をそれぞれ記載量用いて、製造例3と同様の操作で重合を行い、共重合体溶液A-2~A-7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、単量体及び重合開始剤をそれぞれ記載量用いて、製造例3と同様の操作で重合を行い、他の樹脂溶液E-1~E-3を得た。得られた各樹脂溶液の加熱残分、粘度、及び重量平均分子量を測定した。結果を表1に示す。
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、固形分約50%)を得た。得られたキシレン溶液の加熱残分は、50.6%であった。
表2~表4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。
実施例・比較例の塗料組成物について、以下に示す試験を行った。
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、硬質塩ビ板(71×100×1mm)上に、防錆塗料(エポキシビニル系A/C)を乾燥後の厚みが50~250μm程度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300~550μm程度となるよう塗布し、得られた塗布物を40℃で3日間乾燥させることにより、防汚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。
○: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
実施例及び比較例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6ヶ月経過ごとに観察した。
評価は、塗膜表面の状態を目視観察することにより行い、以下の基準で判断した。
○: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、塗膜面が見えない程スライムが厚く付着しており、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。
また、この効果は、塗料組成を種々変更しても、維持されることも明らかである(実施例15~28)。
(エステル化合物(B))
[エステル化合物(3)]
PAiPr:パルミチン酸イソプロピル:商品名「Isopropyl Palmitate」(東京化成(株)製)
DAD:デカン酸デシル:商品名「Decyl Decanoate」(東京化成(株)製)
BAEH:2-エチルヘキシルベンゾエート:商品名「2-Ethylhexyl Benzoate」(東京化成(株)製)
AADBE:アジピン酸ジ2-ブトキシエチル:商品名「Bis(2-butoxyethyl) Adipate」(東京化成(株)製)
AAEH:アジピン酸ジ2-エチルヘキシル:商品名「Bis(2-ethylhexyl) Adipate」(東京化成(株)製)
AADiN:アジピン酸ジイソノニル:商品名「アジピン酸ジイソノニル」(和光純薬工業(株)製)
AzAEH:アゼライン酸ジ2-エチルヘキシル:商品名「Bis(2-ethylhexyl) Azelate」(東京化成(株)製)
DOS:セバシン酸ジ2-エチルヘキシル:商品名「サンソサイザー DOS」(新日本理化(株)製)
DEGDB:ジエチレングリコールジベンゾアート:商品名「Diethylene Glycol Dibenzoate」(東京化成(株)製)
P-1783:トリエチレングリコールジ(2-エチルヘキサノエート):商品名「Proviplast 1783」(三光(株)製)
m-PAEH:イソフタル酸ジ2-エチルヘキシル:商品名「Bis(2-ethylhexyl) Isophthalate」(東京化成(株)製)
p-PAEH: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)
TEHTM: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)
UL-80:ピロメリット酸テトラ2-エチルヘキシル:商品名「UL-80」(ADEKA(株)製)
亜酸化銅:商品名「NC-301」(日進ケムコ(株)製)
ロジン溶液:中国産ガムロジン(WW)の固形分約50%キシレン溶液
ロジン亜鉛塩溶液:製造例13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。
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%。
MP25:商品名「Laroflex(登録商標) MP 25」(BASF社製)
EVA15:商品名「ノバテックTM EVA LV440」(日本ポリエチレン(株)製)
TP-217:商品名「ニチゴーポリエスターTM TP-217」(日本合成化学(株)製)
TP-290:商品名「ニチゴーポリエスターTM TP-290」(日本合成化学(株)製)
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種」(正同化学(株)製)
酸化チタン:商品名「FR-41」(古河機械金属(株)製)
DOP:ジオクチルフタレート:商品名「DOP」(三菱ケミカル(株))
DINP:ジイソノニルフタレート:商品名「フタル酸ジイソノニル」(和光純薬工業(株)製)
DIDP:ジイソデシルフタレート:商品名「フタル酸ジイソデシル」(和光純薬工業(株)製)
ESBO: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)
テトラエトキシシラン:商品名「Tetraethyl Orthosilicate」(東京化成(株)製)
脂肪酸アマイド系揺変剤:商品名「ディスパロンA603-20X」(楠本化成(株)製)
無水石膏:商品名「D-1」(ノリタケカンパニーリミテド(株)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)
ロダン銅:ロダン銅:商品名「チオシアン酸銅(I)」(SIGMA-ALDRICH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)
試験例1(ロータリー試験)と同様の方法で、18ヶ月ロータリー試験を行った後、試験板を25℃で72時間乾燥させ、試験板上に、酸化チタン含有白色水系エポキシ塗料を、乾燥膜厚が200~500μm程度になるように塗付し、25℃で72時間、乾燥させた。
上記操作により保護されたロータリー試験終了後の試験板を、SEM-EDS測定用サンプルとして、最適なサイズになるようにトリミングし、断面切り出しとその表面研磨を行った。
SEM-EDS測定の前処理として、測定サンプルにオスミウム蒸着を施し、SEM-EDS(日本電子(株)製JSM-6335F, JSM-6335F)により、該試験板断面のSEM観察(加速電圧20kV、倍率230倍)、およびEDS分析による元素マッピング(Cu、Fe、Ti)を行い、SEM画像、および元素マッピング画像を得た。EDSの元素マッピング測定時間は約12分である。Cu、Fe、Tiの分布範囲をそれぞれ表示させ、SEM画像を含む各画像(左の小さなは4つの画像)をオーバーラップ表示する事で(右の大きな1つの画像)、防汚剤である亜酸化銅(C)由来のCuが溶出した層(スケルトン層)の有無を確認し、その層の厚さをμmオーダーで測長した。
Cuは亜酸化銅由来、Feはベンガラ由来と考えられるので、塗膜表層において、Cuの分布が認められない層とは、18ヶ月のロータリー試験期間中に防汚薬剤である亜酸化銅(C)が表層から溶出し、ベンガラや樹脂などのその他成分が残存した層であると想定され、この結果は、試験例1のロータリー試験において、塗膜の溶解が続いていても、24ヶ月後には、塗膜状態が悪化している結果や試験例2の防汚試験において、18ヶ月以降の防汚性が低下している結果を支持するものである。
Claims (17)
- 共重合体(A)と、エステル化合物(B)と、亜酸化銅(C)を含み、
前記共重合体(A)は、トリオルガノシリル基含有単量体(a)と、酸素原子含有単量体(b)と、エチレン性不飽和単量体(c)の混合物から得られるトリオルガノシリルエステル含有共重合体であり、
前記単量体(a)は、化学式(1)で表され、
前記単量体(b)は、化学式(2)で表され、
前記単量体(c)は、前記単量体(a)及び前記単量体(b)以外の単量体であって、且つ前記単量体(a)及び前記単量体(b)と共重合可能であり、
前記エステル化合物(B)は、化学式(3)~(9)で表される少なくとも1つのエステル化合物を含有する、防汚塗料組成物。
Y-R ...(2)
(式中、Rは炭素数2~10の酸素原子を有するアルキル基またはアリール基を示し、Yはアクリロイルオキシ基、メタクリロイルオキシ基、マレイノイルオキシ基、フマロイルオキシ基またはイタコノイルオキシ基を示す。)
- 前記エステル化合物(B)は、前記化学式(8)で表されるエステル化合物を含有する、請求項1に記載の防汚塗料組成物。
- 前記化学式(8)のR4~R6は、水素原子である、請求項2に記載の防汚塗料組成物。
- 前記エステル化合物(B)は、前記化学式(7)で表されるエステル化合物を含有する、請求項1~請求項3の何れか1つに記載の防汚塗料組成物。
- 前記化学式(7)のR2は、水素原子である、請求項4に記載の防汚塗料組成物。
- 前記エステル化合物(B)は、前記化学式(6)で表されるエステル化合物を含有する、請求項1~請求項5の何れか1つに記載の防汚塗料組成物。
- 前記化学式(6)のR2~R4は、水素原子である、請求項6に記載の防汚塗料組成物。
- 前記エステル化合物(B)は、前記化学式(9)で表されるエステル化合物を含有する、請求項1~請求項7の何れか1つに記載の防汚塗料組成物。
- 前記化学式(9)のR2は、水素原子である、請求項8に記載の防汚塗料組成物。
- 前記エステル化合物(B)は、前記化学式(4)で表されるエステル化合物を含有する、請求項1~請求項9の何れか1つに記載の防汚塗料組成物。
- 前記化学式(4)のXは、炭素数2~16のアルキレン基である、請求項10に記載の防汚塗料組成物。
- 前記エステル化合物(B)は、前記化学式(5)で表されるエステル化合物を含有する、請求項1~請求項11の何れか1つに記載の防汚塗料組成物。
- 前記化学式(5)は、Xが酸素原子であり、R3及びR4が水素原子である、請求項12に記載の防汚塗料組成物。
- 前記エステル化合物(B)は、前記化学式(3)で表されるエステル化合物を含有する、請求項1~請求項13の何れか1つに記載の防汚塗料組成物。
- 前記化学式(3)は、R1が芳香環を有する、請求項14に記載の防汚塗料組成物。
- 前記化学式(3)は、R1がヘテロ原子を含んでもよい脂肪族炭化水素基である、請求項14に記載の防汚塗料組成物。
- 請求項1~請求項16の何れか1つに記載の防汚塗料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。
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SG11202002094RA SG11202002094RA (en) | 2017-10-04 | 2018-09-27 | Antifouling paint composition and coated object having antifouling coating formed using said composition on surface |
CN201880064316.3A CN111164164A (zh) | 2017-10-04 | 2018-09-27 | 防污涂料组合物、在表面具有利用该组合物形成的防污涂膜的涂装物 |
EP18863866.2A EP3693421B1 (en) | 2017-10-04 | 2018-09-27 | Antifouling paint composition and coated article having antifouling coating formed using said composition on surface |
JP2019546659A JP7217974B2 (ja) | 2017-10-04 | 2018-09-27 | 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 |
KR1020207012144A KR102659595B1 (ko) | 2017-10-04 | 2018-09-27 | 방오 도료 조성물, 이 조성물을 이용하여 형성되는 방오 도막을 표면에 갖는 도장물 |
ES18863866T ES2970508T3 (es) | 2017-10-04 | 2018-09-27 | Composición de pintura antiincrustante y artículo recubierto que tiene un recubrimiento antiincrustante formado usando dicha composición sobre la superficie |
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JP4505661B1 (ja) * | 2008-12-19 | 2010-07-21 | 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、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 |
SG11201506714RA (en) * | 2013-03-15 | 2015-09-29 | Nitto Kasei Co Ltd | Antifouling coating composition, antifouling coating film formed using said composition, and coated article having antifouling coating film on surface |
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JP2001226440A (ja) * | 2000-02-17 | 2001-08-21 | Nippon Paint Co Ltd | 共重合体及び塗料組成物 |
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KR102659595B1 (ko) | 2024-04-19 |
ES2970508T3 (es) | 2024-05-29 |
CN111164164A (zh) | 2020-05-15 |
EP3693421A4 (en) | 2020-12-09 |
EP3693421B1 (en) | 2023-12-20 |
EP3693421A1 (en) | 2020-08-12 |
KR20200062269A (ko) | 2020-06-03 |
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