WO2019131797A1 - Matériau de revêtement anti-encrassement biologique - Google Patents

Matériau de revêtement anti-encrassement biologique Download PDF

Info

Publication number
WO2019131797A1
WO2019131797A1 PCT/JP2018/047943 JP2018047943W WO2019131797A1 WO 2019131797 A1 WO2019131797 A1 WO 2019131797A1 JP 2018047943 W JP2018047943 W JP 2018047943W WO 2019131797 A1 WO2019131797 A1 WO 2019131797A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
paint
coating film
fluorine
paint according
Prior art date
Application number
PCT/JP2018/047943
Other languages
English (en)
Japanese (ja)
Inventor
瑞菜 豊田
俊 齋藤
智亮 中西
幸治 内田
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to JP2019562127A priority Critical patent/JPWO2019131797A1/ja
Publication of WO2019131797A1 publication Critical patent/WO2019131797A1/fr

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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • 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

Definitions

  • the present invention relates to anti-biofouling paints.
  • Fluorine-based paints are used to provide weather resistance to various substrates.
  • a fluorine-based paint a fluorine-containing polymer including units based on fluoroolefins and units based on vinyl ethers is disclosed (see Patent Document 1).
  • An object of this invention is to provide the anti-biofouling coating which can form the coating film excellent in bio-adhesion prevention property in view of the said subject.
  • the present inventors have found that if the paint contains at least one of a fluorine-containing polymer and an additive selected from an acid generator and a base generator, the desired effect is obtained. It has been found that the present invention is obtained. That is, the present inventors found that the above-mentioned subject can be solved by the following modes.
  • An anti-biofouling paint comprising: a fluorine-containing polymer; and at least one additive selected from an acid generator and a base generator.
  • the paint of the above-mentioned [1] which comprises 0.01 to 30 parts by mass of at least one of the additives with respect to 100 parts by mass of the fluorine-containing polymer.
  • the additive has a light absorption peak and is decomposed by irradiation with light having a wavelength ⁇ MAX corresponding to the peak top among the peaks to generate an acid or a base.
  • the biofouling prevention coating which can form the coating film excellent in biofouling prevention property over a long period of time as well as a weather resistance can be provided.
  • the anti-biofouling paint of the present invention since the acid or the base gradually exudes from the coating, the bio-adhesion to the substrate can be prevented for a long time.
  • the meanings of the terms in the present invention are as follows.
  • the numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the unit is a generic term for an atomic group based on one molecule of the above-mentioned monomer, which is directly formed by polymerization of a monomer, and an atomic group obtained by chemical conversion of a part of the above-mentioned atomic group.
  • the content (mol%) of each unit relative to the total units contained in the polymer is determined by analyzing the polymer by nuclear magnetic resonance spectroscopy.
  • the hydrolyzable silyl group is a group that becomes a silanol group by hydrolysis.
  • (Meth) acrylate is a generic term for acrylate and methacrylate
  • (meth) acrylic is a generic term for acrylic and methacryl.
  • the average particle size is a value of D50 determined by a dynamic light scattering method using ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.). In the particle size distribution of particles, D50 is a particle diameter value of 50% by volume of total volume calculated from the side of small particles.
  • the number average molecular weight and the weight average molecular weight are values measured by gel permeation chromatography using polystyrene as a standard substance. The number average molecular weight is also referred to as Mn, and the weight average molecular weight is also referred to as Mw.
  • the acid value and the hydroxyl value are values measured according to the method of JIS K 0070-3 (1992).
  • the mass of the solid content of the paint is the mass of the paint removed of the solvent when the paint contains the solvent.
  • the component which comprises solid content of coating materials other than a solvent even if the property is liquid, it is regarded as solid content.
  • the mass of the solid content of the paint is determined as the mass remaining after heating 1 g of the composition at 130 ° C. for 20 minutes.
  • the film thickness of the coating film is a value measured using an eddy current film thickness meter. In the examples, “EDY-5000” (manufactured by Sanko Electronics Co., Ltd.) was used as the eddy current film thickness meter.
  • a coating film (hereinafter, also referred to as the present coating film) formed using the anti-biofouling paint of the present invention is excellent in anti-biofouling properties.
  • the reason for this is not necessarily clear, but can be estimated as follows. Since the present coating contains at least one of additives selected from an acid generator and a base generator in the present coating, it decomposes with time or irradiation with light or heat to generate an acid or a base. . It is thought that the coating film surface is thereby adjusted to be acidic or basic to create a state in which an organism repels adhesion.
  • the above-mentioned additive is uniformly dispersed and present in the present coating film due to the interaction with the fluorine-containing polymer (mainly the interaction with the fluorine atom contained in the main chain of the fluorine-containing polymer) . Therefore, the rate at which the acid or base generated from the above additive exudes out of the coating is extremely slow. In addition, the present coating film itself is less likely to be deteriorated by the acid or the base. As a result, it is considered that the present coating film can exhibit anti-biofouling properties over a long period of time.
  • the anti-biofouling paint (hereinafter also referred to as the present paint) of the present invention contains a fluorine-containing polymer.
  • the fluoropolymer contains units based on fluoroolefins (hereinafter also referred to as unit F).
  • Fluoroolefins are olefins in which one or more of the hydrogen atoms have been replaced by fluorine atoms. In the fluoroolefin, one or more hydrogen atoms which are not substituted by a fluorine atom may be substituted by a chlorine atom.
  • fluoroolefin CF 2
  • CF 2 CFCl
  • CF 3 CF CH 2
  • Two or more fluoroolefins may be used in combination.
  • the fluorine-containing polymer may contain only the unit F, may contain the unit F and a unit based on a monomer containing a fluorine atom other than fluoroolefin, and is based on a unit F not containing a fluorine atom And a unit.
  • fluorine-containing polymer containing only the unit F examples include homopolymers of fluoroolefins and copolymers of two or more fluoroolefins.
  • Specific examples of the fluorine-containing polymer containing only the unit F include polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride and the like.
  • fluorine-containing polymer containing the unit F and a unit based on a monomer containing a fluorine atom other than fluoroolefins examples include fluoroolefin-perfluoro (alkyl vinyl ether) copolymers and the like. And fluoroethylene-perfluoro (alkyl vinyl ether) copolymers.
  • the content of the unit F is preferably 20 to 100% by mole, more preferably 30 to 70% by mole, with respect to all units contained in the fluoropolymer, in order to maintain the bioadhesiveness of the present coating. 40 to 60 mol% is particularly preferred.
  • the fluorine-containing polymer preferably contains a unit F and a unit based on a monomer not containing a fluorine atom, from the viewpoint that the additive in the present invention is easily retained in the present coating film.
  • Specific examples of the fluorine-containing polymer containing unit F and a unit based on a monomer not containing a fluorine atom include ethylene-tetrafluoroethylene copolymer, chlorotrifluoroethylene-vinyl ether copolymer, chlorotrifluoro Ethylene-vinyl ether-vinyl ester copolymer, chlorotrifluoroethylene-vinyl ester-allyl ether copolymer, tetrafluoroethylene-vinyl ester copolymer, tetrafluoroethylene-vinyl ester-allyl ether copolymer, ethylene-tetra The fluoroethylene copolymer is mentioned.
  • the fluorine-containing polymer preferably contains a unit having a hydrophilic group (hereinafter also referred to as a unit H) as a unit based on a monomer not containing a fluorine atom, from the viewpoint of hydrophilizing the film surface.
  • a unit H a hydrophilic group
  • the acid or base exuding from the coating film is uniformly dispersed on the coating film surface, and thus, the bioadhesion preventing property is more excellent.
  • the hydrophilic group contained in the unit H is a hydroxy group, a carboxy group, an amino group, a hydrolyzable silyl group, a group represented by -OSO 3 - X 1 + , a group represented by -COO - X 1 + , The group etc. which have a hydrophilic polyoxyalkylene chain are mentioned.
  • the above X 1 + is Na + or NH 4 + .
  • the hydrophilic group which unit H has is preferably a group having a hydroxy group, a carboxy group or a hydrophilic polyoxyalkylene chain, from the viewpoint that the surface of the present coating film is suitably hydrophilized.
  • the group having a hydrophilic polyoxyalkylene chain may contain other hydrophilic groups (hydroxy group, carboxy group, etc.).
  • about the group which contains the group which has a hydrophilic polyoxyalkylene chain, and other hydrophilic groups it handles as a group which has a hydrophilic polyoxyalkylene chain.
  • unit 1 has a group having a hydrophilic polyoxyalkylene chain
  • an acid or a base is easily retained by the polyoxyalkylene chain on the surface of the suitably coated main coating film, and the bio-deposition of the present coating film Preventability can be maintained for a longer period of time.
  • the hydrophilic polyoxyalkylene chain means a polyoxyalkylene chain in which at least a part of the plurality of oxyalkylene groups is an oxyethylene group.
  • the unit H may be a unit based on a monomer having a hydrophilic group (hereinafter also referred to as a monomer H), and the hydrophilic group of the fluorine-containing polymer containing the unit H is different from the hydrophilic group.
  • a monomer H a monomer having a hydrophilic group
  • the hydrophilic group of the fluorine-containing polymer containing the unit H is different from the hydrophilic group.
  • It may be a unit obtained by converting into Examples of such units include fluorine-containing polymers containing units having a hydroxy group, polycarboxylic acids and acid anhydrides thereof (5-norbornene-2,3-dicarboxylic acid anhydride, citraconic acid anhydride, maleic acid anhydride, Examples thereof include units obtained by reacting at least one selected from itaconic anhydride, hymic anhydride and the like) to convert part or all of a hydroxy group to a carboxy group.
  • the hydrophilic group contained in the unit H may be crosslinked with a curing agent described later.
  • the hydrophilic group of the unit H crosslinks with a curing agent described later, the hardness of the present coating film is improved, and the durability of the present coating film is excellent. In this case, in the present coating film, the hydrophilic group may be left as long as the effects of the present invention are not lost.
  • -cycloC 6 H 10- represents a cyclohexylene group, and the bonding site of "-cycloC 6 H 10- " is usually 1,4-.
  • a monomer having a carboxy group unsaturated carboxylic acid, (meth) acrylic acid, monomers obtained by reacting a carboxylic acid anhydride with the hydroxy group of the above-mentioned monomer having a hydroxy group, etc.
  • Examples of the monomer having a hydrophilic polyoxyalkylene chain include vinyl ethers, vinyl esters, allyl ethers, allyl esters, (meth) acrylic acid esters having a hydrophilic polyoxyalkylene chain, and the like.
  • the polyoxyalkylene chain in the group having a hydrophilic polyoxyalkylene chain preferably has 6 to 24 of oxyalkylene groups, and more preferably 10 to 20.
  • the alkylene group in the oxyalkylene group is preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms. In this case, the alkylene group may be linear or branched, and is preferably linear.
  • the polyoxyalkylene chain may consist of two or more oxyalkylene groups. In this case, the bonding order of each oxyalkylene group may be random or block.
  • the hydrophilic polyoxyalkylene chain is a polyoxyethylene chain consisting only of an oxyethylene group or has an oxyethylene group and an oxyalkylene group having 3 or 4 carbon atoms, and the ratio of the oxyethylene group to the total of both The polyoxyalkylene chain which is 50 mol% or more is preferable. In the latter case, a polyoxyalkylene chain having an oxyethylene group and an oxypropylene group and having a ratio of the oxyethylene group to the total of both of 70 mol% or more is preferable.
  • Particularly preferred hydrophilic polyoxyalkylene chains are polyoxyethylene chains consisting only of oxyethylene groups.
  • L 1 -Y 1 -Z 1 is preferable.
  • Y 1 is a divalent saturated hydrocarbon group having 2 to 12 carbon atoms.
  • the divalent saturated hydrocarbon group may be linear or branched, may have a ring structure, or may contain a ring structure.
  • the divalent saturated hydrocarbon group is preferably an alkylene group containing an alkylene group having 4 to 12 carbon atoms or a cycloalkylene group having 6 to 8 carbon atoms.
  • the divalent saturated hydrocarbon group is a group represented by -CH 2 -cycloC 6 H 10 -CH 2- , -CH 2 CH 2- , -CH 2 CH 2 CH 2 CH 2 -or -CH 2 CHY 11
  • the binding site of -cycloC 6 H 10- is not particularly limited, and is usually 1,4-.
  • Y 11 represents an alkyl group having 1 to 10 carbon atoms.
  • Z 1 is a group represented by — (OM) m OZ 11 .
  • M is an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably —CH 2 CH 2 —. When the number of carbon atoms is 3 or 4, M may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferable. When a plurality of M are present, M may be the same or different. In addition, when there are a plurality of M, their combination order may be random type or block type.
  • m is an integer of 6 to 24, preferably an integer of 10 to 20.
  • Z 11 is a hydrogen atom, -OSO 3 - Na + , -OSO 3 - NH 4 + , -COO - Na + , or COO - NH 4 + , preferably a hydrogen atom.
  • n13 represents an integer of 6 to 24.
  • the monomer H may be used in combination of two or more.
  • the monomer H having a hydrophilic polyoxyalkylene chain and the monomer H having no hydrophilic polyoxyalkylene chain are used in combination from the viewpoint of excellent bioadhesiveness of the coating film. Is preferred.
  • the fluorine-containing polymer contains the unit H
  • the content of the monomer H is preferably 0.1 to 30% by mole, and more preferably 3 to 20% by mole, relative to all units contained in the fluorine-containing polymer. .
  • the fluorine-containing polymer contains a unit based on a monomer H having a hydrophilic polyoxyalkylene chain and a unit based on a monomer H having no hydrophilic polyoxyalkylene chain, each of them
  • the content of units is, in this order, 0.1 to 5 mol%, preferably 1 to 25 mol%, 0.2 to 3 mol%, 3 to 20 mol% with respect to all units contained in the fluoropolymer. More preferable.
  • the fluorine-containing polymer is a unit (hereinafter referred to as unit D) based on a monomer which does not contain a fluorine atom and does not have a hydrophilic group (hereinafter also referred to as a monomer D) from the viewpoint of processability of the present coating film. It may also be included.
  • the fluoropolymer contains the unit D, the flexibility of the present coating film is excellent, and the present invention can be applied to the case where the substrate having the present coating film is processed into a complicated shape.
  • the monomer D include vinyl ethers, vinyl esters, allyl ethers, allyl esters, (meth) acrylic acid esters, etc. which do not contain a fluorine atom and do not have a hydrophilic group. Preference is given to vinyl ethers or vinyl esters.
  • the monomer D is preferably a monomer represented by the formula: L 2 -Z 2 .
  • Z 2 is a monovalent hydrocarbon group having 2 to 24 carbon atoms.
  • the monovalent hydrocarbon group may be linear or branched, may be a ring structure, or may contain a ring structure.
  • the monovalent hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the monovalent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a cycloalkylalkyl group, and is an alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or 6 carbon atoms.
  • An aryl group of ⁇ 10, an aralkyl group having 7 to 12 carbon atoms, and a cycloalkylalkyl group having 6 to 10 carbon atoms are particularly preferable.
  • alkyl group examples include methyl group, ethyl group, tert-butyl group, hexyl group, nonyl group, decyl group and dodecyl group.
  • a cyclohexyl group is mentioned as a specific example of a cycloalkyl group.
  • aralkyl group examples include benzyl group.
  • a cyclohexylmethyl group is mentioned as a specific example of a cycloalkyl alkyl group.
  • aryl group include a phenyl group and a naphthyl group.
  • the hydrogen atom of the cycloalkyl part of a cycloalkyl group or a cycloalkyl alkyl group, an aryl group, or an aralkyl group may be substituted by the alkyl group.
  • the carbon number of the alkyl group as a substituent is not included in the carbon number of the cycloalkyl group, the aryl group or the aralkyl group.
  • the monomer D examples include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethyl hexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl pivalate, vinyl vinyl neononanoic acid (trade name "Beova 9", HEXION), Examples thereof include neodecanoic acid vinyl ester (HEXION, trade name "Beova 10"), benzoic acid vinyl ester, tert-butyl (meth) acrylate and benzyl (meth) acrylate. Two or more monomers D may be used in combination.
  • the content of the unit D is preferably 0 to 50 mol%, particularly preferably 5 to 40 mol%, based on all units contained in the fluoropolymer.
  • the fluorine-containing polymer comprises 20 to 70% by mole, 0.1 to 30% by mole, and 0 to 50% by mole of the unit F, the unit H and the unit D in this order with respect to all units contained in the fluoropolymer It is preferably contained, and more preferably 40 to 60% by mole, 3 to 20% by mole, and 5 to 40% by mole.
  • a unit based on a monomer H having a hydrophilic polyoxyalkylene chain as the unit H and a unit based on a monomer H having no hydrophilic polyoxyalkylene chain as the fluorine-containing polymer
  • the unit F based on all units contained in the fluorine-containing polymer, a unit based on a monomer H having a hydrophilic polyoxyalkylene chain, and a monomer H not having a polyoxyalkylene chain Preferably, it contains 20 to 70 mol%, 0.1 to 5 mol%, 1 to 25 mol%, 0 to 50 mol%, and 40 to 60 mol% of units based on the above and a unit D in this order. It is more preferable to include 2 to 3 mol%, 3 to 20 mol%, and 5 to 40 mol%.
  • the Mn of the fluorine-containing polymer is preferably 5,000 to 200,000, and more preferably 7,000 to 180,000, from the viewpoint of the impact resistance of the present coating film.
  • the hydroxyl value of the fluorine-containing polymer is preferably 1 to 150 mg KOH / g, more preferably 3 to 100 mg KOH / g, and further preferably 10 to 60 mg KOH / g from the viewpoint of the hydrophilicity of the present coating film. g is particularly preferred.
  • the acid value of the fluorine-containing polymer is preferably 1 to 150 mg KOH / g, more preferably 3 to 100 mg KOH / g, and further preferably 5 to 50 mg KOH, from the viewpoint of the hydrophilicity of the present coating film. / G is particularly preferred.
  • the fluorine-containing polymer may have either one or both of an acid value and a hydroxyl value.
  • the fluorine-containing polymer is manufactured using a known method, and solution polymerization, emulsion polymerization and the like can be mentioned.
  • the fluorine-containing polymer may be dissolved or dispersed in an organic solvent, may be dispersed in the form of particles in water, or may be powder particles containing neither an organic solvent nor water.
  • the water may contain a water-soluble organic solvent described later.
  • the average particle diameter of the particles of the fluoropolymer is preferably 30 to 300 nm and 50 to 200 nm in terms of water resistance of the present coating film. More preferable.
  • the fluoropolymer When the fluoropolymer is present in the form of particles dispersed in water, it may be a particle of the fluoropolymer alone, and the fluoropolymer and a polymer other than the fluoropolymer are It may be particles forming a core-shell structure.
  • the particles forming the core-shell structure preferably have a core portion of a fluoropolymer and a shell portion of a polymer other than a fluoropolymer, which is located on the surface of the core portion.
  • the shell portion may cover a part of the surface of the core portion, or may cover the entire core portion.
  • the fluorine-containing polymer in this case, at least one homopolymer of fluoroolefin is preferable, and as the above-mentioned polymer other than the fluorine-containing polymer, a (meth) acrylic polymer is preferable.
  • the paint contains at least one additive selected from an acid generator and a base generator.
  • disassembles and emits an acid or a base by irradiation of light is preferable.
  • the acid generator is also referred to as a photoacid generator
  • the base generator is also referred to as a photobase generator.
  • the additive preferably has a molecular weight of 100 to 1,000, more preferably 300 to 700, and particularly preferably 350 to 500, from the viewpoint of dispersibility in the present coating film.
  • the additive is preferably a compound having a ring structure from the viewpoint of easy retention in the fluoropolymer.
  • the ring structure may be a carbocyclic ring or a heterocyclic ring.
  • the carbocyclic ring and the heterocyclic ring may have an unsaturated bond or may be an aromatic ring.
  • the ring structure may be a fused ring.
  • the above ring structure is preferably a carbocyclic ring or a heterocyclic ring and a ring having aromaticity, from the viewpoint that the hydrophobicity of the additive is increased and the additive is easily dispersed uniformly in the fluoropolymer.
  • the compound having a ring structure preferably has at least one group selected from the group consisting of a cycloalkyl group, a cycloalkylene group, a phenyl group, an arylene group, a furyl group, a thiophenyl group, and a naphthyl group.
  • the compound having at least one group selected from the group consisting of a phenyl group, a phenylene group, a furyl group, and a triazinyl group is more preferable in terms of easy retention in the fluoropolymer.
  • a plurality of at least one group selected from the group consisting of a phenyl group, a phenylene group, a furyl group, and a triazinyl group may be provided for each group.
  • a compound having two or more groups selected from the group consisting of a phenyl group and a phenylene group, or a compound having a furyl group and a triazyl group is preferable, and a compound having three or more phenyl groups or phenylene groups is more preferable.
  • the compound having three or more groups selected from the group consisting of a phenyl group and a phenylene group include salts of a cation having three or more groups selected from a phenyl group and a phenylene group, and an anion.
  • Examples of the cation include sulfonium ions, ammonium ions, phosphonium ions, iodonium ions, selenium ions and bromonium ions.
  • the cation is preferably a sulfonium ion or a phosphonium ion, and more preferably a sulfonium ion, from the viewpoint of excellent generation of an acid or a base.
  • the anion examples include triflate ion, fluorophosphate ion which may have a substituent, hexafluoroantimonate ion, tetrafluoroborate ion, sulfate ion, carboxylate ion and the like.
  • a triflate ion and a fluorophosphate ion which may have a substituent are preferable, and a triflate ion is more preferable, from the viewpoint of excellent bioadhesive preventing property of the present coating film.
  • the substituent in the fluorophosphate ion which may have a substituent is preferably a fluoroalkyl group.
  • the photoacid generator When the acid generator is a photoacid generator, the photoacid generator has an absorption peak of light and, of the peaks, light of a wavelength corresponding to the peak top (hereinafter, also referred to as wavelength ⁇ MAX ). It decomposes upon irradiation to generate an acid.
  • the base generator is a photobase generator
  • the photobase generator has an absorption peak of light and is decomposed by irradiation with light of wavelength ⁇ MAX to generate a base.
  • the wavelength ⁇ MAX in the photoacid generator and the photobase generator is preferably in the range of 150 to 500 nm, more preferably in the range of 200 to 400 nm, and particularly preferably in the range of 200 to 250 nm.
  • the photoacid generator and the photobase generator may have two or more wavelengths ⁇ MAX , and for example, when having two wavelengths ⁇ MAX , the smaller one is at 150 to 300 nm, and the larger one is more than 300 nm. It is preferably 500 nm or less, and in particular, the smaller one is 200 to 280 nm, and the larger one is more preferably 300 to 400 nm.
  • the photoacid generator and the photobase generator may be used in combination of two or more.
  • two or more kinds of different photoacid generators may be used in combination, or two or more kinds of different photobase generators may be used in combination, one or more kinds of photoacid generators And one or more photobase generators may be used in combination.
  • the coating is disposed on a structure in water and the wavelength and amount of light transmitted into the water differ depending on time or season, a sufficient amount of acid or base can always be generated. Excellent in anti-biofouling properties.
  • the absolute value of the difference between the wavelength ⁇ MAX and the wavelength ⁇ MAX is preferably 10 to 200 nm, and more preferably 50 to 100 nm.
  • the acid generator include Tris (4-methylphenyl) sulfonium trifluoromethansulfonate (molecular weight: 455, ⁇ MAX : 242 nm), Tris (4-methylphenyl) sulfone hexafluorophosphate (molecular weight: 450, ⁇ MAX : 242 nm), 2- [ 2- (Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (molecular weight: 408, ⁇ MAX : 370 nm), 2- [2- (5-Methylfuran-2-yl) ethenyl ] -4,6-bis (trichloromethyl) -s -triazine ( molecular weight: 422, ⁇ MAX: 392nm) , 2- ( ethoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine ( molecular
  • the acid generator may be a commercially available product, for example, TS-01, TS-91, TFE-triazine, TME-triazine, MP-triazine, MOP-triazine, dimethoxytriazine (all, trade names of Sanwa Chemical Co., Ltd.) , CPI-100P, CPI-101A, CPI-200K (all trade names of Sanyo Chemical Industries, Ltd.), and the like.
  • the base generator examples include 1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate (molecular weight: 622, ⁇ MAX : 254 nm), 1,2-Diisopropyl-3- [Bis (dimethylamino) Methylene] guanidium 2- (3-benzoylphenyl) propionate (molecular weight: 496, ⁇ MAX : 254 nm) and the like.
  • the base generator may be a commercially available product, and examples thereof include WPBG-266, WPBG-300 (all trade names of Wako Pure Chemical Industries, Ltd.) and the like.
  • the present paint preferably contains at least one of additives in a total amount of 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the fluoropolymer. It is particularly preferable to include 2 to 6 parts by mass.
  • the paint contains an additive in an amount of 0.01 parts by weight or more in total, the effect of the present coating for preventing biofouling can be sustained.
  • the coating contains 30 parts by mass or less of additives in total, the weather resistance of the coating is excellent.
  • the acid generator and the base generator may be dispersed in the paint solvent if the paint is an aqueous paint or solvent type paint containing the paint solvent (dispersion medium), or may be dissolved in the paint solvent Good.
  • the paint of the present invention may be any of water-based paint, solvent-based paint, and powder-free paint without solvent, and from the viewpoint of the dispersibility of additives, water-based paint and solvent-based paint are preferable. In particular, when the additive in the present invention is dissolved in water or an organic solvent, the additive is well retained in the present coating film.
  • the present paint preferably contains 10 to 90% by weight, and particularly preferably 40 to 80% by weight, of the solid content based on the total weight of the present paint.
  • the content of the fluorine-containing polymer in the present coating is preferably 10 to 90% by mass, and more preferably 20 to 70% by mass, with respect to the total mass of the present coating.
  • the coating composition preferably contains 5 to 95% by mass, and particularly preferably 60 to 90% by mass of the fluoropolymer, based on the total solid content of the coating composition.
  • the content of one or more selected from the acid generator and the base generator in the present coating is preferably 0.001 to 20% by mass, and 0.1 to 10% by mass with respect to the total mass of the present coating. More preferably, 1 to 5% by mass is particularly preferable.
  • the paint may contain a fluorescent material.
  • a fluorescent substance is a component that emits fluorescence, and includes, for example, a substance that is excited when irradiated with ultraviolet light (wavelength: 254 to 380 nm) and emits visible light.
  • the fluorescent material may be an organic fluorescent material or an inorganic fluorescent material, and from the viewpoint of the weather resistance of the present coating film, an inorganic fluorescent material is preferable.
  • an inorganic fluorescent substance an inorganic fluorescent pigment is preferable.
  • organic fluorescent substances include brilliant sulfoflavin, thioflavin, basic yellow HG, fluorescein, eosin, rhodamine 6G, rhodamine B and the like.
  • inorganic fluorescent substances include chelate compounds of heavy metals and rare earth oxides.
  • metal oxides or sulfides such as aluminum, calcium, barium, magnesium, zinc, cadmium and strontium, which are activated by an activator such as heavy metal and rare earth oxide, are preferable.
  • the activator includes at least one oxide selected from europium, neodymium, antimony, manganese, lead, tin, cerium, and terbium, with at least one oxide selected from europium and neodymium being preferred.
  • Examples of fluorescent inorganic pigments 3Ca 3 (PO 4) 2 ⁇ Ca (F, Cl) 2: Sb 3+, 3Ca 3 (PO 4) 2 ⁇ Ca (F, Cl) 2: Sb 3+, Mn 2+, BaMg 2 Al 16 O 27 : Eu 2+, (Sr, Ca) 10 (PO 4) 6 Cl 2: Eu 2+, Sr 4 Al 14 O 25: Eu 2+, BaMg 2 Al 16 O 27: Eu 2+ Mn 2+ , CaWO 4 , CaWO 4 : Pb 2+ , Sr 2 P 2 O 7 : Sn 2+ , Y 2 O 3 : Eu 3+ , 3.5MgO ⁇ 0.5MgF 2 GeO 2 : Mn 4+ , Y (PV) O 4 : Eu 3+, (Sr, Mg) 3 (PO 4) 2: Sn 2+, 6MgO ⁇ As 2 O 5: Mn 4+, (Ca, Sr) SiO 3: Pb 2
  • a fluorescent phosphorescent pigment such as an aluminium oxide activated by at least one oxide selected from europium and neodymium is preferable in that the fluorescence lasts for a long time.
  • Two or more fluorescent substances may be used in combination.
  • the coating material preferably contains the fluorescent substance in an amount of 5 to 200 parts by mass, particularly preferably 10 to 100 parts by mass, and particularly preferably 30 to 60 parts by mass with respect to 100 parts by mass of the fluoropolymer.
  • the present paint preferably contains 5 to 50% by mass, and particularly preferably 15 to 30% by mass of a fluorescent substance based on the total solid content of the present paint.
  • the paint When the paint is an aqueous paint containing water, and the fluoropolymer is dispersed in water, the paint contains only water or a mixture of water and a water-soluble organic solvent as a paint solvent.
  • the water-soluble organic solvent in the mixed solution include methanol, ethanol, propanol, butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether and tripropylene glycol.
  • the content of the water-soluble organic solvent in the mixed solution is preferably 1 to 40 parts by mass with respect to 100 parts by mass of water.
  • the paint When the paint is a water-based paint, it is preferable to contain 10 to 90% by weight of water or the above mixed solution with respect to the total weight of the paint.
  • the paint is a solvent type paint containing an organic solvent
  • examples of the organic solvent include toluene, xylene, mineral spirits, ethyl acetate, butyl methyl ethyl ketone acetate, methyl isobutyl ketone, cyclohexanone and the like.
  • the paint is a solvent-based paint, it preferably contains 1 to 99% by mass, and more preferably 3 to 60% by mass of an organic solvent based on the total mass of the paint.
  • the additive may be mixed as a separate particle from the powder particles containing the fluorine-containing polymer, and the powder containing the fluorine-containing polymer The particles may be mixed as identical particles.
  • the anti-biofouling coating of the present invention may contain components other than the fluoropolymer and the additive (hereinafter, also referred to as other components).
  • components other than the fluoropolymer and the additive hereinafter, also referred to as other components.
  • the above components may be used in combination of two or more.
  • alkyd resin alkyd resin, amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, vinyl acetate resin, (meth) acrylic resin, vinyl chloride resin, phenol resin, modified polyester resin And acrylic silicone resins and silicone resins.
  • the resins other than the fluorine-containing polymer may be used in combination of two or more.
  • the curing agent include compounds having two or more of an isocyanate group, a blocked isocyanate group, an epoxy group, a carbodiimide group, an oxazoline group or a ⁇ -hydroxyalkylamide group in one molecule.
  • the curing agent may be used in combination of two or more.
  • the present paint is produced by mixing a fluorine-containing polymer, at least one of additives and, if necessary, other components.
  • the paint-coated substrate is obtained by applying the paint on the surface of the substrate to form a coating layer, and drying to form a paint film.
  • heating is not essential when drying the said coating layer, when this coating material contains a thermosetting hardener, it is preferable to heat. In this case, since the fluoropolymer and the curing agent crosslink in the coating, the coating is cured.
  • the paint is a powder paint
  • the paint-coated substrate is obtained by applying the paint on the surface of the substrate to form a coating layer, and heating to form a paint film. In this case, when the coating layer is heated, the particles of the powder coating are melted to form a uniform coating film.
  • the heating temperature is usually 20 to 300 ° C., and the heating time is usually 1 minute to 2 weeks.
  • the film thickness of the present coating film is preferably 5 to 300 ⁇ m from the viewpoint that the bioadhesion preventing property of the present coating film is maintained.
  • the method of applying the present paint may be a method using a coating apparatus such as a brush, roller, dipping, spray, roll coater, die coater, applicator, spin coater, etc. Can be mentioned.
  • the coating method of the coating includes electrostatic coating, electrostatic spraying, electrostatic immersion, spraying, flow immersion, spraying, spraying, spraying, plasma The thermal spraying method etc. are mentioned.
  • the substrate include resins, rubber, organic materials such as wood, concrete, glass, ceramics, inorganic materials such as stone, iron, iron alloys, aluminum, and aluminum alloys.
  • the present coating film may be formed directly on the substrate, or may be formed on the substrate after surface treatment.
  • the coated substrate may have a primer coating film or an intermediate coating film between the substrate and the coating film.
  • the base material with a coating film has a coating film (hereinafter, also referred to as a fluorescent coating film) containing the above-described fluorescent substance as a coating film other than the coating film.
  • a coating film hereinafter, also referred to as a fluorescent coating film
  • the coating does not contain, or if it contains, a smaller amount of the fluorescent substance than the fluorescent coating contains.
  • the order of lamination with the fluorescent coating on the substrate is not particularly limited. Moreover, you may have another coating film between a base material or each coating film.
  • the substrate with a coated film is preferably a coated film having a substrate, a fluorescent coating, and a coated film in this order. In particular, when the resistance to water of the fluorescent material is low, the anti-biofouling property is more sustained by arranging the present coating on the surface side of the fluorescent coating.
  • the fluorescent coating film may contain a fluorescent substance and a resin for dissolving or dispersing the fluorescent substance, and examples of the resin include the fluorine-containing polymer and the resins described above as the resin other than the fluorine-containing polymer.
  • the fluorescent coating film preferably contains 5 to 200 parts by mass, particularly preferably 10 to 100 parts by mass, and particularly preferably 30 to 60 parts by mass with respect to 100 parts by mass of the resin.
  • the fluorescent coating film preferably contains 5 to 50% by mass, and particularly preferably 15 to 30% by mass of the fluorescent material based on the total mass of the fluorescent coating.
  • the fluorescent coating film may be formed of a fluorescent paint including a fluorescent material, a resin, and, if necessary, a paint solvent.
  • the base film-coated substrate having the present coating film and the fluorescent coating film further contain a colored coating film.
  • the colored coating film is a coating film which contains no fluorescent substance or contains a smaller amount of fluorescent substance than the fluorescent coating film, and is colored by a pigment or the like.
  • the coated substrate preferably has a colored coating on the substrate side of the fluorescent coating. That is, it is preferable that the base material with a present coating film has a base material, a colored coating film, a fluorescent coating film, and the present coating film in this order. In this case, light incident on the coated substrate is reflected and scattered on the surface of the colored coating.
  • the fluorescent substance can efficiently accumulate light, and the effect of light emission is sustained, so that the bioadhesiveness of the present coating film is improved. Therefore, as the colored coating film, a coating film having a high light reflectance is preferable, and a coating film which is white by a white pigment such as titanium oxide is particularly preferable.
  • the present paint is suitable for coating on a structure that is required to have anti-biofouling properties.
  • Such structures include underwater structures, floating structures and the like used in the ocean, lakes, rivers and their vicinity. More specifically, critical facilities (intake and outlet of power plant, water distribution pipe of power plant (cooling water piping), bridge, breakwater, submarine cable, tank, pipeline, subsea drilling equipment etc.), fishing net, wave extinction
  • critical facilities intake and outlet of power plant, water distribution pipe of power plant (cooling water piping), bridge, breakwater, submarine cable, tank, pipeline, subsea drilling equipment etc.
  • fishing net wave extinction
  • wave extinction There are blocks, floats, the hull of a ship (in particular, the bottom and draft of a ship), the screw of a ship, and the anchor of a ship.
  • this paint can be used also for indoor water articles such as a water pipe, a sewage pipe, a water tank, a drainage unit, a bath tub, a toilet bowl, a handwasher, a ventilation fan and the like.
  • the present paint is particularly suitable for coating a structure which is exposed to severe environments such as seaside equipment and ship bottoms and which is required to have weatherability.
  • organisms from which the antifouling effect can be obtained by the present paint include aquatic organisms such as shellfish, algae and crustaceans, and organisms living in a wet environment or a wet environment.
  • organisms that can be particularly effective include marine organisms (such as barnacles and mussels).
  • a method of forming a coating on a surface of a substrate using a coating containing at least one of a fluorine-containing polymer and an additive to prevent organisms from adhering to the substrate Be done.
  • the acid or the base gradually exudes from the present coating, it is possible to prevent the attachment of organisms to the substrate over a long period of time.
  • a method of forming a coating film on a substrate by a paint containing an active substance such as copper oxide or tin oxide, or forming a biodegradable resin into a sheet There is a method of using as a base material and the like.
  • the present paint has less environmental impact as compared to the case of using a paint containing an active substance such as copper oxide or tin oxide.
  • this paint since this paint is easy to apply on site, it can be applied and repainted directly on critical facilities or on the hull of a ship as compared to biodegradable resins that need to be molded and applied. Excellent in quality.
  • it is also preferable in that there is no deterioration from the sticking part which becomes a problem when sticking a sheet-like molded article.
  • it is excellent also in the sustainability of bioadhesion prevention property rather than the case where it is made coating material and uses biodegradable resin. Therefore, according to the present invention, it is possible to provide an excellent method for preventing the attachment of organisms, particularly in marine equipment and marine vessels.
  • Examples 1 to 15 and 19 to 24 are the paints of Examples, and the paints of Examples 16 to 18 Comparative Examples.
  • Test plates 1 to 15, 19 to 24, and 31 to 34 are test plates having a coating film using the paint of the example, and test plates 16 to 18 and 25 to 30 use the paint of the example It is a test board which does not have a coating film.
  • CCTFE Chlorotrifluoroethylene
  • CH 2 CHO-CH 2 -cycloC 6 H 10 -CH 2- (OCH 2 CH 2 ) 15 OH
  • CM-EOVE Monomer having a polyoxyalkylene chain ), 4-hydroxymethylcyclohexylmethyl vinyl ether (CHMVE), hydroxybutyl vinyl ether (HBVE), cyclohexyl vinyl ether (CHVE), ethyl vinyl ether (EVE),
  • Nonionic surfactant Newcol-2320 (manufactured by Nippon Emulsifier)
  • Anionic surfactant sodium lauryl sulfate (manufactured by Nikko Chemicals)
  • Coalescent 2,2,4-trimethyl-1,3-pentadiol mono (2-methylpropanate) Thickener: Reo Reo 288 (manufactured by Elementis Japan)
  • Curing agent 1 Water-dispersed isocyanate curing agent (Bayhydur 3100, manufactured by Sumika Bayer Co., Ltd.)
  • Curing agent 2 Nurate type polyisocyanate resin of hexamethylene diisocyanate (HDI) (Corronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.)
  • Curing catalyst dibutyltin dilaurate
  • Additive 1 Tris (4-methylphenyl) sulfonyl hexafluorophosphate (molecular weight 450, ⁇ MAX 242 nm, photoacid generator)
  • Additive 2 Tris (4-methylphenyl) sulfonium trifluoromethansulfonate (molecular weight 455, ⁇ MAX 242 nm, photoacid generator)
  • Additive 3 Tris (aryl) sulfonium hexafluoroantimonate (molecular weight 606, ⁇ MAX 365 nm, photoacid generator)
  • Additive 4 1,2-Diisopropyl-3- [Bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate (molecular weight 495.67, ⁇ MAX 254 nm, photo base generator)
  • Additive 5 1,2-Dicyclohexyl-4,4,5,5-tetra
  • Pigment 1 V-300M (manufactured by Nemoto Special Chemical Co., Ltd., aluminum oxide activated by oxides of europium and neodymium. Inorganic fluorescent phosphorescent pigment) Pigment 2: D-918 (product of Toho Chemical Industry Co., Ltd., white pigment containing titanium oxide)
  • the fluoropolymer 1 contains 50 mol%, 2 mol%, and 28 mol% of units based on CTFE, CM-EOVE, CHVE, and EVE in this order relative to all units contained in the fluoropolymer 1. It was a polymer having a hydroxyl value of 11 mg KOH / g, containing 20 mol%.
  • the fluorine-containing polymer 2 contains 50 mol% and 0.5 mol% of units based on CTFE, CM-EOVE, CHMVE, CHVE and EVE in this order relative to all units contained in the fluorine-containing polymer 2. It was a polymer having a hydroxyl value of 49 mg KOH / g, containing 10 mol%, 17 mol%, and 22.5 mol%.
  • the fluorine-containing polymer 3 contains 50 mol%, 10 mol%, 15 mol%, and 25 mol% of units based on CTFE, HBVE, CHVE, and EVE in this order relative to all units contained in the fluorine-containing polymer 2. %, And the polymer had a hydroxyl value of 52 mg KOH / g.
  • Examples 1 to 5 Production of paints s1 to s5
  • a film forming aid 7.5 g
  • a thickener 0.1 g
  • a curing agent 1 5.4 g
  • an additive 1 2.4 g
  • Examples 6 to 10 Production of paints s6 to s10
  • the same procedure as in the preparation of the coatings s1 to s5 was carried out except that the aqueous dispersion 1 was changed to the aqueous dispersion 2 as shown in Table 1, to obtain coatings s6 to s10, respectively.
  • Examples 11 to 15 Production of paints s11 to s15
  • a curing catalyst diluted 10 -4 times with xylene to 3 g
  • a curing agent 2 6.5 g
  • an additive 1 2.4 g
  • the same procedure was carried out except that the additive 1 was changed to the additives 2 to 5 to obtain paints s12 to s15, respectively.
  • Examples 16-18 Production of paints 16-18
  • the same procedure as in the preparation of the paints s1, s6 and s11 was repeated except that the additive 1 was not added, to obtain paints s16 to s18, respectively.
  • Examples 19-24 Production of paints s19-s24
  • the same procedure as in the preparation of paints s1, s5, s6, s10, s11 and s15 is carried out except that the amounts of additives used in each example are changed as shown in Table 1, and paints s19 to s24, respectively. I got
  • test plate 1 Brush coated with epoxy resin paint (made by China Paint Co., Ltd .; product name "SEAJET 013 main agent” and product name “SEAJET 013 Curing agent” at a mass ratio of 4: 1) on both sides of the aluminum base After drying for 1 week at room temperature (25 ° C.), an aluminum substrate with an undercoat film (film thickness 60 ⁇ m) was obtained. A paint s1 is coated with an applicator on the undercoat film of the obtained substrate, dried at normal temperature for 2 weeks, and a test with a coating (film thickness 30 ⁇ m) including the fluoropolymer 1 and the additive 1 I got a board 1.
  • test plates 2 to 24 The same procedure as in the preparation of test plate 1 was repeated except that paints s2 to s24 were used instead of paint s1 to obtain test plates 2 to 24.
  • test plate 25 A solution containing hydrolysable polymer a obtained by dehydration condensation of hydroxybenzoic acid and cyclohexanedicarboxylic acid (50% by mass of polymer a) and additive 1 are mixed on the coating film of test plate 16 The resulting topcoat paint a1 was applied by an applicator and then dried at 25 ° C. for 1 week to form a hydrolyzable film (film thickness 30 ⁇ m). Thus, a coated test plate 25 was obtained, which was formed on the coating film of the test plate 16 and contained the polymer a and the additive described in Table 3 and did not contain the fluorine-containing polymer.
  • test plate 26 was obtained in the same manner as in the manufacture of the test plate 25 except that the test plate 17 was used instead of the test plate 16.
  • test plate 27 was obtained in the same manner as described above except that the test plate 18 was used instead of the test plate 16.
  • test plates 28 to 30 In the production of the test plates 25 to 27, the test was carried out in the same manner as in the test plate 28 except that the top coat a2 obtained by mixing the solution containing the polymer a and the additive 5 was used instead of the paint a1. I got ⁇ 30.
  • a paint s23 is applied by an applicator on the fluorescent coating, dried at normal temperature (25 ° C.) for one week, and a top coat (film thickness 30 ⁇ m) containing the fluoropolymer 3 and the additive 1 Formed.
  • a test plate 31 was obtained in which the undercoating film, the colored coating film, the fluorescent coating film, and the topcoating film containing the fluoropolymer 1 and the additive 1 were laminated in this order.
  • test plate 32 A test plate 32 in which an undercoat film, two layers of a colored film, and a topcoat film are laminated in this order in the same manner except that a colored paint is used instead of the fluorescent paint in the manufacture of the test plate 31.
  • a colored paint is used instead of the fluorescent paint in the manufacture of the test plate 31.
  • A Adhesion of barnacles and shellfish was observed in an area of 20% or more and 50% or less of the coating film surface.
  • B Adhesion of barnacles and shellfish was observed in an area of 50% or more and 70% or less of the coating film surface.
  • C Adhesion of barnacles and shellfish was observed in an area of more than 70% of the coating film surface.
  • the evaluation results described above are shown in Tables 1 to 4.
  • the “paint number” and “paint component” in Tables 1 to 3 are those of the paint used to form the coating disposed on the outermost surface of each test plate.
  • “XF” in Tables 1 and 2 is the content (mass part) of the additive with respect to 100 mass parts of the fluoropolymer in a coating material.
  • “XC” in Table 3 is content (mass part) of the additive with respect to 100 mass parts of the hydrolysable polymer in a coating material.
  • Table 4 the presence or absence of the fluorescence coating film in a test plate was described in the fluorescence coating film column, and the coating material used for formation of the top coating film was described in the top coating film column.
  • the paint containing the fluorine-containing polymer and at least one of the additives forms a coating film having excellent bioadhesiveness. Those coatings were particularly excellent in preventing adhesion to the larvae of barnacles. Moreover, the coating film containing the fluorine-containing polymer and the photoacid generator was particularly excellent in preventing adhesion of shellfish and shellfish, and the coating film containing the fluorine-containing polymer and the photobase generator was particularly excellent in preventing adhesion of algae. .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un matériau de revêtement anti-encrassement biologique pouvant former un film possédant d'excellentes performances anti-encrassement biologique. Ce matériau de revêtement anti-encrassement biologique est caractérisé en ce qu'il contient un polymère contenant du fluor et au moins un additif choisi parmi un générateur d'acide et un générateur de base.
PCT/JP2018/047943 2017-12-28 2018-12-26 Matériau de revêtement anti-encrassement biologique WO2019131797A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019562127A JPWO2019131797A1 (ja) 2017-12-28 2018-12-26 生物付着防止塗料

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017253750 2017-12-28
JP2017-253750 2017-12-28
JP2018147780 2018-08-06
JP2018-147780 2018-08-06

Publications (1)

Publication Number Publication Date
WO2019131797A1 true WO2019131797A1 (fr) 2019-07-04

Family

ID=67067506

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/047943 WO2019131797A1 (fr) 2017-12-28 2018-12-26 Matériau de revêtement anti-encrassement biologique

Country Status (2)

Country Link
JP (1) JPWO2019131797A1 (fr)
WO (1) WO2019131797A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021016303A (ja) * 2019-07-17 2021-02-15 住友電気工業株式会社 ダイナミックケーブル、ダイナミックケーブルの製造方法およびダイナミックケーブルの布設方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009535214A (ja) * 2006-05-04 2009-10-01 イーストマン ケミカル カンパニー 親水性汚れ剥離コーティングおよびその使用
JP2012057007A (ja) * 2010-09-07 2012-03-22 Kaneka Corp 塗料用樹脂組成物
WO2013051669A1 (fr) * 2011-10-05 2013-04-11 旭硝子株式会社 Composition comprenant un copolymère fluoré d'oléfine/alcool de vinyle et un composé d'alcoxysilane, articles durcis formés à partir de ladite composition, et film comprenant ledit article durci
JP2015086312A (ja) * 2013-10-31 2015-05-07 旭硝子株式会社 蛍光塗料組成物及び物品
US20160312040A1 (en) * 2012-11-13 2016-10-27 3M Innovative Properties Company Curable Antifouling Composition, Method of Use, and Articles
JP2017101205A (ja) * 2015-12-04 2017-06-08 クレハ合繊株式会社 成形体並びにこれを用いたシート、繊維、糸、及び魚網
WO2017104766A1 (fr) * 2015-12-18 2017-06-22 旭硝子株式会社 Dispersion liquide aqueuse, composition de matériau de revêtement contenant du fluor et article revêtu

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009535214A (ja) * 2006-05-04 2009-10-01 イーストマン ケミカル カンパニー 親水性汚れ剥離コーティングおよびその使用
JP2012057007A (ja) * 2010-09-07 2012-03-22 Kaneka Corp 塗料用樹脂組成物
WO2013051669A1 (fr) * 2011-10-05 2013-04-11 旭硝子株式会社 Composition comprenant un copolymère fluoré d'oléfine/alcool de vinyle et un composé d'alcoxysilane, articles durcis formés à partir de ladite composition, et film comprenant ledit article durci
US20160312040A1 (en) * 2012-11-13 2016-10-27 3M Innovative Properties Company Curable Antifouling Composition, Method of Use, and Articles
JP2015086312A (ja) * 2013-10-31 2015-05-07 旭硝子株式会社 蛍光塗料組成物及び物品
JP2017101205A (ja) * 2015-12-04 2017-06-08 クレハ合繊株式会社 成形体並びにこれを用いたシート、繊維、糸、及び魚網
WO2017104766A1 (fr) * 2015-12-18 2017-06-22 旭硝子株式会社 Dispersion liquide aqueuse, composition de matériau de revêtement contenant du fluor et article revêtu

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021016303A (ja) * 2019-07-17 2021-02-15 住友電気工業株式会社 ダイナミックケーブル、ダイナミックケーブルの製造方法およびダイナミックケーブルの布設方法

Also Published As

Publication number Publication date
JPWO2019131797A1 (ja) 2020-12-24

Similar Documents

Publication Publication Date Title
JP6696677B2 (ja) 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
JP6676654B2 (ja) 防汚塗料組成物、防汚塗膜、防汚基材、および該防汚基材の製造方法
JP6663928B2 (ja) 防汚性複合塗膜、防汚基材、および該防汚基材の製造方法
EP3480267B1 (fr) Composition de matériau de revêtement antisalissure, film de revêtement antisalissure, substrat doté d'un film de revêtement antisalissure et procédé de production associé, et procédé antisalissure
US20130102708A1 (en) Antifouling coating composition, antifouling coating film, and antifouling method for substrate
JP6909894B2 (ja) 防汚塗料組成物、防汚塗膜、防汚基材及びその製造方法
CN1618828A (zh) 船舶涂料用含三芳基甲硅烷基（甲基）丙烯酰基的共聚物
EP3147336A1 (fr) Film monocouche hydrophile
WO2019131797A1 (fr) Matériau de revêtement anti-encrassement biologique
WO2017104766A1 (fr) Dispersion liquide aqueuse, composition de matériau de revêtement contenant du fluor et article revêtu
CN102365339B (zh) 常温固化性树脂涂料组合物
JP2018168220A (ja) 水性分散液
US11015065B2 (en) Anti-biofouling coating material
JP2015086312A (ja) 蛍光塗料組成物及び物品
CN113444418A (zh) 防污涂料组合物
JPH09302328A (ja) 防汚染付着剤および塗料用組成物
JP6992757B2 (ja) 生物付着防止塗料
WO2017110926A1 (fr) Matériau de revêtement antisalissures
JP2019031582A (ja) 海洋生物付着防止塗料
JP2018062547A (ja) 生物付着防止塗料
JP2022024015A (ja) 防汚塗料組成物
JP2021123712A (ja) 組成物、硬化膜、積層体、船舶、水中構造物、医療デバイス、及び、マイクロ流路チップ
WO2018194068A1 (fr) Dispersion aqueuse, revêtement aqueux, et article revêtu
JP2006283160A (ja) 被覆鋼材

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: 18897153

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019562127

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18897153

Country of ref document: EP

Kind code of ref document: A1