WO2019078097A1 - Matériau de revêtement antirouille, film de revêtement et corps stratifié - Google Patents

Matériau de revêtement antirouille, film de revêtement et corps stratifié Download PDF

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Publication number
WO2019078097A1
WO2019078097A1 PCT/JP2018/038025 JP2018038025W WO2019078097A1 WO 2019078097 A1 WO2019078097 A1 WO 2019078097A1 JP 2018038025 W JP2018038025 W JP 2018038025W WO 2019078097 A1 WO2019078097 A1 WO 2019078097A1
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Prior art keywords
aluminum
fluorine
metal
containing copolymer
copper
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PCT/JP2018/038025
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English (en)
Japanese (ja)
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真由美 飯田
田中　義人
琢磨 川部
井本　克彦
恵子 鷲野
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ダイキン工業株式会社
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Priority to JP2019549237A priority Critical patent/JP6863469B2/ja
Publication of WO2019078097A1 publication Critical patent/WO2019078097A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09D5/08—Anti-corrosive paints

Definitions

  • the present invention relates to an anticorrosion paint, a coating film and a laminate.
  • paints containing a fluorine-containing copolymer are conventionally known as paints containing a fluorine-containing copolymer.
  • Patent Document 1 contains a fluorine-containing copolymer (A) and a pigment (B), and the fluorine-containing copolymer (A) is represented by a unit represented by the following formula (1), and a unit represented by the following formula: And a unit represented by (2), wherein the fluorine-containing copolymer (A) has a number average molecular weight of 10,000 to 100,000, and the content of the pigment (B) is A paint composition characterized in that it is 20 to 200 parts by mass with respect to 100 parts by mass of the fluorocopolymer (A) is described.
  • X and Y are each independently H, F, CF 3 or Cl.
  • a water-based surface treatment agent used to form an insulating film on the surface of a magnetic steel sheet which is a unit based on fluoroolefin, vinyl ether, allyl ether or vinyl carboxylate, A unit based on monomer A having an alicyclic alkyl group, and a single amount having a vinyl ether, allyl ether or vinyl carboxylate, and at least one crosslinkable group selected from a hydroxyl group, a carboxy group and an amino group
  • An aqueous surface treatment agent which comprises a fluoropolymer having a unit based on Body B, a crosslinking agent, and a metal salt.
  • the present invention can sufficiently prevent the corrosion of a specific metal and the corrosion of a dissimilar metal joint, and can form a coating film excellent in transparency, antifouling property and adhesion.
  • the purpose is to provide paint.
  • Another object of the present invention is to provide a coating film which can sufficiently prevent the corrosion of a specific metal and the corrosion of a dissimilar metal joint and is also excellent in transparency, antifouling property and adhesion. Do.
  • the metal base or the dissimilar metal joint is not easily corroded, and the high transparency of the coating film can sufficiently exhibit the aesthetics of the metal base or the dissimilar metal joint, and the antifouling property and the adhesion Also aims to provide an excellent laminate.
  • a fluorine-containing copolymer containing a specific monomer unit contains a specific water vapor permeability, a specific oxygen permeability coefficient and a specific oxygen permeability coefficient.
  • the present invention is a rust preventive paint comprising a fluorine-containing copolymer comprising a fluorine-containing olefin unit and a vinyl alcohol unit, wherein the fluorine-containing copolymer has the characteristics (a) to (c). is there.
  • the said fluorine-containing copolymer is 3.0 or less in conversion haze value per 30 micrometers.
  • the hydroxyl value of the said fluorine-containing copolymer is 400 mgKOH / g or more.
  • the anticorrosion paint of the present invention is preferably for a dissimilar metal joint.
  • the dissimilar metal joint is preferably a dissimilar metal joint of a wire or a dissimilar metal joint of piping.
  • the different metals are aluminum or aluminum alloy and copper, aluminum or aluminum alloy and iron, aluminum or aluminum alloy and zinc, aluminum or aluminum alloy and nickel, aluminum or aluminum alloy and tin, copper and iron, copper and zinc, copper and the like Preferably, it is nickel or copper and tin.
  • the anti-corrosive paint of the present invention is preferably for steel plate, for cast iron, for high-temperature and high-pressure cast steel, or for aluminum-zinc alloy-plated steel plate.
  • the above-mentioned anticorrosive paint can further contain a curing agent.
  • the said fluorine-containing copolymer has the solubility to alcohol solvent.
  • the above-mentioned anticorrosion paint preferably further contains a solvent.
  • the present invention is also a coating film characterized in that it is formed from the above-mentioned anticorrosion paint.
  • the present invention is also a laminate comprising a metal substrate and the above-mentioned coating film.
  • the anticorrosion paint of the present invention can sufficiently prevent corrosion of metal and dissimilar metal joints, and can form a coating excellent in transparency, antifouling property and adhesion.
  • the coating film of the present invention can sufficiently prevent corrosion of metal and dissimilar metal bonding portions, and is also excellent in transparency, antifouling property and adhesion.
  • the laminate of the present invention is resistant to corrosion of the metal base and the dissimilar metal joint, and can sufficiently exhibit the aesthetics of the metal base and the dissimilar metal joint due to the high transparency of the coating film, and has antifouling properties and adhesion. It is also excellent in In particular, when the above-mentioned metal is a steel plate, cast iron, cast steel for high temperature and high pressure, or aluminum zinc alloy plated steel plate, it exhibits excellent corrosion resistance.
  • the anti-corrosive paint of the present invention is characterized in that it contains a fluorine-containing copolymer, and the above-mentioned fluorine-containing copolymer has the characteristics (a) to (c).
  • Samples for measuring the water vapor permeability, the oxygen permeability coefficient, and the water absorption rate are prepared by the following method.
  • a fluorocopolymer is dissolved in dimethylacetamide (DMAC) or isopropyl alcohol (IPA) solvent to a concentration of 15% by mass, formed on a polypropylene plate using a 10 mil doctor blade, and then formed for 30 minutes at room temperature.
  • DMAC dimethylacetamide
  • IPA isopropyl alcohol
  • the coated film is similarly formed on a glass plate or an aluminum plate and dried to prepare a coated plate.
  • a highly peelable polypropylene board as said polypropylene board.
  • the water vapor permeability is measured according to the cup method (JIS Z0208-1976), condition B (temperature 40 ⁇ 0.5 ° C., relative humidity 90 ⁇ 2%). Assuming that the measured value is Q (g / m 2 ⁇ day) and the film thickness value is T ( ⁇ m), the water vapor transmission rate Q T per 100 ⁇ m can be calculated by the following equation.
  • Q T Q ⁇ T / 100
  • the oxygen permeability coefficient is measured according to JIS K 7126-1. Specifically, measurement can be performed according to JIS K 7126-1 using a differential pressure type gas / vapor permeability measurement device.
  • the differential pressure is 1 atm
  • the test temperature is 23 ⁇ 2 ° C.
  • the drying condition is measured
  • the detector is measured by a gas chromatograph (thermal conductivity detector) by a differential pressure method according to JIS K 7126-1.
  • the differential pressure type gas / vapor permeability measuring apparatus for example, GTR Tech Inc. GTR-30XAD2, Yanako Technical Science Inc. G2700T • F can be used.
  • Water vapor permeability per above 100 ⁇ m is less 25g / m 2 ⁇ day, 22g / m 2 ⁇ day or less are preferred, 20 g / m or less, more preferably 2 ⁇ day, although a lower limit is not particularly limited, 0.1 g It may be / m 2 ⁇ day.
  • oxygen permeability coefficient is preferably at most 2.0E-13cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg, more preferably not more than 1.5E-13cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg, but the lower limit is not particularly limited , 1.0 E-15 cc cm / cm 2 sec cm Hg.
  • 10 mass% or less is preferable, 8 mass% or less is more preferable, and although a minimum is not specifically limited, 0.1 mass% may be sufficient.
  • the said fluorine-containing copolymer is 3.0 or less in conversion haze value per 30 micrometers.
  • the converted haze value is more preferably 2.5 or less.
  • the said converted haze value is measured according to JISK7136 using a haze meter.
  • a haze meter As a haze meter, a haze meter (made by Nippon Denshoku Co., Ltd. HAZE MATER NDH7000SP) can be used.
  • the haze value was measured using a haze meter H, the value of the film thickness when the T ( ⁇ m), converted haze value H T per 30 ⁇ m can be calculated by the following equation.
  • H T H ⁇ 30 / T
  • the sample for measuring the said conversion haze value is prepared by the same method as the sample for measuring a water vapor transmission rate, an oxygen transmission coefficient, and a water absorption.
  • the fluorine-containing copolymer has a fluorine-containing olefin unit and a vinyl alcohol unit (—CH 2 —CH (OH) —).
  • the fluorine-containing olefin unit represents a polymerization unit based on a fluorine-containing olefin.
  • the fluorine-containing olefin is a monomer having a fluorine atom.
  • PAVE perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], perfluoro (butyl vinyl ether) and the like, among them PMVE , PEVE or PPVE is more preferred.
  • Rf 2 is a perfluoroalkyl group having 1 to 3 carbon atoms
  • CF 2 CFCF—OCH 2 —CF 2 CF 3 is more preferable.
  • At least 1 sort (s) selected from the group which consists of TFE, CTFE, and HFP is more preferable, and TFE is still more preferable.
  • the water vapor permeability, the oxygen permeability coefficient, and the water absorption can be adjusted mainly by adjusting the content of the fluorine-containing olefin unit and the vinyl alcohol unit.
  • the fluorine-containing copolymer it is preferable that the fluorine-containing olefin unit is 15 to 45 mol% and the vinyl alcohol unit is 55 to 85 mol%.
  • the content of each monomer unit is more preferably 20 to 40% by mole, and more preferably 60 to 80% by mole of the vinyl alcohol unit.
  • the fluorine-containing copolymer preferably has an alternating rate of 50% or less of a fluorine-containing olefin unit and a vinyl alcohol unit.
  • the alternating ratio is in such a range, effects of high transparency of the coating film and high solvent solubility are obtained. More preferably, it is 45% or less, and particularly preferably 35% or less. Moreover, Preferably it is 1% or more, More preferably, it is 3% or more, More preferably, it is 5% or more. If the alternating ratio is too low, the heat resistance may be reduced, which is not preferable.
  • the alternating ratio of the fluorine-containing olefin unit and the vinyl alcohol unit is measured with the fluorine-containing copolymer before hydroxylation.
  • the fluorine-containing copolymer before hydroxylation represents a polymer of a fluorine-containing olefin unit and a vinyl ester unit.
  • the fluorine-containing copolymer can be synthesized, for example, by hydrolysis of a polymer of a fluorine-containing olefin unit and a vinyl ester unit. It is difficult to use for polymerization because vinyl monomers corresponding to vinyl alcohol units are chemically unstable and decompose in the first place.
  • the alternating ratio of the fluorine-containing olefin unit and the vinyl alcohol unit in the present invention is one obtained by measuring the fluorine-containing copolymer before hydroxylation.
  • the number of V units of A, B and C is a vinyl ester unit (-CH 2 -
  • the unit R is preferably an alkyl group having 1 to 11 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferably, it is an alkyl group having 1 to 3 carbon atoms.
  • vinyl ester monomer units monomer units derived from the following vinyl esters are exemplified.
  • Vinyl benzoate vinyl versatate.
  • monomer units derived from vinyl acetate, vinyl propionate and vinyl versatate are preferable. More preferably, they are a vinyl acetate monomer unit and a vinyl propionate monomer unit, and still more preferably a vinyl acetate monomer unit.
  • the content of the vinyl ester monomer unit is the total content of the fluorine-containing olefin unit and the vinyl alcohol unit.
  • the vinyl ester monomer unit content is preferably 1 to 30 mol%, and more preferably 1 to 20 mol%.
  • the alternating ratio of the fluorine-containing olefin unit and the vinyl alcohol unit and the vinyl ester monomer unit is 50% or less Is preferred.
  • the alternating ratio is in such a range, effects of high transparency of the coating film and high solvent solubility are obtained. More preferably, it is 45% or less, and particularly preferably 35% or less.
  • it is 1% or more, More preferably, it is 3% or more, More preferably, it is 5% or more. If the alternating ratio is too low, the heat resistance may be reduced, which is not preferable.
  • the alternating ratio of the fluorine-containing olefin unit and the vinyl alcohol unit and the vinyl ester monomer unit is the same as the alternating ratio of the fluorine olefin unit and the vinyl alcohol unit, and the fluorine-containing copolymer before hydroxylation is used. That is, when the structural unit before hydroxylation is a vinyl ester monomer unit, 1 H-NMR measurement of the fluorine-containing copolymer is carried out using a solvent in which the fluorine-containing copolymer such as heavy acetone is dissolved, and the following formula It can be calculated as an alternating rate of 3 chains.
  • Alteration rate (%) C / (A + B + C) ⁇ 100
  • the higher the alternating ratio of the fluoroolefin unit and the vinyl alcohol unit of the fluorocopolymer the better the dispersibility of the pigment and the uniformity of the crosslinking improve.
  • the alternating ratio of the fluoroolefin unit and the vinyl alcohol unit is increased, the heat resistance is improved, but the crystallinity is also improved. It was found that the film was likely to be opaque (the haze value was increased) due to scattering. This is a big problem when it is desired to use a clear paint without adding a pigment. Therefore, the alternating rate is preferably 50% or less, for example.
  • the above-mentioned fluorine-containing copolymer may have other monomer units other than a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit in the range which does not impair the effect of the present invention.
  • a monomer not containing a fluorine atom for example, ethylene, propylene, 1-butene, 2-butene, vinyl chloride, At least one fluorine-free ethylenic monomer selected from the group consisting of vinylidene chloride, vinyl ether monomer, and unsaturated carboxylic acid is preferred.
  • the total content of the other monomer units is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, of the total monomer units of the fluorine-containing copolymer, and 0 to 50 More preferably, it is 30 mol%.
  • each monomer unit constituting the fluorine-containing copolymer can be calculated by appropriately combining NMR, FT-IR, and elemental analysis according to the type of the monomer.
  • the weight-average molecular weight of the fluorine-containing copolymer is not particularly limited, but is preferably 9,000 or more, and more preferably 10,000 or more. More preferably, it is 20,000 to 2,000,000, and particularly preferably 30,000 to 1,000,000.
  • the weight average molecular weight is preferably 200,000 or less, may be 150,000 or less, and may be 100,000 or less.
  • the weight average molecular weight can be determined by gel permeation chromatography (GPC).
  • the hydroxyl value of the above-mentioned fluorine-containing copolymer is 200 mg KOH / g or more because it can form a coating film which is further excellent in anti-corrosion effect and excellent in transparency, stain resistance and adhesion. Is preferred.
  • 400 mgKOH / g or more is more preferable, 500 mgKOH / g or more is still more preferable, 1000 mgKOH / g or less is preferable, and 800 mgKOH / g or less is more preferable.
  • the above-mentioned hydroxyl value can be measured by the method according to JIS K 0070 or the calculation from the nuclear magnetic resonance method.
  • the anticorrosion paint of the present invention is suitable for preventing corrosion for dissimilar metal joints.
  • the dissimilar metal joint include the dissimilar metal joint of the electric wire shown in FIG. 2, and the dissimilar metal joint of the pipe shown in FIG.
  • different metals are two metals respectively (A) and (B), and when their standard electrode potentials are EA and EB, a combination of EA and EB with a difference of 0.1 volt or more is different metal I will call.
  • the standard electrode potential is separated by 0.1 volt or more, when the metals come in contact with each other, the corrosion is more likely to progress than when each metal is present alone.
  • the combinations exemplified here are specific examples of the dissimilar metals.
  • the dissimilar metals include aluminum or aluminum alloy and copper, aluminum or aluminum alloy and iron, aluminum or aluminum alloy and zinc, aluminum or aluminum alloy and nickel, aluminum or aluminum alloy and tin, copper and iron, copper and zinc, copper and the like Nickel or copper and tin are preferred. Since oxygen and moisture are required for the progress of corrosion accompanying this dissimilar metal bonding, the anticorrosion paint of the present invention exhibits high barrier properties against oxygen and water vapor, and low water absorption, so it is effective to rust effectively. Occurrence is suppressed.
  • the dissimilar metal indicates the state at the joint portion generated when the article (A) and the article (B) are joined, and does not indicate the state of the dissimilar metal internally generated in an alloy such as SUS.
  • the dissimilar metal species is not iron but tin or zinc on the outermost surface. That is, when the article (A) is a tinplate, it is tin as the metal species, and when the article (B) is tin, it is zinc as the metal species.
  • the dissimilar metal joining portion refers to a dissimilar metal joining portion of an electric wire, or a dissimilar metal joining portion of a pipe, or a joining portion in the case of fixing a metal plate or a metal member with a metal screw or bolt, a metal duct And the joint portion of the metal wall portion.
  • dissimilar metal junctions junctions of aluminum core wires and copper core wires, junctions of aluminum pipes and SUS pipes, metal plates of tin (tin) and tin (zinc) and SUS The fixed part etc. with a manufactured screw are mentioned.
  • the present invention is also applied to the joint portion between the core wire of aluminum and copper such as a printed circuit board. Can be suitably employed. It has been found that the anticorrosion paint of the present invention exhibits particularly excellent anticorrosion to a dissimilar metal joint by being composed of a fluorine-containing copolymer having the following characteristics.
  • the anti-corrosive paint of the present invention exhibits excellent anti-corrosion properties for steel plates, cast irons, high-temperature and high-pressure cast steels, or aluminum-zinc alloy plated steel plates, and has transparency, anti-staining properties and adhesion. It is possible to form an excellent coating film for marine structures, kitchen appliances, metal pipes for automobiles, exteriors with high designability, piping for water and water treatment facilities, wiring for various power generation facilities or prevention of piping. It can be suitably used as a rust paint.
  • dissimilar metal joint examples include a dissimilar metal joint of a wire, a dissimilar metal joint of a pipe, and the like.
  • the dissimilar metal joint may be joined with a dissimilar metal, and may be mechanically joined or chemically joined.
  • the dissimilar metals include aluminum or aluminum alloy and copper, aluminum or aluminum alloy and iron, aluminum or aluminum alloy and zinc, aluminum or aluminum alloy and nickel, aluminum or aluminum alloy and tin, copper and iron, copper and zinc, copper and the like Preferably, it is nickel or copper and tin.
  • aluminum alloy aluminum 2000 series (Al-Cu-Mg series: aluminum copper magnesium alloy) aluminum alloy, aluminum 3000 series (Al-Mn series: aluminum manganese alloy) aluminum alloy, aluminum 4000 series (Al-Si) System: Aluminum silicon alloy) Aluminum alloy, Aluminum 5000 series (Al-Mg: Aluminum magnesium alloy) Aluminum alloy, Aluminum 6000 series (Al-Mg-Si system: Aluminum magnesium silicon alloy) Aluminum alloy, Aluminum 7000 series (Al- Zn—Mg-based: Aluminum Zinc Magnesium Alloy) Aluminum alloy or aluminum 8000-based (Li-added system: Aluminum-lithium alloy) aluminum alloy is preferable.
  • the duralumin is an aluminum 7000 series aluminum alloy.
  • the anticorrosion paint of the present invention preferably contains a curing agent. Since the said fluorine-containing copolymer has a hydroxyl group, a cured coating film can be formed from the rustproofing coating material of this invention. The cured coating film formed from the rust-preventing paint of the present invention exhibits a further excellent rust-preventing effect as compared with a non-cured coating film, and is further excellent in transparency, antifouling property and adhesion.
  • the curing agent may be of any type as long as it is capable of crosslinking the hydroxyl group in the fluorine-containing copolymer, but is preferably an isocyanate curing agent, an amino resin curing agent or the like.
  • XDI xylylene diisocyanate
  • H6XDI bis (isocyanatomethyl) cyclohexane
  • hexa At least one selected from the group consisting of blocked isocyanate compounds based on methylene diisocyanate (HDI), polyisocyanate compounds derived from hexamethylene diisocyanate (HDI), and polyisocyanate compounds derived from isophorone diisocyanate (IPDI) Compounds are preferred.
  • HDI methylene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • isocyanate (i) isocyanate selected from the group consisting of xylylene diisocyanate (XDI) and bis (isocyanatomethyl) cyclohexane (hydrogenated XDI, H6XDI) as a curing agent.
  • XDI xylylene diisocyanate
  • H6XDI bis (isocyanatomethyl) cyclohexane
  • a polyisocyanate compound (hereinafter, also referred to as polyisocyanate compound (I)) is used, the adhesion between the cured coating film obtained from the rust-preventive coating of the present invention and the metal substrate becomes more excellent. .
  • polyisocyanate compound (I) for example, an adduct obtained by addition polymerization of the isocyanate (i) and an aliphatic polyhydric alcohol having a valence of 3 or more, an isocyanurate structure (nurate comprising the isocyanate (i) And the biuret comprising the above-mentioned isocyanate (i).
  • R 6 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • R 7 represents a phenylene group or a cyclohexylene group.
  • K is an integer of 3 to 20.
  • R 6 in the general formula (3) is a hydrocarbon group based on the trivalent or higher aliphatic polyhydric alcohol, and is preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms. Aliphatic hydrocarbon groups are more preferred.
  • R 7 is a phenylene group, 1,2-phenylene group (o-phenylene group), 1,3-phenylene group (m-phenylene group), and 1,4-phenylene group (p-phenylene group) It may be either. Among these, 1,3-phenylene group (m-phenylene group) is preferable. In addition, all of R 7 in the general formula (3) may be the same phenylene group, or two or more types may be mixed. When R 7 is a cyclohexylene group, it may be any of a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group. Among these, 1,3-cyclohexylene is preferable.
  • R 7 in the general formula (3) may be the same cyclohexylene group, or two or more kinds may be mixed.
  • the above k is a number corresponding to the valence of a trivalent or higher aliphatic polyhydric alcohol.
  • the above k is more preferably an integer of 3 to 10, and still more preferably an integer of 3 to 6.
  • the isocyanurate structure has the following general formula (4): And one or more isocyanurate rings represented by As said isocyanurate structure, the trimer obtained by trimerization reaction of the said isocyanate, the pentamer obtained by pentamerization reaction, the heptamer obtained by heptamerization reaction etc. can be mentioned.
  • Trimer is preferably represented by. That is, it is preferable that the said isocyanurate structure is a trimer of at least 1 sort (s) of isocyanate selected from the group which consists of xylylene diisocyanate and bis (isocyanate methyl) cyclohexane.
  • the above biuret has the following general formula (6): (Wherein, R 7 has the general formula (3) is the same as R 7 in.) Is a compound having a structure represented by, under different conditions than the case of obtaining the isocyanurate structure, the It can be obtained by trimerizing an isocyanate.
  • an example of the trivalent or more aliphatic polyhydric alcohol is glycerol Trimethylolpropane (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris (bishydroxymethyl) propane, 2,2 -Trihydric alcohols such as bis (hydroxymethyl) butanol-3; tetrahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols such as arabitol, ribitol and xylitol (pentitol); sorbit, mannit, galactitol, allodulcit and the like Hexavalent alcohol (hexit) etc. That.
  • TMP Trimethylolpropane
  • 1,2,6-hexanetriol trimethylolethane
  • 2,4-dihydroxy-3-hydroxymethylpentane 1,1,1-tris (bishydroxymethyl) propane
  • xylylene diisocyanate (XDI) used as a component of the above adduct 1,3-xylylene diisocyanate (m-xylylene diisocyanate), 1,2-xylylene diisocyanate (o-xylylene diisocyanate), 1 And 4-xylylene diisocyanate (p-xylylene diisocyanate).
  • 1,3-xylylene diisocyanate m-xylylene diisocyanate
  • p-xylylene diisocyanate 1,3-xylylene diisocyanate (m-xylylene diisocyanate) is preferable.
  • Preferred in the present invention by addition polymerization of at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanatomethyl) cyclohexane and an aliphatic polyhydric alcohol having 3 or more valences as described above.
  • R 8 represents a phenylene group or a cyclohexylene group
  • R 8 represents a phenylene group or a cyclohexylene group
  • TMP trimethylolpropane
  • the phenylene group or cyclohexylene group represented by R 8 in the general formula (7) is as described for R 7 in the general formula (3).
  • the said polyisocyanate compound (I) is an isocyanurate structure
  • Takenate D121N The Mitsui Chemicals make, H6XDI nurate, NCO content 14.0%
  • Takenate D127N the Mitsui Chemicals make, H6XDI nurate, trimer of H6XDI, NCO content 13.5%
  • the rustproofing coating of the present invention has a longer pot life (useful time) .
  • blocked isocyanate those obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate (hereinafter, also referred to as polyisocyanate compound (II)) with a blocking agent are preferable.
  • polyisocyanate compound (II) for example, an adduct obtained by addition polymerization of hexamethylene diisocyanate and an aliphatic polyhydric alcohol having a valence of 3 or more, an isocyanurate structure (nurate structure) comprising hexamethylene diisocyanate, And biurets composed of hexamethylene diisocyanate.
  • R 9 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms, and k is an integer of 3 to 20).
  • R 9 in the above general formula (8) is a hydrocarbon group based on the trivalent or higher aliphatic polyhydric alcohol, and an aliphatic hydrocarbon group having 3 to 10 carbon atoms is more preferable, and 3 to 6 carbon atoms are more preferable. Aliphatic hydrocarbon groups are more preferred.
  • the above k is a number corresponding to the valence of a trivalent or higher aliphatic polyhydric alcohol. The above k is more preferably an integer of 3 to 10, and still more preferably an integer of 3 to 6.
  • the isocyanurate structure has the following general formula (4): And one or more isocyanurate rings represented by As said isocyanurate structure, the trimer obtained by trimerization reaction of the said isocyanate, the pentamer obtained by pentamerization reaction, the heptamer obtained by heptamerization reaction etc. can be mentioned.
  • trimer represented by is preferable.
  • the above biuret has the following general formula (10): It is a compound which has a structure represented by these, and can be obtained by trimerizing hexamethylene diisocyanate under the conditions different from the case where the said isocyanurate structure is obtained.
  • a compound having active hydrogen as the blocking agent.
  • the compound having an active hydrogen it is preferable to use, for example, at least one selected from the group consisting of alcohols, oximes, lactams, active methylene compounds, and pyrazole compounds.
  • the above-mentioned blocked isocyanate is obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate with a blocking agent, and the above-mentioned blocking agent includes alcohols, oximes, lactams, active methylene compounds It is one of the preferred embodiments of the present invention to be at least one selected from the group consisting of pyrazole compounds.
  • the polyisocyanate compound (II) for obtaining the above-mentioned blocked isocyanate is an adduct of hexamethylene diisocyanate and a trivalent or higher aliphatic polyhydric alcohol
  • specific examples of the trivalent or higher aliphatic polyhydric alcohol include Glycerol, trimethylolpropane (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris (bishydroxymethyl) propane Trihydric alcohols such as 2,2-bis (hydroxymethyl) butanol-3; tetrahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols such as arabit, ribitol and xylitol (pentitol); sorbit, mannit and ga Lactitol, allodulcit It includes hexavalent alcohols (hexites) or the like is.
  • trimethylolpropane and pentaerythritol are particularly preferable.
  • the adduct is obtained by the addition polymerization of hexamethylene diisocyanate and the trivalent or higher aliphatic polyhydric alcohol as described above.
  • Specific examples of the compound having active hydrogen to be reacted with the above-mentioned polyisocyanate compound (II) include alcohols such as methanol, ethanol, n-propanol, isopropanol and methoxypropanol; acetone oxime, 2-butanone oxime, cyclohexanone Oximes such as oxime; lactams such as caprolactam; active methylene compounds such as methyl acetoacetate, ethyl malonate; pyrazole compounds such as 3-methylpyrazole, 3,5-dimethylpyrazole, 3,5-diethylpyrazole, etc. These may be used alone or in combination of two or more. Among them, active methylene compounds and oximes are preferable, and active methylene compounds are more preferable.
  • a polyisocyanate compound derived from hexamethylene diisocyanate (HDI) (hereinafter also referred to as polyisocyanate compound (III)) can also be used as a curing agent.
  • polyisocyanate compound (III) what was mentioned above as polyisocyanate compound (II) is mentioned.
  • polyisocyanate compound (III) Coronate HX (manufactured by Nippon Polyurethane Co., Ltd., isocyanurate structure of hexamethylene diisocyanate, NCO content 21.1%), Sumidule N 3300 (manufactured by Sumika Bayer Co., Ltd., hexamethylene) Isocyanurate structure of diisocyanate), Takenate D 170 N (Mitsui Chemical Co., Ltd., isocyanurate structure of hexamethylene diisocyanate), Sumidule N 3800 (Suumi Chemical Bayer, isocyanurate structure prepolymer type of hexamethylene diisocyanate), etc. Can be mentioned.
  • Coronate HX manufactured by Nippon Polyurethane Co., Ltd., isocyanurate structure of hexamethylene diisocyanate, NCO content 21.1%
  • Sumidule N 3300 manufactured by Sumika Bayer Co., Ltd., he
  • a polyisocyanate compound derived from isophorone diisocyanate (IPDI) (hereinafter, also referred to as a polyisocyanate compound (IV)) can be used.
  • polyisocyanate compound (IV) examples include an adduct obtained by addition polymerization of isophorone diisocyanate and an aliphatic polyhydric alcohol having a valence of 3 or more, an isocyanurate structure (nulate structure) comprising isophorone diisocyanate, and Mention may be made of biuret consisting of isophorone diisocyanate.
  • R 10 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • R 11 represents a group represented by the following general formula (12): Is a group represented by k is an integer of 3 to 20. What has a structure represented by) is preferable.
  • R 10 in the general formula (11) is a hydrocarbon group based on the trivalent or higher aliphatic polyhydric alcohol, and is preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms Aliphatic hydrocarbon groups are more preferred.
  • the above k is a number corresponding to the valence of a trivalent or higher aliphatic polyhydric alcohol. The above k is more preferably an integer of 3 to 10, and still more preferably an integer of 3 to 6.
  • the isocyanurate structure has the following general formula (4): And one or more isocyanurate rings represented by Examples of the isocyanurate structure include trimers obtained by trimerization reaction of isophorone diisocyanate, pentamers obtained by pentamerization reaction, heptamers obtained by heptamerization reaction, and the like.
  • Trimer is preferably represented by. That is, the isocyanurate structure is preferably a trimer of isophorone diisocyanate.
  • the above biuret has the following general formula (14): (Wherein, R 11 has the general formula (11) in the same as R 11 in.) Is a compound having a structure represented by, under different conditions than the case of obtaining the isocyanurate structure, isophorone It can be obtained by trimerizing diisocyanate.
  • the polyisocyanate compound (IV) is preferably at least one selected from the group consisting of the adduct and the isocyanurate structure. That is, the polyisocyanate compound (IV) is selected from the group consisting of an adduct obtained by addition polymerization of isophorone diisocyanate and an aliphatic polyhydric alcohol having a valence of 3 or more, and an isocyanurate structure comprising isophorone diisocyanate. Preferably, it is at least one selected from the group consisting of
  • polyisocyanate compound (IV) is an adduct of isophorone diisocyanate and a trivalent or higher aliphatic polyhydric alcohol
  • examples of the trivalent or higher aliphatic polyhydric alcohol include glycerol and trimethylol.
  • TMP Propane
  • 1,2,6-hexanetriol trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris (bishydroxymethyl) propane, 2,2-bis Trihydric alcohols such as hydroxymethyl) butanol-3; tetrahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols such as arabitol, ribitol and xylitol (pentitol); hexavalents such as sorbit, mannit, galactitol, allodulcit and the like Alcohol (hexit) etc. It is. Among these, trimethylolpropane and pentaerythritol are particularly preferable.
  • An adduct suitably used in the present invention can be obtained by addition polymerization of isophorone diisocyanate and a trivalent or higher aliphatic polyhydric alcohol as described above.
  • R 12 has the following general formula (12): Is a group represented by And a polyisocyanate compound obtained by addition polymerization of isophorone diisocyanate and trimethylolpropane (TMP).
  • TMP trimethylolpropane
  • TMP adduct of isophorone diisocyanate represented by the above general formula (12)
  • Takenate D140N manufactured by Mitsui Chemicals, Inc., NCO content: 11%) and the like can be mentioned.
  • isocyanurate structure which consists of isophorone diisocyanate, Desmodur Z4470 (The Sumika Bayer urethane company make, NCO content 11%) etc. are mentioned.
  • the curing agent Takenate D120N (manufactured by Mitsui Chemicals, Inc., NCO content: 11%) and Sumidule N3300 (manufactured by Sumika Bayer Co., Ltd., isocyanurate structure of hexamethylene diisocyanate) are more preferable.
  • the above-mentioned isocyanate curing agent may be used alone or in combination of two or more.
  • amino resin-based curing agent examples include polyamine compounds, melamine resins, urea resins, benzoguanamine resins, and glycoluril resins.
  • polyamine compound examples include low molecular weight diamines such as 1,2-ethanediamine, 1,3- and 1,2-propanediamine, and 1,4-butanediamine; tetraamines such as 1,2,5-pentanetriamine; Examples include tetraamines such as 1,2,4,5-benzenetetraamine.
  • the methylol melamine derivative obtained by condensing melamine and formaldehyde is made to react with methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol etc. as a lower alcohol, the compound and etherified, and mixtures thereof Can be mentioned preferably.
  • methylolmelamine derivative examples include monomethylolmelamine, dimethylolmelmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine and the like.
  • the melamine resin is classified into a completely alkyl type, a methylol group type, an imino group type and a methylol / imino group type according to the ratio to be alkoxylated, and any of them can be used in the present invention.
  • a polyisocyanate compound, a polyamine compound or a melamine resin is used among the above-mentioned curing agents, since the curing agent has a relatively large molecular weight, the flexural modulus and toughness as a coating film are increased by suppressing the elastic modulus after curing. Can be preferred. In addition, the scratching property of the surface of the coating is also suppressed, and the self-repairing property is also developed.
  • the curing agent is preferably blended in an equivalent ratio of 0.5 to 1.5, more preferably 0.8 to 1.2, in terms of the equivalent ratio to the hydroxyl group moiety of the fluorine-containing copolymer. .
  • the anticorrosion paint of the present invention may optionally contain a curing catalyst.
  • the curing catalyst is used to accelerate the curing reaction and impart excellent chemical and physical performance to the cured film.
  • a known catalyst can be used as the curing catalyst, and may be appropriately selected according to the type of the curing agent. For example, when the curing agent is an isocyanate curing agent or a blocked isocyanate curing agent, a tin catalyst, a zirconium catalyst or the like is preferable as the curing catalyst.
  • the tin catalyst examples include tin octylate, tributyltin dilaurate, dibutyltin dilaurate and the like.
  • a zirconium catalyst a zirconium chelate etc. are mentioned, for example.
  • commercially available products of zirconium catalysts include “K-KAT XC-4205” (trade name, manufactured by Kushimoto Chemical Co., Ltd.).
  • a blocked acid catalyst is preferable as the curing catalyst.
  • the blocked acid catalyst include amine salts of various acids such as carboxylic acid, sulfonic acid and phosphoric acid.
  • the curing catalyst may be used alone or in combination of two or more.
  • the content of the curing catalyst is preferably 0.00001 to 10% by mass, and more preferably 0.0001 to 5% by mass, based on the total amount of the fluorine-containing copolymer and the curing agent.
  • the said fluorine-containing copolymer has the solubility to an alcohol solvent from having excellent handleability.
  • having solubility means that when 5% by mass of the fluorine-containing copolymer is dissolved in an alcohol solvent, the fluorine-containing copolymer can not be visually recognized.
  • having solubility in an alcohol solvent may be dissolved in at least one alcohol solvent, and it is not necessary to dissolve in all alcohol solvents.
  • the alcohol-based solvent is preferably an alcohol having 1 to 10 carbon atoms, and examples thereof include methanol, ethanol, normal propyl alcohol, isopropyl alcohol, normal butanol, isobutyl alcohol, tertiary butyl alcohol, pentanol, hexanol, heptanol, octanol and the like. It can be mentioned. It is preferable that the said fluorine-containing copolymer especially has the solubility to methanol.
  • the anticorrosion paint of the present invention can be prepared by a conventional method in the form of a solvent type paint, an aqueous type paint, a powder type paint or the like.
  • the solvent-type paint is preferable in terms of ease of film formation, good drying property, and the like. That is, the rustproofing paint of the present invention preferably further contains a solvent. By including a solvent, thin film coating becomes easier, and the resulting coating can be made thinner.
  • organic solvents are preferable, and esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; , Cyclic ethers such as dioxane; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; aromatic hydrocarbons such as xylene, toluene and solvent naphtha; glycols such as propylene glycol methyl ether and ethyl cellosolve Ethers; Diethylene glycol esters such as carbitol acetate; n-pentane, n-hexane, n-heptane, n-octane,
  • the concentration of the fluorocopolymer is preferably 5 to 95% by mass, more preferably 10 to 70% by mass, based on 100% by mass of the total amount of the paint. preferable.
  • Other polymers may be added to the rustproofing paint of the present invention as long as the effects of the present invention are not impaired.
  • Another polymer is a polymer which does not correspond to the above-mentioned fluorine-containing copolymer.
  • the other polymer may or may not have a curable group.
  • a hardenable group a hydroxyl group, a carboxy group, an amino group, an epoxy group, an alkoxy silyl group, an isocyanate group etc. are mentioned.
  • fluorine-containing polymers other than the above-mentioned fluorine-containing copolymer; acrylic resin, polyester resin, acrylic polyol resin, polyester polyol resin, urethane resin, acrylic silicone resin, silicone resin, alkyd resin, epoxy Non-fluororesins, such as resin, oxetane resin, an amino resin, etc. are mentioned.
  • the other polymers may be used alone or in combination of two or more.
  • a polymer which is compatible with the above-mentioned fluorine-containing copolymer and which can obtain a uniform cured film is preferable since the cured film tends to have gloss.
  • the other polymer may be a thermosetting resin or a thermoplastic resin.
  • the thermosetting resin is contained as another polymer, it is preferable that the other polymer can be linked to the fluorine-containing copolymer by a curing agent.
  • a polyester resin or an acrylic resin having a hydroxyl group, an epoxy group, a carbonyl group or the like at the terminal or side chain is preferable.
  • the other polymer preferably contains a polar group which interacts with the hydroxyl group of the fluorine-containing copolymer, for example, an ester group.
  • polyester resins or acrylic resins having no curable group are preferred.
  • the content of the other polymer described above is preferably 0 to 100 parts by mass, and more preferably 5 to 75% by mass with respect to 100 parts by mass of the fluorine-containing copolymer.
  • additives can be added to the anticorrosion paint of the present invention in accordance with the required characteristics within the range that does not impair the effects of the present invention.
  • additives include pigments, coupling agents, silica, pigment dispersants, antifoaming agents, leveling agents, ultraviolet light absorbers, light stabilizers, thickeners, adhesion improvers, matting agents and the like.
  • the anticorrosion paint of the present invention is highly transparent, so the corrosion state inside can be confirmed with the naked eye. Therefore, it is very effective in the field where durability is required, for example, metal piping inside a car, metal wiring, and an ocean structure such as a bridge. Moreover, it is suitable as an anticorrosion coating of the metal surface which needs designability.
  • the present invention is also a coating film characterized in that it is formed from the above-mentioned anticorrosion paint.
  • the coating film may be a non-cured coating film or a cured coating film.
  • the non-cured coating film is obtained from the above-mentioned anticorrosion paint which does not contain the curing agent (but which does not contain the curing agent).
  • the said non-hardened coating film can be manufactured by, for example, apply
  • the said cured coating film is obtained from the above-mentioned anticorrosion paint containing the said hardening
  • the said cured coating film can be manufactured by, for example, apply
  • the above-mentioned curing is preferably carried out at 10 to 300 ° C., preferably 100 to 200 ° C., for 30 seconds to 3 days in the case of a solvent-based paint. In the case of a solvent-based paint or a water-based paint, it is preferable to dry the coating. Drying may be performed simultaneously with the above curing or separately. After curing (and drying) of the coating, it may be cured. Curing is preferably performed at 20 to 300 ° C. for 1 minute to 3 days.
  • the thickness of the coating film is preferably 5 to 1000 ⁇ m from the viewpoint of rust prevention. More preferably, it is 7 to 500 ⁇ m, and still more preferably 10 to 100 ⁇ m.
  • the coating film of the present invention can sufficiently prevent the corrosion of metals and dissimilar metal joints, and is excellent in transparency, antifouling property and adhesion, so it is suitable for dissimilar metal joints, marine structures, It can be suitably used as a coating for kitchen appliances, metal piping for automobiles, exterior for high designability, piping for water and water treatment facilities, wiring in various power generation facilities or a coating for piping.
  • the above-mentioned is for preventing corrosion of wiring or piping in pipes of various kinds of metal joints, marine structures, kitchen appliances, metal pipes for automobiles, exteriors with high designability, pipes in water and water treatment facilities, or various power generation facilities.
  • the use of a coating of is also one of the preferred embodiments of the present invention.
  • the anticorrosion paint of the present invention and the coating film of the present invention can be applied to glass substrates, resin substrates, ceramic substrates, ceramic substrates, concrete substrates, metal substrates, etc. It is preferable to apply to the said metal base material from having.
  • the present invention is also a laminate comprising the above-mentioned metal base and the above-mentioned coating film.
  • Examples of materials for forming the metal base include steel plate, cast iron, high-temperature and high-pressure cast steel, and aluminum-zinc alloy-plated steel plate.
  • An example of cast iron is FC200.
  • An example of high temperature and high pressure casting steel is SCPH2.
  • metals, metal compounds such as aluminum, nickel, titanium, molybdenum, magnesium, manganese, copper, silver, lead, tin, chromium, beryllium, tungsten, cobalt, and alloys composed of two or more of them are mentioned, And can be selected according to the application.
  • the metal substrate may have a dissimilar metal joint to which dissimilar metals are joined. When the metal substrate has a dissimilar metal joint, corrosion can be particularly suppressed.
  • alloys include stainless steel, alloy steel such as permalloy, aluminum alloy such as Al-Cu, Al-Mg, Al-Si, Al-Cu-Ni-Mg, Al-Si-Cu-Ni-Mg, etc. Brass, bronze (bronze), silicon bronze, silicon brass, nickel-white, copper alloys such as nickel bronze, nickel-manganese (D-nickel), nickel-aluminum (Z-nickel), nickel-silicon, monel metal, constantan, nichrome inconel, hastelloy And other nickel alloys.
  • alloy steel such as permalloy
  • aluminum alloy such as Al-Cu, Al-Mg, Al-Si, Al-Cu-Ni-Mg, Al-Si-Cu-Ni-Mg, etc.
  • the metal surface is electroplated, hot-dip plated, chrominizing, siliconizing, calorizing, shella jig, thermal spraying, etc. to coat other metals, or by phosphate treatment
  • a phosphate film may be formed, a metal oxide may be formed by anodization or thermal oxidation, or electrochemical corrosion protection may be applied.
  • the metal substrate subjected to hot-dip plating include hot-dip galvanized steel sheets, hot-dip zinc-aluminum-magnesium alloy-plated steel sheets, hot-dip aluminum-galvanized steel sheets, hot-dip aluminum plated steel sheets and the like.
  • the metal surface is subjected to a conversion treatment with phosphate, sulfuric acid, chromic acid, oxalic acid, etc., sand blast, shot blast, grit blast, horning, paper scratch, wire scratch Surface roughening treatment such as hairline treatment may be performed, and for the purpose of design, the metal surface may be colored, printed, etched or the like.
  • the laminate may have a primer layer.
  • the formation of the primer layer is carried out by a conventional method using a conventionally known primer coating material.
  • a paint for a primer an epoxy resin, a urethane resin, an acrylic resin, a silicone resin, a polyester resin etc. are mentioned as a representative example, for example.
  • the laminate is also preferable for the laminate to be in direct contact with the metal base and the above-mentioned coating film, and excellent adhesion can be obtained even if the laminate is directly in contact.
  • the above-mentioned coating is a cured coating, higher adhesion can be obtained.
  • the metal base is resistant to corrosion, and the high transparency of the coating film can sufficiently exhibit the aesthetics of the metal base and is excellent in antifouling property and adhesion, so that dissimilar metal bonding It can be suitably used as a laminate for parts, marine structures, kitchen appliances, metal pipes for automobiles, exteriors with high designability, piping for water and water treatment facilities, wiring for various power generation facilities or piping. .
  • the above-mentioned is for preventing corrosion of wiring or piping in pipes of various kinds of metal joints, marine structures, kitchen appliances, metal pipes for automobiles, exteriors with high designability, pipes in water and water treatment facilities, or various power generation facilities.
  • the use of laminates is also one of the preferred embodiments of the present invention.
  • the electric wire which has a dissimilar-metal junction part and has a coating film formed from the said anticorrosion paint on a dissimilar-metal junction part is also one of this invention.
  • a wire having a dissimilar metal joint since current flows, corrosion is apt to occur due to a slight amount of water or oxygen, and in particular, it is required to suppress the corrosion of the dissimilar metal joint.
  • the electric wire of the present invention can suppress the corrosion of the dissimilar metal joint by having the coating film formed of the above-mentioned rust preventive paint on the dissimilar metal joint.
  • the electric wire of the present invention includes a first core wire made of metal (A) and a second core wire made of metal (B) different from metal (A), and the dissimilar metal joining of the first core wire and the second core wire is carried out. It is preferable to include a portion and to have a coating film formed from the above-mentioned rust preventive paint on the dissimilar metal joint portion.
  • the dissimilar metal joint may be mechanically joined as long as the metal (A) and the metal (B) are joined, and the metal (A) and the metal (B) are chemically linked. It may be joined.
  • the combination of metal (A) and metal (B) is not particularly limited, and the combination of the different metals mentioned above may be mentioned, but in particular, aluminum and copper, aluminum and gold, aluminum and nickel, aluminum And tin or aluminum and silver are preferred.
  • the electric wire of the present invention preferably has a covering layer covering the first core wire and the second core wire, as required.
  • the material, thickness, and the like of the coating layers of the first core wire and the second core wire are not particularly limited, and conventionally known resins, thicknesses, and the like used in electric wires can be adopted.
  • a first core wire A1 made of a metal (A) and a second core wire B1 made of a metal (B) different from the metal (A) The form which has the different-metal junction part D1 to which it joined, and has the coating film C1 formed from the said anticorrosion paint on a dissimilar-metal junction part D1 is mentioned.
  • a pipe having a dissimilar metal joint and having a coating film formed from the above-mentioned anticorrosive paint on the dissimilar metal joint is also one of the preferred embodiments of the present invention.
  • a pipe having a dissimilar metal joint when corrosion occurs in the joint, the internal fluid leaks or the outside air acts on the internal fluid, so it is required to suppress corrosion of the dissimilar metal joint, in particular.
  • the pipe of the present invention can suppress the corrosion of the dissimilar metal joint by having the coating film formed of the above-mentioned rust preventive paint on the dissimilar metal joint.
  • the pipe of the present invention includes a first pipe made of metal (A) and a second pipe made of metal (B) different from metal (A), and the first pipe and the second pipe described above It is preferable to have the coating film formed from the said anticorrosion paint on a dissimilar-metal junction part including the dissimilar-metal junction part.
  • the dissimilar metal joint may be mechanically joined as long as the metal (A) and the metal (B) are joined, and the metal (A) and the metal (B) are chemically linked. It may be joined.
  • the combination of metal (A) and metal (B) is not particularly limited, and the combination of the different metals mentioned above may be mentioned, but in particular, aluminum and copper, SUS and iron, or aluminum and iron Is preferred.
  • the structures, thicknesses, and the like of the first and second pipes are not particularly limited, and conventionally known structures, thicknesses, and the like can be adopted.
  • a first piping A2 made of a metal (A) and a second piping B2 made of a metal (B) different from the metal (A) The form which has the different metal junction part D2 to which it joined, and has the coating film C2 formed from the said anticorrosion paint on a dissimilar metal junction part D2 is mentioned.
  • Test condition B After coating, the paint prepared on Galvarium steel plate (registered trademark) was air dried at normal temperature for 30 minutes, and then heat dried under conditions of 80 ° C. for 2 hours to prepare a coated plate. The periphery of the coated plate was protected by aluminum tape, and a solution (50 g / L) was sprayed to the extent that the entire plate was wet, and after holding for 4 days at 35 ° C 90% RT, the surface condition was visually confirmed .
  • the criteria are that the substrate is ⁇ , no change, ⁇ is rust on a portion of the substrate, and x is rust on the entire substrate.
  • the polymers used are as follows.
  • Reference Examples 1-1 to 1-3 and Reference Comparative Examples 1-1 to 1-4 The solvent solubility of the solvent-soluble polymers 1 to 3 and the comparative polymers 1 and 2 was measured. The results are summarized in Table 3.
  • Examples 1-1 to 1-3 and Comparative Example 2 A 15% by mass solution of polymer 1 in dimethylacetamide was prepared, and formed into a film on a PP (polypropylene) plate using a 10 mil doctor blade. After air-drying at room temperature for 30 minutes, it was dried at 80 ° C. for 2 hours to obtain a coating. Thereafter, the coating was peeled from the PP plate to obtain a film. Films were similarly produced for Polymers 2 and 3 and Comparative Polymers 1 and 2.
  • Comparative Polymer 1 and Evar (R) L104B were 20.6% and 20.3%, respectively.
  • Poval polyvinyl alcohol
  • Examples 2-1 and 2-2 A 15% by mass solution of polymer 1 in dimethylacetamide was prepared, and 20% by mass of Sumidule N3300 manufactured by Sumika Bayer Urethane Co., Ltd. as a curing agent was added to the polymer to prepare a paint. After forming a film on a variety of substrates using a doctor blade of 10 mils, the film was air-dried at room temperature for 30 minutes, dried at 80 ° C. for 4 hours, and then evaluated for adhesion. The polymer 2 was similarly formed into a film, and the adhesion was evaluated. The results are shown in Table 7.
  • Examples 3-1 and 3-2 and Comparative Examples 3-1 to 3-3 Antirust Test 1 A 15% by mass solution of polymer 1 in dimethylacetamide was prepared and used as a paint. The anticorrosion test was done using the paint. The rust prevention test was similarly conducted on Polymer 2, Comparative Polymer 1, L104B and Poval. The results are shown in Table 9.
  • Examples 4-1 and 4-2 Hot Water Test The hot water test was conducted using the samples formed on the glass plates prepared in Examples 2-1 and 2-2. The results are shown in Table 10.
  • Example 5 and Comparative Examples 5-1 to 5-3 Antirust Test 2 A 15% by mass solution of polymer 2 in dimethylacetamide was prepared, and 20% by mass of Sumidule N3300 manufactured by Sumika Bayer Urethane Co., Ltd. was added as a curing agent to the polymer to prepare a coating. After forming a film using a doctor blade of 10 mils on various metal plates, it was air-dried at room temperature for 30 minutes and then dried at 80 ° C. for 4 hours to obtain a metal-painted plate. After that, in order to remove the influence of the surroundings, the circumference of the metal coated plate was protected by aluminum tape. After immersion in 5% brine and holding at 50 ° C. for 7 days, the appearance was visually evaluated. Each evaluation standard is as follows. ⁇ : No change, ⁇ : Partial rusting, ⁇ : Overall rusting Similarly to Comparative Polymers 1 and 2 and L104B, rusting was evaluated. The results are summarized in Table 11.
  • Dissimilar metal bonding (copper plate-aluminum foil) As shown in FIG. 1, a hole of 3 mm is drilled in a copper plate 1 of 0.5 mm in thickness, an aluminum foil 2 of 50 ⁇ m in thickness is cut into 4 mm square, a hole of 3 mm in diameter is made in the center, It was crimped with a SUS screw 3 and a nut 4 and tightly fixed on the copper plate 1 so that the aluminum foil 2 was partially exposed. Thereafter, the paints prepared in Example 5 and Comparative Example 5-2 are applied so as to completely cover screw 3, nut 4, aluminum foil 2 and copper plate 1, air-dried at room temperature for 30 minutes, and dried at 80 ° C for 4 hours I did.
  • a saline solution 6 (50 g / L) was dropped onto the coating film 5 and held at 35 ° C. and 90% RT for 4 days, and the state of the interface 7 between the aluminum foil 2 and the copper plate 1 was visually confirmed.
  • the results are shown in Table 12.
  • the criteria in Table 12 are the surface of the aluminum foil and the copper plate to which the saline solution was dropped, ⁇ : no change, ⁇ : rust partially generated, and ⁇ : rust entirely generated.
  • FC200-Aluminum foil Dissimilar metal bonding (FC200-Aluminum foil) Further, the appearance evaluation of dissimilar metal bonding was performed in the same manner as in the case of copper plate-aluminum foil except that FC200 was used instead of the copper plate. The results are shown in Table 13.

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  • Laminated Bodies (AREA)

Abstract

L'invention concerne un matériau de revêtement antirouille permettant d'empêcher de manière adéquate la corrosion d'un métal spécifique et la corrosion d'un joint en métal différent, et permettant de former un film de revêtement présentant également une transparence, des propriétés antisalissure et une adhérence excellentes. Un matériau de revêtement antirouille est caractérisé en ce qu'il comprend un copolymère contenant du fluor, comprenant des motifs oléfine contenant du fluor et des motifs alcool vinylique, le copolymère contenant du fluor présentant les caractéristiques (a) à (c). Caractéristique (a) : une perméabilité à la vapeur d'eau pour 100 µm inférieure ou égale à 25 g/m2∙ jour. Caractéristique (b) : un coefficient de perméation de l'oxygène inférieur ou égal à 2,0 E-13cc∙cm/cm2∙sec∙cm d'Hg. Caractéristique (c) : une absorption d'eau inférieure ou égale à 10 % en masse.
PCT/JP2018/038025 2017-10-20 2018-10-12 Matériau de revêtement antirouille, film de revêtement et corps stratifié WO2019078097A1 (fr)

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JPH07118599A (ja) * 1993-10-25 1995-05-09 Asahi Glass Co Ltd 塗料用樹脂、塗料、および建築材料
JPH10513217A (ja) * 1995-02-03 1998-12-15 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー フルオロ単量体／官能化された炭化水素単量体共重合方法および共重合体生成物
JP2000274754A (ja) * 1999-03-24 2000-10-06 Japan Gore Tex Inc 加湿用シート及び加湿エレメント
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JP2013103172A (ja) * 2011-11-14 2013-05-30 Asahi Glass Co Ltd 金属板の被覆方法、および被覆された金属板
DE112015001167T5 (de) * 2014-03-10 2016-12-01 Asahi Glass Company, Limited Beschichtungsmaterialzusammensetzung, Beschichtungsmaterial auf Lösungsmittelbasis, wässriges Beschichtungsmaterial, Pulverbeschichtungsmaterial und beschichteter Gegenstand

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JPH07118599A (ja) * 1993-10-25 1995-05-09 Asahi Glass Co Ltd 塗料用樹脂、塗料、および建築材料
JPH10513217A (ja) * 1995-02-03 1998-12-15 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー フルオロ単量体／官能化された炭化水素単量体共重合方法および共重合体生成物
JP2000274754A (ja) * 1999-03-24 2000-10-06 Japan Gore Tex Inc 加湿用シート及び加湿エレメント
JP2014001369A (ja) * 2012-05-24 2014-01-09 Daikin Ind Ltd 含フッ素重合体及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108610784A (zh) * 2016-12-02 2018-10-02 中国科学院宁波材料技术与工程研究所 一种粉末冶金金属表面的防腐层及其制备方法
CN108610784B (zh) * 2016-12-02 2021-02-26 中国科学院宁波材料技术与工程研究所 一种粉末冶金金属表面的防腐层及其制备方法

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