WO2020209245A1 - Composition de revêtement anticorrosion - Google Patents

Composition de revêtement anticorrosion Download PDF

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Publication number
WO2020209245A1
WO2020209245A1 PCT/JP2020/015641 JP2020015641W WO2020209245A1 WO 2020209245 A1 WO2020209245 A1 WO 2020209245A1 JP 2020015641 W JP2020015641 W JP 2020015641W WO 2020209245 A1 WO2020209245 A1 WO 2020209245A1
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anticorrosive coating
coating film
epoxy resin
mass
composition
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PCT/JP2020/015641
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English (en)
Japanese (ja)
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政武 西澤
友久 住田
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中国塗料株式会社
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Priority to JP2021513637A priority Critical patent/JP7146071B2/ja
Priority to CN202080020741.XA priority patent/CN113574124B/zh
Publication of WO2020209245A1 publication Critical patent/WO2020209245A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • 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

  • One embodiment of the present invention relates to an anticorrosive coating composition, an anticorrosive coating film, a base material with an anticorrosive coating film, or a method for producing a base material with an anticorrosive coating film.
  • an epoxy resin-based paint composition having excellent corrosion resistance, water resistance, chemical resistance, etc. has been used as an anticorrosive paint composition to be applied to ships and steel structures, especially in ballast tanks in a harsh corrosive environment. Therefore, an epoxy resin-based coating composition in which an epoxy resin and an amine curing agent are reacted is widely used because a coating film having particularly excellent corrosion resistance can be formed.
  • a coating composition having a low content of volatile organic compounds (VOCs), that is, a high content of non-volatile components and a low content of volatile organic components is required for environmental friendliness. There is.
  • Patent Document 1 describes a curing agent containing a main component containing a specific epoxy resin, an epoxy adduct of xylylenediamine, and an epoxy adduct of polyamide.
  • a high solid type anticorrosion coating composition containing an ingredient is disclosed.
  • a coating composition When a coating composition is applied to a base material, for example, a ballast tank to form a coating film, the volatile components of the solvent contained in the coating composition tend to stay near the floor surface due to the structure of the ballast tank. Drying tends to proceed in a solvent atmosphere, and it is difficult to control the drying temperature due to the large coating area. For example, it may be dried at a low temperature in winter.
  • Water is injected into such ballast tanks, but since the amount of water injected is enormous, water quality controlled water is not used, and seawater in which various bacteria are present. And industrial water are usually used.
  • a resin having a low viscosity is used in order to obtain a coating composition having a low VOC content.
  • a resin usually has a small average molecular weight and easily bleeds to the surface of the coating film.
  • the amine curing agent easily bleeds on the surface of the anticorrosive coating film formed from the anticorrosive coating composition having a low VOC content containing an amine curing agent as described in the above patent document.
  • a biofilm is formed on the surface of such an anticorrosive coating film, especially on the surface of the coating film dried under a solvent atmosphere or a low temperature, by contact with seawater or industrial water in which various bacteria are present. It was confirmed that. It is considered that this is because the amine curing agent bleeds on the surface of the anticorrosive coating film to promote the adhesion of bacteria to the surface of the coating film, and the bacteria and their metabolites proliferate on the surface of the coating film.
  • the formation of the biofilm on the coating film in this way causes a structural change of the amine curing agent due to contact with the biofilm, formation of a complex with the metabolite, and the like, and the metabolite. It was confirmed that the coating film was discolored, which is presumed to be caused by the fact that the coating film adhered to the surface of the coating film.
  • One embodiment of the present invention provides an anticorrosive coating composition capable of forming an anticorrosive coating film having excellent anticorrosive properties by suppressing discoloration caused by contact with bacteria even when dried in a solvent atmosphere or at a low temperature.
  • a configuration example of the present invention is as follows.
  • ⁇ 1> Contains an epoxy resin (A), an amine curing agent (B), a silane coupling agent (C), and an extender pigment (D). Pigment volume concentration (PVC) is 30-45% The amine curing agent (B) contains ethylenediamine or a modified product thereof.
  • the epoxy resin (A) contains an epoxy resin having an epoxy equivalent of 270 or less. Anticorrosive paint composition.
  • ⁇ 2> Contains an epoxy resin (A), an amine curing agent (B), a silane coupling agent (C), and an extender pigment (D). Pigment volume concentration (PVC) is 30-45% The amine curing agent (B) contains ethylenediamine or a modified product thereof. The content of volatile organic compounds (VOC) is 340 g / L or less. Anticorrosive paint composition.
  • the amine curing agent (B) contains a polyamided product of ethylenediamine, an epoxy adduct of the polyamide product, a Mannich modified product of ethylenediamine, or an epoxy adduct of the Mannich modified product.
  • the anticorrosion coating composition according to the above.
  • ⁇ 6> An anticorrosive coating film formed from the anticorrosive coating composition according to any one of ⁇ 1> to ⁇ 5>.
  • ⁇ 7> A base material with an anticorrosive coating film containing the anticorrosive coating film and the base material according to ⁇ 6>.
  • a method for producing a base material with an anticorrosive coating film which comprises the following steps [1] and [2]. [1] Step of coating the base material with the anticorrosive coating composition according to any one of ⁇ 1> to ⁇ 5> [2] Step of drying the applied anticorrosive coating composition to form an anticorrosive coating film.
  • the present invention is excellent in salt water resistance, high temperature and humidity resistance, corrosion resistance and adhesion to a substrate, and even if it is dried in a solvent atmosphere or low temperature, discoloration caused by contact with bacteria is exhibited. It is possible to form an anticorrosive coating film that can be suppressed.
  • FIG. 1 is a schematic view of a notched test plate used in the test of the example.
  • the anticorrosive coating composition (hereinafter, also referred to as “the present composition”) according to one embodiment of the present invention includes an epoxy resin (A), an amine curing agent (B), a silane coupling agent (C), and an extender pigment (D). ) Is contained, the pigment volume concentration (PVC) is 30 to 45%, the amine curing agent (B) contains ethylenediamine or a modified product thereof, and the following (i) or (ii) is satisfied. (I) The epoxy resin (A) contains an epoxy resin having an epoxy equivalent of 270 or less. (Ii) The content of a volatile organic compound (VOC) is 340 g / L or less.
  • VOC volatile organic compound
  • an anticorrosive coating film having the above-mentioned effect.
  • a conventional anticorrosive coating film is dried in a solvent atmosphere or low temperature to form an anticorrosive coating film
  • the obtained anticorrosive coating film discolors when it comes into contact with bacteria, but according to this composition, it is discolored in a solvent atmosphere or low temperature.
  • the anticorrosive coating film is formed by drying with, the obtained anticorrosive coating film can suppress discoloration caused by contact with bacteria. Therefore, it can be said that this composition is a discoloration-suppressing coating composition due to bacteria.
  • the present composition comes into contact with a portion that can be indirectly indirect to bacteria for a long period of time, specifically, seawater or industrial water for a long period of time. Places where seawater and industrial water are stored, places where drying progresses in a solvent atmosphere, places where it is difficult to control the drying temperature, especially on the inner surface of tanks such as ballast tanks and inside ships other than tanks Suitable for painting.
  • the present composition may be a one-component type composition, but is usually a two-component type composed of a main component containing an epoxy resin (A) and a curing agent component containing an amine curing agent (B). It is a composition of. Further, if necessary, a composition of three or more components may be used. These main agent components and curing agent components are usually stored, stored, transported, etc. in separate containers, and are mixed and used immediately before use.
  • the anticorrosive coating film is likely to be discolored due to contact with bacteria, while the anticorrosive coating film is discolored due to contact with bacteria. It was not easy to obtain a coating composition having a low VOC content in an attempt to suppress the above. That is, conventionally, there has not been an anticorrosive coating composition that can simultaneously satisfy the low VOC content and the suppression of discoloration of the anticorrosive coating film due to contact with bacteria.
  • the anticorrosive coating film is discolored due to contact with seawater or industrial water in which bacteria are present, even if it is dried in a solvent atmosphere or at a low temperature, although it has a low VOC content. Is unlikely to occur. Therefore, from the viewpoint of environmental protection, safety of the working environment, etc., the present composition is preferably a coating composition having a low VOC content, and specifically, the VOC content in the present composition is preferably preferable. It is 340 g / L or less, more preferably 300 g / L or less, and particularly preferably 270 g / L or less.
  • the VOC content can be calculated from the following formula (1) using the values of the composition specific gravity and the heating residue ratio (mass ratio of non-volatile components).
  • the specific gravity of the composition and the residual heating ratio may be values calculated from the raw materials used or measured values measured as follows.
  • VOC content (g / L) composition specific gravity x 1000 x (100-heating residue ratio) / 100 ... (1)
  • the specific gravity of the composition (g / ml) can be calculated as follows. Under the temperature condition of 23 ° C., the composition (in the case of the two-component composition, the composition immediately after mixing the main component and the curing agent component) is filled in a specific gravity cup having an internal volume of 100 ml, and the composition is prepared. It is calculated by calculating the mass of an object.
  • the heating residue (nonvolatile content) of the present composition can be calculated as follows. According to JIS K 5601-1-2: 2008, weigh 1 ⁇ 0.1 g of this composition (in the case of the above-mentioned two-component type composition, the composition immediately after mixing the main component and the curing agent component) on a flat-bottomed dish. It is taken, spread uniformly using a wire of known mass, left at 23 ° C. for 24 hours, dried at 110 ° C. for 1 hour under normal pressure, and calculated by measuring the heating residue and the mass of the wire. The heating residue (mass%) is a value of the mass percentage of the heating residue (nonvolatile content) in the present composition.
  • solid content the components other than the solvent in the main ingredient or the raw material (eg, epoxy resin (A)) constituting the curing agent component, the main agent component, and the curing agent component are referred to as "solid content”.
  • the pigment volume concentration (PVC) in the present composition is 30% or more, preferably 32% or more, more preferably 34% or more, 45% or less, preferably 43% or less, more preferably. It is 42% or less.
  • PVC pigment volume concentration
  • a composition having excellent drying properties can be obtained, excellent in high temperature and high humidity resistance and adhesion to a substrate, and an anticorrosive coating film in which discoloration caused by contact with bacteria is further suppressed can be easily obtained. Obtainable. If the PVC is less than 30%, the high temperature and high humidity resistance is inferior, the drying property of the composition is lowered, and the discoloration resistance to contact with bacteria is lowered. On the other hand, when PVC exceeds 45%, the film-forming property of the anticorrosive coating film to be formed is lowered, so that the adhesion to the substrate and the anticorrosive property are lowered.
  • the PVC refers to the total volume concentration of all pigments including the extender pigment (D) and the following coloring pigments, and can be specifically calculated by the following formula.
  • PVC [%] total volume of all pigments in the composition x 100 / volume of non-volatile components in the composition
  • the volume of the non-volatile component in the present composition can be calculated from the mass and true density of the non-volatile component of the present composition.
  • the mass and true density of the non-volatile component may be measured values or values calculated from the raw materials used.
  • the volume of the pigment can be calculated from the mass and true density of the pigment used.
  • the mass and true density of the pigment may be measured values or values calculated from the raw materials used.
  • the measured value can be calculated, for example, by separating the pigment and other components from the non-volatile content of the present composition and measuring the mass and true density of the separated pigment.
  • Epoxy resin (A) examples include polymers or oligomers containing two or more epoxy groups in the molecule, and polymers or oligomers produced by the ring-opening reaction of the epoxy groups.
  • the epoxy resin (A) may be used alone or in combination of two or more.
  • the epoxy equivalent is preferably 270 or less, more preferably 100 to 270, and particularly preferably 100 to 200, from the viewpoint that a coating composition having a low VOC content can be easily obtained. It is desirable that the epoxy resin is contained, and it is more desirable that the epoxy resin has an epoxy equivalent in the above range. Examples of the epoxy resin having an epoxy equivalent in such a range include a liquid or semi-solid epoxy resin. When the epoxy equivalent is in the above range, a coating composition having a low VOC content can be easily obtained, and the effect of the present invention is more exhibited, which is preferable. When the epoxy equivalent exceeds 270, it tends to be difficult to obtain a coating composition having a low VOC content. The epoxy equivalent is calculated based on the solid content of the resin based on JIS K 7236: 2001.
  • An epoxy resin having an epoxy equivalent of more than 270 can be used in combination with the composition as long as the effect of the present invention is not impaired, and the ratio of the epoxy resin having an epoxy equivalent of more than 270 to the epoxy resin (A). Is preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less, from the viewpoint that a coating composition having a low VOC content can be easily obtained.
  • Examples of the epoxy resin (A) include bisphenol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, novolak type epoxy resin, cresol type epoxy resin, dimer acid modified epoxy resin, aliphatic epoxy resin, and alicyclic. Examples thereof include group epoxy resins and epoxidized oil-based epoxy resins.
  • bisphenol type epoxy resin and novolak type epoxy resin are preferable, and bisphenol A type or bisphenol F type epoxy resin is preferable from the viewpoint that an anticorrosion coating film having excellent adhesion to a substrate can be easily formed. More preferably, bisphenol A type epoxy resin is particularly preferable.
  • Examples of the epoxy resin (A) include epichlorohydrin-bisphenol A epoxy resin (bisphenol A diglycidyl ether type); epichlorohydrin-bisphenol AD epoxy resin; epichlorohydrin-bisphenol F epoxy resin; epoxynovolac resin; 3,4-epoxyphenoxy-.
  • bisphenol A type epoxy resin examples include bisphenol A diglycidyl ether, bisphenol A (poly) propylene oxide diglycidyl ether, bisphenol A (poly) ethylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol A.
  • bisphenol A type diglycidyl ethers and other reduced polymers such as (poly) propylene oxide diglycidyl ethers.
  • epoxy resin (A) a compound synthesized by a conventionally known method may be used, or a commercially available product may be used.
  • the commercially available product is "E-028" (manufactured by Meishin Otake Chemical Co., Ltd., bisphenol A diglycidyl ether, solid content 100%) as a liquid product at room temperature (temperature of 15 to 25 ° C., the same applies hereinafter).
  • the content of the epoxy resin (A) with respect to 100% by mass of the non-volatile content of the present composition is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 40% by mass or less, and more preferably 30% by mass. % Or less.
  • the epoxy resin (A) is included in the main component when the composition is a two-component composition composed of a main component and a curing agent component.
  • the content of the epoxy resin (A) in the main agent component is preferably 5 to 80% by mass, more preferably 5 to 50% by mass.
  • the amine curing agent (B) includes ethylenediamine or a modified product thereof.
  • an epoxy resin having an epoxy equivalent of 270 or less, or a liquid or semi-solid epoxy resin was used. Even if the coating composition is dried in a solvent atmosphere or at a low temperature, it is possible to form an anticorrosion coating film capable of suppressing discoloration caused by contact with bacteria.
  • the amine curing agent (B) may be used alone or in combination of two or more.
  • modified ethylenediamine examples include a polyamide product of ethylenediamine (polyamidoamine) such as a modified fatty acid of ethylenediamine, an epoxy adduct of the polyamide product, an amine adduct of ethylenediamine and an epoxy compound, and a Mannig modified product of ethylenediamine (eg,).
  • polyamidoamine such as a modified fatty acid of ethylenediamine, an epoxy adduct of the polyamide product, an amine adduct of ethylenediamine and an epoxy compound
  • a Mannig modified product of ethylenediamine eg,).
  • a polyamide amine, a polyamide amine epoxy adduct, a Mannig modified product, and a Mannig modified epoxy adduct are preferable from the viewpoint that an anticorrosion coating film having better drying property can be easily obtained, and the polyamide amine epoxy adduct is preferable.
  • Mannig modified epoxy adduct is more preferable, and polyamideamine epoxy adduct is particularly preferable from the viewpoint that an anticorrosion coating film having better discoloration resistance can be easily obtained.
  • polyamide product examples include dehydration condensates of ethylenediamine and one or more carboxylic acids such as dimer acid.
  • carboxylic acid containing 10% by mass or more of a monomeric acid (a compound having one carboxylic acid in one molecule) as the carboxylic acid.
  • the amount of the carboxylic acid used with respect to 100 parts by mass of ethylenediamine is preferably 50 to 300 parts by mass.
  • the dimer acid is a dimer of unsaturated fatty acid and usually contains a small amount of monomer or trimer.
  • the unsaturated fatty acid has a number of carbon atoms including carbon atoms of the carboxyl group, preferably 12 or more, more preferably 16 or more, preferably 24 or less, more preferably 18 or less, and A carboxylic acid having one or more unsaturated bonds in one molecule is desirable.
  • unsaturated fatty acids include fatty acids having one unsaturated bond such as oleic acid and elaidic acid; fatty acids having two unsaturated bonds such as linoleic acid; and unsaturated bonds such as linolenic acid and arachidonic acid. Examples include fatty acids having 3 or more. Further, fatty acids obtained from animals and plants can also be used, and examples of the fatty acids include soybean oil fatty acid, tall oil fatty acid, and linseed oil fatty acid.
  • Mannich modified product examples include Mannich-modified amine obtained by Mannich condensation of one or more phenols, one or two or more aldehydes, and ethylenediamine.
  • the phenols may be monovalent or multivalent, and may be mononuclear or polynuclear, but monovalent mononuclear phenol is preferable.
  • Specific examples of the phenols include phenol which is a monovalent mononuclear phenol; resorcinol and hydroquinone which are divalent mononuclear phenols; 1,5-dihydroxynaphthalene and 2, which are divalent polynuclear phenols.
  • alkylphenol alkyl group carbon number: 1 to 10, preferably 1 to 5
  • halogenated phenol alkoxyphenol (alkoxy group carbon number: 1 to 1 to 5). 10 preferably 1 to 5
  • bisphenol A bisphenol F can be mentioned.
  • examples of the alkylphenol include monovalent phenols such as methylphenol (o, m or p-cresol), ethylphenol, butylphenol, t-butylphenol, octylphenol, nonylphenol, dodecylphenol, and dinonylphenol.
  • examples of the halogenated phenol include monovalent phenols such as chlorophenol, and examples of the alkoxyphenols include methoxyphenols.
  • the phenols may be unsaturated substituent-containing phenols, and the unsaturated substituent-containing phenols contain at least one monohydroxyphenyl group in the molecule and hydrogen in the phenyl group.
  • the unsaturated substituent-containing phenols include a compound in which a part of the atom, that is, 1 to 5 hydrogen atoms are substituted with an unsaturated hydrocarbon group.
  • the unsaturated hydrocarbon group include an alkylene group having 1 to 30 carbon atoms and a phenyl group containing an alkylene group having 1 to 30 carbon atoms.
  • unsaturated substituent-containing phenols include cardanol, isopropenylphenol, diisopropenylphenol, butenylphenol, isobutenylphenol, cyclohexenylphenol, and monostyrene phenol (C 6).
  • unsaturated substituent-containing phenols include cardanol, isopropenylphenol, diisopropenylphenol, butenylphenol, isobutenylphenol, cyclohexenylphenol, and monostyrene phenol (C 6).
  • H 5 -CH CH-C 6 H 4- OH
  • Cardanol is preferable as the phenols.
  • aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde and the like, and formaldehyde is preferable among these.
  • phenols, aldehydes, and ethylenediamine may be used in equimolar amounts in theory, but usually 0.5 mol of aldehydes is used for 1 mol of phenols.
  • Ethylenediamine may be used in an amount of about 2.5 mol and ethylenediamine may be used in an amount of 0.5 to 2.5 mol and heated at a temperature of about 50 to 180 ° C. for about 3 to 12 hours. After the reaction is completed, the reaction product may be heated under reduced pressure to remove water and unreacted products.
  • the epoxy adduct As a specific example of the epoxy adduct, one or more amines such as ethylenediamine, the polyamide compound, and the Mannich modified product are reacted with one or more epoxy resins such as bisphenol A type epoxy resin. Examples of the compound obtained by the above.
  • the amount of the epoxy resin used with respect to 100 parts by mass of the amines is preferably 5 to 50 parts by mass.
  • epoxy resin examples include (alkyl) phenols such as bisphenol A diglycidyl ether; bisphenol F diglycidyl ether; styrene oxide; cyclohexene oxide; phenol, cresol, and t-butylphenol, butanol, 2-ethylhexanol, and carbon number.
  • alkyl phenols such as bisphenol A diglycidyl ether; bisphenol F diglycidyl ether; styrene oxide; cyclohexene oxide; phenol, cresol, and t-butylphenol, butanol, 2-ethylhexanol, and carbon number.
  • Glysidyl ethers such as alcohols 8 to 14; alkyl glycidyl ethers (eg, Epodil 759 [manufactured by Evonik]) can be mentioned.
  • the amine curing agent (B) may contain other amine curing agents other than ethylenediamine and its modified products.
  • the other amine curing agent is not particularly limited, and conventionally known amine curing agents can be used. Specifically, aliphatic, alicyclic, aromatic, heterocyclic amines, and heterocyclic amines, and , These modified products can be used.
  • Examples of the aliphatic amine include alkylene polyamines, polyalkylene polyamines, and alkylaminoalkylamines.
  • alkylene polyamine examples include 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, and 1,7-diaminoheptane.
  • alkylene polyamine examples include 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane and trimethylhexamethylenediamine.
  • polyalkylene polyamine examples include diethylenetriamine, dipropylenetriamine, triethylenetetramine (TETA), tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, and bis (hexamethylene). Examples thereof include triamine and triethylene-bis (trimethylene) hexamine.
  • alkylaminoalkylamine examples include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine and dimethylaminobutylamine.
  • aliphatic amines other than these include tetra (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, 1,3-bis (2'-aminoethylamino) propane, and tris (2-amino).
  • Ethyl) amine bis (cyanoethyl) diethylenetriamine, polyoxyalkylene polyamine (particularly diethylene glycol bis (3-aminopropyl) ether), bis (aminomethyl) cyclohexane, mensendiamine (MDA), o-xylylenediamine, m- Xylylenediamine (MXDA), p-xylylenediamine, bis (aminomethyl) naphthalene, bis (aminoethyl) naphthalene, 1,4-bis (3-aminopropyl) piperazine, 1- (2'-aminoethyl piperazine) , 1- [2'-(2''-aminoethylamino) ethyl] piperazine.
  • MDA mensendiamine
  • MXDA o-xylylenediamine
  • MXDA m- Xylylenediamine
  • alicyclic amine examples include cyclohexanediamine, isophoronediamine (IPDA), diaminodicyclohexylmethane (particularly 4,4′-methylenebiscyclohexylamine), 4,4′-isopropyridenebiscyclohexylamine, and norbornandiamine. , 2,4-Di (4-aminocyclohexylmethyl) aniline.
  • aromatic amine examples include an aromatic polyamine compound having two or more primary amino groups bonded to a benzene ring. More specifically, as the aromatic amine, phenylenediamine, naphthalenediamine, diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone.
  • heterocyclic amine examples include 1,4-diazacycloheptane, 1,11-diazacycloeikosan, and 1,15-diazacyclooctacosane.
  • modified products of aliphatic, alicyclic, aromatic, and heterocyclic amines include polyamide products (polyamide amines) such as fatty acid modified products, epoxy adducts of the polyamide products, and amines with epoxy compounds.
  • polyamide amines such as fatty acid modified products, epoxy adducts of the polyamide products, and amines with epoxy compounds.
  • Adduct, Mannich modified products (eg, phenalkamine, phenalcamide), epoxy adducts of the Mannich modified products, Michael adducts, ketimides, aldiminates and the like can be mentioned.
  • an aliphatic amine such as triethylenetetramine and an alicyclic amine such as isophoronediamine are preferable, and in particular, a polyamide product of an aliphatic amine such as triethylenetetramine, isophoronediamine and the like are used.
  • a Mannig modified product of the alicyclic amine of is preferred.
  • the content of ethylenediamine and its modified product in the amine curing agent (B) is 50% by mass from the viewpoint that an anticorrosive coating film having better discoloration resistance can be easily obtained. It is preferable to use the above amount.
  • amine curing agent (B) a compound synthesized by a conventionally known method may be used, or a commercially available product may be used.
  • the commercially available products include "PA-205" (manufactured by Otake Meishin Kagaku Co., Ltd.), which is an ethylenediamine polyamide adduct (ethylenediamine polyamide adduct), and ethylenediamine phenalkamine adduct (ethylenediamine phenalkami).
  • PA-205" manufactured by Otake Meishin Kagaku Co., Ltd.
  • Epoxy adduct Cardolite NC-556X80
  • Cardlight Co., Ltd. can be mentioned.
  • the active hydrogen equivalent of the amine curing agent (B) is preferably 50 or more, more preferably 80 or more, preferably 1000 or less, and more, from the viewpoint that an anticorrosive coating film having better anticorrosive properties can be easily obtained. It is preferably 400 or less.
  • the amine curing agent (B) preferably has a reaction ratio calculated by the following formula (1) from the viewpoint that an anticorrosive coating film having excellent corrosion resistance, coating film strength and drying property can be easily obtained. It is desirable to use it in an amount such that it is 0.3 or more, more preferably 0.5 or more, preferably 1.5 or less, and more preferably 1.0 or less. When the reaction ratio is within the above range, it is possible to easily obtain an anticorrosion coating film having excellent discoloration resistance, corrosion resistance and adhesion to a substrate.
  • Reaction ratio ⁇ (Amine curing agent (B) compounding amount / Amine curing agent (B) active hydrogen equivalent) + (Epoxy resin (A) compounding amount / Epoxy resin (A) Functional group equivalent of a component that is reactive with respect to) ⁇ / ⁇ (blending amount of epoxy resin (A) / epoxy equivalent of epoxy resin (A)) + (reactive with amine curing agent (B)) Blending amount of component / Functional group equivalent of component having reactivity with amine curing agent (B)) ⁇ ... (1)
  • examples of the "component having reactivity with the amine curing agent (B)" in the formula (1) include a silane coupling agent (C) described later and a (meth) acrylic acid ester (F).
  • a silane coupling agent (C) described later can be mentioned.
  • the “functional group equivalent” of each of the above components means the mass (g) per 1 mol functional group obtained by dividing the mass of 1 mol of these components by the number of mols of the functional groups contained therein.
  • a silane coupling agent having an amino group or an epoxy group can be used as the reactive group. Therefore, depending on the type of the reactive group, the silane coupling agent may be an epoxy resin ( It is necessary to determine whether it is reactive with A) or with the amine curing agent (B) and calculate the reaction ratio.
  • the amine curing agent (B) is included in the curing agent component.
  • the curing agent component is preferably a component prepared so that the solid content is 50 to 100% by mass, and the viscosity measured by the E-type viscometer at that time is excellent in handleability and coatability. From the point of view, it is preferably 100,000 mPa ⁇ s / 25 ° C. or lower, and more preferably 50 to 10,000 mPa ⁇ s / 25 ° C.
  • the composition comprises a silane coupling agent (C).
  • a silane coupling agent (C) By using the silane coupling agent (C), not only the adhesion of the obtained anticorrosive coating film to the substrate can be further improved, but also the anticorrosion property and high temperature and high humidity resistance of the obtained anticorrosion coating film can be improved. Can be made to.
  • the silane coupling agent (C) may be used alone or in combination of two or more.
  • the silane coupling agent (C) is not particularly limited, and conventionally known compounds can be used. However, the silane coupling agent (C) has at least two functional groups in the same molecule, and the adhesion to the substrate is improved. is preferably a compound capable of contributing to the reduction or the like of the viscosity, for example, the formula: wherein: "X-SiMe n Y 3-n" [n is 0 or 1, X is capable of reaction with the organic reactive group ( Example: Amino group, vinyl group, epoxy group, mercapto group, halogen group, a group in which a part of a hydrocarbon group is substituted with these groups, or a group in which a part of a hydrocarbon group is substituted with an ether bond or the like.
  • Me is a methyl group
  • Y is a hydrolyzable group (eg, an alkoxy group such as a methoxy group or an ethoxy group). ] Is more preferable.
  • silane coupling agent (C) a compound having an epoxy group or an amino group as a reactive group is preferable, a compound having an epoxy group is more preferable, and specifically, "KBM-403" ( ⁇ -glycidoxy). Examples thereof include propyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "Sila Ace S-510" (manufactured by JNC Co., Ltd.).
  • the content of the silane coupling agent (C) with respect to 100% by mass of the non-volatile content of the present composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 10% by mass or less. , More preferably 5% by mass or less.
  • the content of the silane coupling agent (C) is within the above range, the performance of the anticorrosive coating film such as adhesion to the substrate is improved, and the viscosity of the present composition can be lowered, so that the coating workability is improved. To do.
  • the present composition contains an extender pigment (D).
  • an extender pigment (D) By using the extender pigment (D), it is possible to form an anticorrosion coating film which is excellent not only in terms of cost of the obtained composition but also in corrosion resistance, salt water resistance, high temperature and high humidity resistance and the like.
  • the extender pigment (D) one type may be used alone, or two or more types may be used.
  • extender pigment (D) zinc oxide, talc, silica, mica, clay, potash valer, glass flakes, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium sulfate (eg, barium powder). ), Fibrous fillers such as gypsum, rock wool, and glass fiber.
  • talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, potassium orthoclase, gypsum, and glass flakes are preferable.
  • mica or glass flakes which are scaly pigments, from the viewpoints that an anticorrosive coating film having excellent corrosion resistance, salt water resistance, high temperature and high humidity resistance, etc. can be easily formed, and the average aspect ratio is high. More preferably, it contains a scaly pigment of 30-90.
  • the average aspect ratio is calculated by "median diameter (D50) / average thickness".
  • the D50 can be measured using a laser scattering diffraction type particle size distribution measuring device, for example, "SALD 2200" (manufactured by Shimadzu Corporation).
  • the average thickness is measured horizontally with respect to the main surface (largest area surface) of the scaly pigment using a scanning electron microscope (SEM), for example, "XL-30” (manufactured by Philips). By measuring the thickness of ten to several hundred pigment particles, it can be calculated as the average value.
  • SEM scanning electron microscope
  • mica is more preferable because it is inexpensive, easily available, and can form an anticorrosive coating film having more excellent effects.
  • examples of the mica include "Suzolite mica 200-HK” (manufactured by West Japan Trading Co., Ltd., aspect ratio: 40 to 60).
  • the content of the extender pigment (D) with respect to 100% by mass of the non-volatile content of the present composition is such that an anticorrosive coating film having excellent corrosion resistance, salt water resistance, high temperature and high humidity resistance, etc. can be easily formed. It is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 80% by mass or less, and more preferably 70% by mass or less.
  • the content of the scaly pigment with respect to 100% by mass of the non-volatile content of the present composition is preferably 1% by mass or more from the viewpoint of improving the performance of the anticorrosive coating film such as water corrosion resistance and bending resistance. It is more preferably 3% by mass or more, preferably 40% by mass or less, and more preferably 20% by mass or less.
  • the present composition preferably contains a liquid compound (E) having a phenol skeleton from the viewpoint that the flexibility of the anticorrosive coating film obtained from the coating composition having a low VOC content can be improved.
  • the liquid compound (E) may be used alone or in combination of two or more.
  • liquid compound means a compound that is liquid at 25 ° C., specifically, the viscosity measured by an E-type viscometer at 25 ° C. is 10,000 mPa ⁇ s or less. It refers to a compound that is.
  • the liquid compound (E) is not particularly limited as long as it has a basic skeleton in which a hydroxy group is bonded to a benzene ring, but alkylphenols such as phenol, cresol and cardanol, and phenol-modified hydrocarbon resins are used. Can be mentioned. Among these, a phenol-modified hydrocarbon resin is preferable from the viewpoint of good compatibility with the epoxy resin (A).
  • phenol-modified hydrocarbon resin examples include diolefins contained in cracked oil distillates of petroleum and coal, as described in JP-A-9-268209 and JP-A-7-196793. Examples thereof include resins obtained by copolymerizing monoolefins or ⁇ -methylstyrene with phenols (phenol compounds).
  • the phenol-modified hydrocarbon resin is a C5 (aliphatic) petroleum resin made from a C5 distillate; a C9 (aromatic) petroleum resin made from a C9 distillate; C5 / C9. Copolymerized petroleum resin; Dicyclopentadiene resin made from dicyclopentadiene obtained by thermally dimerizing cyclopentadiene contained in C5 distillate; ⁇ -methylstyrene; etc., and a resin obtained by reacting phenols Can be mentioned.
  • a resin obtained by addition-polymerizing styrene, vinyltoluene, kumaron, indene, ⁇ -methylstyrene and the like contained in the cracked oil fraction of petroleum and coal with phenols is preferable.
  • the average molecular weight of the phenol-modified hydrocarbon resin is usually 200 to 1000, and the viscosity is usually 30 to 10,000 mPa ⁇ s / 25 ° C.
  • phenol-modified hydrocarbon resin a commercially available product may be used, and examples of the commercially available product include “NEVOXY EPX-L” and “NEVOXY EPX-L2” (all manufactured by Nevile Chemical / phenol-modified hydrocarbon). Resin), "HIRENOL PL-1000S” (manufactured by KOLON / phenol-modified hydrocarbon resin).
  • the liquid compound (E) is used with respect to 100% by mass of the non-volatile content of the present composition from the viewpoint of obtaining an anticorrosion coating film having excellent crack resistance and the like.
  • the content is preferably 1% by mass or more, more preferably 3% by mass or more, preferably 50% by mass or less, and more preferably 30% by mass or less.
  • the present composition preferably contains a (meth) acrylic acid ester (F) from the viewpoint that the curing rate and low-temperature curability of the composition can be further improved.
  • the (meth) acrylic acid ester (F) may be used alone or in combination of two or more.
  • the (meth) acrylic acid ester (F) is not particularly limited, but a polyfunctional acrylic acid ester is preferable, and a compound having three or more (meth) acryloyloxy groups in one molecule is more preferable, and from the viewpoint of reactivity. Compounds having three or more acryloyloxy groups in one molecule are more preferable.
  • the number of (meth) acryloyloxy groups contained in one molecule of the (meth) acrylic acid ester (F) is preferably 3 or more, more preferably 4 or more, preferably 40 or less, and more preferably 20 or less. is there.
  • the (meth) acrylic acid ester (F) has a functional group equivalent of less than 200 (meth) acryloyloxy groups because a coating composition having a low viscosity and excellent curability can be easily obtained.
  • Compounds are preferred, compounds less than 100 are more preferred.
  • (meth) acrylic acid ester (F) a commercially available product may be used, and examples of the commercially available product include "M-Cure 400" (manufactured by SARTOMER, functional group equivalent 85).
  • the coating composition having excellent curing speed, low-temperature curability, etc. can be obtained, and the present composition has a non-volatile content of 100% by mass.
  • the content of the (meth) acrylic acid ester (F) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, preferably 15% by mass or less, and more preferably 10% by mass or less. Particularly preferably, it is 5% by mass or less.
  • the present composition contains an organic solvent, a coloring pigment, other resins other than the above (A) and (E), a sagging / anti-settling agent, and a curing, if necessary.
  • Accelerators, plasticizers other than the above (E), inorganic dehydrating agents (stabilizers), dispersants, antifoaming agents, antifouling agents and the like may be contained within a range that does not impair the object of the present invention.
  • these other components include conventionally known ones used in anticorrosive coating compositions. Each of the other components may be used alone or in combination of two or more.
  • Organic solvent is not particularly limited, but for example, an aromatic hydrocarbon solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an ester solvent such as butyl acetate, isopropanol, n-butanol, 1 -Alcohol solvents such as methoxy-2-propanol and benzyl alcohol, mineral spirits, n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane, cyclohexane, methylcyclohexane and other aliphatic hydrocarbons Hydrocarbon solvent can be mentioned.
  • an aromatic hydrocarbon solvent such as toluene or xylene
  • a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone
  • an ester solvent such as butyl
  • the content of the organic solvent is not particularly limited and may be appropriately adjusted according to the coating method at the time of coating the present composition, but the VOC in the present composition It is preferable that the content is within the above range.
  • the coloring pigment is not particularly limited as long as it is a pigment other than the above (D), and examples thereof include titanium white, a valve handle, a yellow valve handle, and carbon black.
  • the content of the coloring pigment is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the non-volatile content of the present composition. It is preferably 15% by mass or less, and more preferably 10% by mass or less.
  • Examples of the resin other than the above (A) and (E) include polyester resin, fluororesin, polybutene resin, silicone rubber, urethane resin (rubber), polyamide resin, vinyl chloride resin, and chloride rubber (resin). Chlorinated olefin resin, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, kumaron resin, silyl resin, petroleum resin, ketone resin, formaldehyde resin, polyvinyl alkyl ether resin, rosin (eg gum rosin, wood rosin, tall) Oil rosin) can be mentioned.
  • a commercially available product may be used, and examples of the commercially available product include "Neopolymer E-100” manufactured by JXTG Energy Co., Ltd., which is a hydroxyl group-containing petroleum resin.
  • the content of the other resin is, for example, 20% by mass or less with respect to 100% by mass of the non-volatile content of the composition.
  • the anti-sag / sedimentation preventive agent examples include organic clay waxes such as stearate salts of Al, Ca and Zn, lecithin salts and alkyl sulfonates, polyethylene wax, amido wax, hydrogenated castor oil wax and synthetic fine powder silica.
  • Conventionally known waxes such as polyethylene oxide wax can be used, but among them, amide wax, synthetic fine powder silica, polyethylene oxide wax and organic clay wax are preferable.
  • anti-sag and anti-settling agents examples include "Disparon 305", “Disparon 4200-20", and “Disparon 6650” manufactured by Kusumoto Kasei Co., Ltd .; “ASAT-250F” manufactured by Ito Essential Oil Co., Ltd .; Examples include products such as “Floron RCM-300” manufactured by Kyoeisha Chemical Co., Ltd .; “Benton SD-2” manufactured by Elementis Specialties and Inc.
  • the content of the anti-sagging agent / anti-settling agent is preferably 0.3 to 3% by mass with respect to 100% by mass of the non-volatile content of the present composition. %.
  • the composition preferably contains a curing accelerator that can contribute to the adjustment of the curing rate, particularly the acceleration.
  • the curing accelerator include conventionally known curing accelerators used in anticorrosive coating compositions, but from the viewpoints of obtaining a coating composition excellent in curing speed and low temperature curability, tertiary amines and the like can be used. Is preferable.
  • the tertiary amine is not particularly limited, and is, for example, triethanolamine, dialkylaminoethanol, triethylenediamine [1,4-diazabicyclo (2,2,2) octane], 2,4,6-tri (dimethylaminomethyl).
  • Phenol example: trade name "Versamine EH30" (manufactured by BASF Japan Ltd.), trade name "Ancamine K-54" (manufactured by Ebony Japan Co., Ltd.)
  • the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass, based on 100% by mass of the non-volatile content of the present composition. % Or more, preferably 5% by mass or less, and more preferably 3% by mass or less.
  • the present composition preferably contains an antifoaming agent from the viewpoints of suppressing the generation of air bubbles and improving the appearance of the obtained anticorrosive coating film.
  • an antifoaming agent for example, various conventionally known defoaming agents such as polymer type, acrylic type, silicone type, mineral oil type and olefin type can be used. Among them, polymer type and olefin type defoamers can be used. Foaming agents are preferred.
  • antifoaming agents examples include “BYK-1788”, “BYK-1790”, and “BYK-1794” manufactured by Big Chemie Japan Co., Ltd .; “AFCONA-2290” manufactured by AFCONA ADDITIVE; manufactured by ExxonMobil Chemical Company. Examples of products such as “SpectraSin 40”, “SpectraSin Elite150”, and “SpectraSin Elite65”.
  • the content of the defoaming agent is preferably 0.01% by mass or more, more preferably 0.05 with respect to 100% by mass of the non-volatile content in the present composition. It is 0% by mass or more, preferably 4% by mass or less, and more preferably 2% by mass or less.
  • the anticorrosive coating film according to one embodiment of the present invention is not particularly limited as long as it is formed from the present composition.
  • the base material with an anticorrosive coating according to an embodiment of the present invention is not particularly limited as long as the anticorrosive coating and the base material are included, but the composition is coated after the base material is coated with the present composition. It is preferable that the product is dried, preferably obtained by a method of drying and curing the coated composition. This method can be said to be a method for preventing corrosion of the base material.
  • the base material is not particularly limited, but is preferably a base material that is required to have anticorrosive properties because the effects of the present invention can be more exerted.
  • a base material a base material made of steel, non-ferrous metal (zinc, aluminum, etc.), stainless steel, etc. is preferable, and structures such as ships, land structures, and bridges made of these materials, particularly ship structures, are more preferable. preferable.
  • the base material may come into contact with bacteria at a place where drying proceeds in a solvent atmosphere or a place where it is difficult to control the drying temperature.
  • a location, particularly a location that can be indirectly indirect with bacteria-containing water such as seawater or industrial water for a long period of time is preferable.
  • the ballast tank is more preferable as the base material.
  • the ballast tank may be provided with anticorrosion by installing an anode such as zinc or zinc-aluminum.
  • the current density during the electrocorrosion protection is preferably about 1 to 10 mA / m 2 .
  • the surface of the base material is treated as necessary in order to remove rust, oil and fat, moisture, dust, slime, salt and the like, and to improve the adhesion of the obtained anticorrosive coating film.
  • it may be blasted (ISO8501-1 Sa2 1/2), rubbing method, degreasing to remove oil and dust), etc., from the viewpoint of corrosion resistance, weldability, shearing property, etc. of the base material.
  • the surface of the base material may be coated with a conventionally known primary rust preventive paint (shop primer) or other primer and dried.
  • the method of applying the present composition to the base material is not particularly limited, and conventionally known methods can be used without limitation, but the workability and productivity are excellent, and even a large-area base material can be easily applied.
  • Spray coating is preferable because it can be coated and the effects of the present invention can be more exerted.
  • the conditions for spray coating may be appropriately adjusted according to the thickness of the anticorrosive coating film to be formed.
  • the primary (air) pressure about 0.4 to 0.8 MPa
  • the secondary (paint). ) Pressure The coating conditions may be set to about 10 to 26 MPa and the gun moving speed to about 50 to 120 cm / sec.
  • the film thickness of the anticorrosive coating film may be appropriately selected according to the desired application, but is preferably 100 ⁇ m or more, more preferably 250 ⁇ m or more, preferably 250 ⁇ m or more, from the viewpoint of providing an anticorrosive coating film having excellent anticorrosive properties. Is 450 ⁇ m or less, more preferably 400 ⁇ m or less.
  • an anticorrosive coating film having a desired thickness may be formed by one coating (one coating), or twice (depending on the anticorrosive property). If necessary, more) may be applied to form an anticorrosive coating film having a desired thickness. From the viewpoint that an anticorrosive coating film having excellent anticorrosive properties can be formed with good workability, it is preferable to form an anticorrosive coating film having a thickness within the above range by two coatings.
  • the method for drying and curing the composition is not particularly limited, and the composition may be dried and cured by heating at about 5 to 60 ° C. in order to shorten the drying and curing time, but usually, the composition is dried and cured.
  • the composition is dried and cured by leaving it at room temperature and in the air for about 1 to 14 days. Further, when the composition is dried and cured by leaving it at a low temperature of about 8 ° C. or lower for about 1 to 14 days, the effect of the present invention, particularly discoloration resistance, is more exhibited.
  • the effect of the present invention is further improved. It is demonstrated.
  • Example 1 In a container, 19 parts by mass of epoxy resin 1 (Note 1), 10 parts by mass of petroleum resin (Note 3), 4 parts by mass of liquid hydrocarbon resin (Note 4), 10.4 parts by mass of xylene, 2 parts by mass of butanol, 1- 1 part by mass of methoxy-2-propanol, 1 part by mass of silane coupling agent (Note 5), 24 parts by mass of talc (Note 7), 6 parts by mass of mica (Note 8), 15 parts by mass of potash long stone (Note 9), titanium Add 6 parts by mass of white (Note 10), 0.1 part by mass of carbon black (Note 11), and 1.5 parts by mass of anti-sag agent (Note 13), and use a high-speed disperser at 56-60 ° C. After mixing the components of the above, the main component was prepared by cooling to 30 ° C. or lower.
  • ethylenediamine (EDA) polyamide adduct 14 parts by mass of ethylenediamine (EDA) polyamide adduct (Note 15), 0.2 parts by mass of tertiary amine (Note 21), and 0.8 parts by mass of 1-methoxy-2-propanol were added to the high-speed disper.
  • the curing agent component was prepared by mixing using.
  • a coating composition was prepared by mixing the obtained main agent component and curing agent component before coating.
  • Examples 2 to 11 and Comparative Examples 1 to 5 A coating composition was prepared in the same manner as in Example 1 except that the raw materials and the blending amounts to be blended in the main agent component and the curing agent component were changed as shown in Table 1.
  • the numerical values in the columns of the main agent component and the curing agent component in Table 1 indicate parts by mass.
  • the details of the raw materials in Table 1 are shown in Table 2.
  • the salt water resistance of the coating film was measured according to JIS K 5600-6-1: 2016. Specifically, it was carried out as follows. On a blasted steel sheet (hereinafter, also referred to as “test plate”) having dimensions of 150 mm ⁇ 70 mm ⁇ 1.6 mm (thickness), the coating compositions obtained in the above-mentioned Examples and Comparative Examples were put on a dry film. Spray coating was performed so as to have a thickness of about 320 ⁇ m, and the obtained test plate with a coating film was dried at 23 ° C. and 50% RH for 7 days.
  • test plate blasted steel sheet having dimensions of 150 mm ⁇ 70 mm ⁇ 1.6 mm (thickness)
  • Spray coating was performed so as to have a thickness of about 320 ⁇ m, and the obtained test plate with a coating film was dried at 23 ° C. and 50% RH for 7 days.
  • a notch 2 reaching the steel plate from the coating film side was made at the position shown in FIG. 1 of each test plate.
  • the test plate 1 having the notch 2 was immersed in 3% salt water at 40 ° C. for 180 days so that the notch 2 side was facing down (in the direction shown in FIG. 1). After immersion, 11 cuts 3 are made upward in order from the left end of the cuts 2 so that the cuts 2 are equally divided at 5 mm intervals, and the steel plate and the coating film are formed at 10 measuring portions 4 between the cuts 3.
  • the peeling length (length from the notch 2) was measured. The average value of the measured peeling lengths at 10 points was evaluated according to the following criteria.
  • the high temperature and high humidity resistance of the test plate with a coating film prepared in the same manner as the above salt water resistance test was evaluated in accordance with JIS K 5600-7-2: 1999. Specifically, it was carried out as follows.
  • the test plate 1 having the notch 2 prepared in the same manner as the salt water resistance test was held in a tester at a temperature of 50 ° C. and a humidity of 95% for 90 days, and then a cut 3 was made in the same manner as in the salt water resistance test, and each cut was made.
  • the peeling length (length from the notch 2) between the steel plate and the coating film was measured at 10 measuring units 4 between 3. The average value of the measured peeling lengths at 10 points was evaluated in the same manner as in the salt water resistance test.
  • the color difference is measured in accordance with JIS K 5600-4-5: 1999, using a spectroscopic colorimeter (model SD 5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and JIS K 5600-4-6. : The color difference ⁇ E was calculated according to 1999.
  • biofilm was collected from the surface of the tank soaked in the sea for more than half a year.
  • the collected biofilm was immediately diluted 40-fold with seawater to prepare an immersion liquid. There was no big difference in the results depending on the location of the sea where the tank was immersed, the time when the tank was immersed, and the type of tank.
  • Test plate 2 Notch 3: Cut 4: Measuring unit

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Abstract

Un mode de réalisation de la présente invention concerne une composition de revêtement anticorrosion, un film de revêtement anticorrosion, un substrat pourvu d'un film de revêtement anticorrosion, et un procédé de production d'un substrat pourvu d'un film de revêtement anticorrosion. La composition de revêtement anticorrosion contient une résine époxyde (A), un agent de durcissement amine (B), un agent de couplage au silane (C) et un pigment de charge (D). La concentration en volume de pigment (PVC) est comprise entre 30 et 45 %, l'agent de durcissement amine (B) comprend de l'éthylène diamine ou une forme modifiée de cette dernière, et la composition satisfait (i) ou (ii).　(i) la résine époxyde (A) comprend une résine époxyde ayant un équivalent époxy de 270 ou moins. (Ii) la teneur en composés organiques volatils (COV) est de 340 g/l ou moins.
PCT/JP2020/015641 2019-04-12 2020-04-07 Composition de revêtement anticorrosion WO2020209245A1 (fr)

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CN112920679A (zh) * 2021-01-29 2021-06-08 南京工业大学 一种防腐涂料及其制备方法与应用

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