WO2012153382A1 - Anti-corrosive coating composition and method for forming coating film - Google Patents

Anti-corrosive coating composition and method for forming coating film Download PDF

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Publication number
WO2012153382A1
WO2012153382A1 PCT/JP2011/060663 JP2011060663W WO2012153382A1 WO 2012153382 A1 WO2012153382 A1 WO 2012153382A1 JP 2011060663 W JP2011060663 W JP 2011060663W WO 2012153382 A1 WO2012153382 A1 WO 2012153382A1
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WIPO (PCT)
Prior art keywords
epoxy resin
coating composition
resin
anticorrosion
anticorrosion coating
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PCT/JP2011/060663
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French (fr)
Japanese (ja)
Inventor
弘一 鍛治
愼一 石原
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日本ペイントマリン株式会社
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Priority to PCT/JP2011/060663 priority Critical patent/WO2012153382A1/en
Publication of WO2012153382A1 publication Critical patent/WO2012153382A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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

Definitions

  • the present invention relates to an anticorrosion coating composition, and more particularly to an anticorrosion coating composition having excellent anticorrosion properties and excellent adhesion to an object to be coated and a top coat film. Moreover, this invention relates to the coating-film formation method using the said anticorrosion coating composition.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-211464
  • Patent Document 2 Japanese Patent Laid-Open No. 10-259351
  • Patent Document 3 Japanese Patent Laid-Open No. Hei 10-214951. No. 08-092349.
  • the anticorrosion coating film On the anticorrosion coating formed from the anticorrosion coating, various top coatings are applied to form an overcoating according to the environment in which the article to be coated or its part is placed.
  • the anticorrosion coating film In order for such a composite coating film to exhibit excellent anticorrosion properties, the anticorrosion coating film needs to have excellent adhesion to the substrate surface and interlaminar adhesion to the top coating film.
  • the present invention provides an anticorrosion coating composition that is excellent in adhesion to both an object to be coated and a top coating film, and can form a coating film that exhibits high anticorrosion performance over a long period of time even in a harsh environment.
  • the other objective of this invention is to provide the anticorrosion coating film formed from the said anticorrosion coating composition, the composite coating film which has the said anticorrosion coating film, and its formation method.
  • the present invention provides an anticorrosion coating composition
  • the alicyclic hydrocarbon resin-modified epoxy resin (b) is preferably a dicyclopentadiene type epoxy resin (b ′).
  • the dicyclopentadiene type epoxy resin (b ′) preferably has an epoxy equivalent of 245 or more and 280 or less and a softening point of 54 ° C. or more and 85 ° C. or less.
  • the solid content ratio (b) / (a) of the alicyclic hydrocarbon resin-modified epoxy resin (b) to the bisphenol-type epoxy resin (a) is preferably 5/100 or more and 65/100 or less by mass ratio. .
  • the solid content ratio (c) / ⁇ (a) + (b) ⁇ of the amine curing agent (c) with respect to the total of the bisphenol type epoxy resin (a) and the alicyclic hydrocarbon resin-modified epoxy resin (b) is The mass ratio is preferably 15/100 or more and 50/100 or less.
  • the amine curing agent (c) is preferably a dimer acid-modified amine curing agent (c ′).
  • the anticorrosion coating composition of the present invention can further contain a silane coupling agent (d).
  • the solid content of the silane coupling agent (d) is preferably 0.3% by mass or more and 3% by mass or less in the solid content of the anticorrosive coating composition.
  • the present invention also includes a step of forming an anticorrosion coating film by applying the above-mentioned anticorrosion coating composition to an object to be coated, and a step of forming an overcoat coating film on at least a part of the anticorrosion coating film.
  • a film forming method is provided.
  • a suitable example of the object to be coated is a ship.
  • the coating film forming method of the present invention applies the anticorrosion coating composition to the ship bottom, propeller, water line, outer shell, deck, upper structure, hold, and ballast tank.
  • a step of forming an anti-fouling coating film a step of forming an anti-fouling coating composition by coating the anti-fouling coating composition on at least the bottom and water line anti-corrosion coatings, an outer shell part, a deck part
  • epoxy resin paint, chlorinated rubber resin paint, vinyl chloride resin paint, alkyd resin paint, silicone alkyd resin paint Selected from the group consisting of acrylic resin paints, urethane resin paints, fluororesin paints, polyester resin paints, silicone resin paints, and epoxy acrylic resin paints Even without by painting one top coating may include forming a top coating film.
  • the anticorrosive coating composition of the present invention is excellent in adhesion to an object to be coated and a top coat film, and can form an anticorrosion coating film that exhibits high anticorrosion performance over a long period of time even in a harsh environment.
  • the anticorrosive coating composition of the present invention comprises a bisphenol type epoxy resin (a), an alicyclic hydrocarbon resin-modified epoxy resin (b), and an amine-based curing agent (c).
  • a bisphenol type epoxy resin
  • b alicyclic hydrocarbon resin-modified epoxy resin
  • c amine-based curing agent
  • the bisphenol type epoxy resin (a) used in the anticorrosive coating composition of the present invention can be a general bisphenol type epoxy resin, and may be a bisphenol A type or a bisphenol F type.
  • Examples of commercial products of bisphenol type epoxy resins that can be used in the present invention include, for example, Epicoat # 828 (bisphenol A type liquid epoxy resin, epoxy equivalent of 184 to 194, molecular weight of about 380, oil Epicoat # 834-90X (bisphenol A type solid epoxy resin, epoxy equivalent 230-270, molecular weight about 470, manufactured by Yuka Shell Co.); Epicoat # 1001 (bisphenol A type solid epoxy resin, epoxy equivalent 450) Epicoat # 1004 (bisphenol A type solid epoxy resin, epoxy equivalent 875 to 975, molecular weight about 1600, made by Yuka Shell Co.); Epicoat # 1007 (bisphenol A type solid) Epoxy resin, epoxy equivalent 1 50-2200, molecular weight of about 2900, manufactured by Yuka Shell); Epicoat # 807 (bisphenol F type liquid epoxy resin, epoxy equivalent of 160-175, molecular weight of about 330, manufactured by Yuka Shell); jER1001-70X (bisphenol A type) Epoxy resin, epoxy equivalent 450-500, molecular weight
  • the bisphenol type epoxy resin (a) one having an appropriate viscosity can be selected according to the viscosity of other components, and the shape thereof may be solid or liquid.
  • the shape thereof may be solid or liquid.
  • the epoxy equivalent of the bisphenol type epoxy resin (a) is preferably 100 or more and 3000 or less, more preferably 150 or more and 1000 or less. If it is less than 100, the flexibility of the anticorrosion coating film may be lowered due to an increase in the crosslinking density. On the other hand, when it exceeds 3000, curability may be inferior (sufficient crosslinking density may not be obtained) or the toughness of the anticorrosive coating film may be inferior.
  • the number average molecular weight of the bisphenol type epoxy resin (a) is preferably 200 or more and 5000 or less, more preferably 300 or more and 2000 or less. If it is less than 200, the physical properties of the coating film may be inferior, and if it exceeds 5000, the workability may be inferior, such as the need to add a large amount of solvent in order to adjust the viscosity to an appropriate level for coating.
  • the number average molecular weight here is a polystyrene equivalent value measured by gel permeation chromatography (GPC: Gel Permeation Chromatography).
  • Bisphenol type epoxy resin may be used alone or in combination of two or more.
  • the alicyclic hydrocarbon resin-modified epoxy resin (b) used in the anticorrosion coating composition of the present invention is at least partially a norbornene skeleton represented by the following general formula (1) (m is an integer of 1 to 20)
  • a modified epoxy resin having a structural unit of By adding an alicyclic hydrocarbon resin-modified epoxy resin containing a structural unit represented by the following general formula (1) to the anticorrosion coating composition, adhesion to the coating object and the top coating film is improved, The water resistance of the coating is improved. As a result, anticorrosion performance can be improved.
  • m is preferably an integer of 1 or more and 10 or less.
  • structural units represented by the general formula (1) particularly preferred structural units include structural units derived from dicyclopentadiene represented by the following general formula (2).
  • the structural unit derived from dicyclopentadiene has low hygroscopicity and high softening point. For this reason, by including a structural unit derived from dicyclopentadiene, the hygroscopicity of the alicyclic hydrocarbon resin-modified epoxy resin can be reduced, and the softening point can be appropriately increased, thereby providing excellent anticorrosion of the coating film.
  • the coating film strength can be increased while maintaining the performance.
  • dicyclopentadiene type epoxy resins (b ′) give flexibility to the coating film by having a flexible cyclopentane ring and also absorb moisture of the coating film by having a high hydrophobicity of the cyclopentane ring. Therefore, the adhesion of the anticorrosion paint to a wide range of materials and the anticorrosion can be imparted. Further, by reducing the molecular weight of the dicyclopentadiene type epoxy resin (b ′), the compatibility with the bisphenol type epoxy resin (a) can be increased.
  • the said dicyclopentadiene type epoxy resin may be used individually by 1 type, and may use 2 or more types together.
  • the epoxy equivalent of the dicyclopentadiene type epoxy resin (b ′) is preferably 230 or more and 280 or less, more preferably 245 or more and 280 or less, and further preferably 250 or more and 275 or less. If it is less than 230, the flexibility of the anticorrosive coating film tends to decrease due to the increase in the crosslinking density. On the other hand, if it exceeds 280, the curability may be inferior or the toughness of the anticorrosive coating film may be inferior.
  • the epoxy equivalent a value measured based on JIS K 7236 is adopted.
  • the softening point of the dicyclopentadiene type epoxy resin (b ′) is preferably 54 ° C. or higher and 85 ° C. or lower. If the temperature is lower than 54 ° C., when the top coating film is further formed on the anticorrosion coating film, the anticorrosion coating film may not be sufficiently heat-resistant, so that the anticorrosion coating film may be plastically deformed. When it exceeds 85 degreeC, the adhesiveness with to-be-coated object may fall, or the smoothness of the coating film obtained may fall.
  • the softening point of said epoxy resin shall employ
  • the anticorrosive coating composition of the present invention comprises a bisphenol type epoxy resin (a) and an alicyclic hydrocarbon resin-modified epoxy resin (b) such as a dicyclopentadiene type epoxy resin (b ′) in combination. While improving the adhesiveness with a to-be-coated object, the adhesiveness with the top coat film formed on an anticorrosion coating film can also be improved.
  • the dicyclopentadiene type epoxy resin (b ′) has good compatibility with the bisphenol type epoxy resin (a), and the structural unit derived from dicyclopentadiene has a branched structure.
  • anticorrosion coating composition can be applied also to raw materials, such as brass, for which it was difficult to ensure adhesiveness until now.
  • the solid content ratio (b) / (a) of the alicyclic hydrocarbon resin-modified epoxy resin (b) to the bisphenol-type epoxy resin (a) is preferably 5/100 or more and 65/100 or less by mass ratio. More preferably, it is 10/100 or more and 35/100 or less. If it is less than 5/100, the anticorrosion performance may not be sufficiently obtained. If it exceeds 65/100, the anticorrosion coating film becomes too hard, and the adhesion to the article to be coated is reduced. Easy to peel.
  • the alicyclic hydrocarbon resin-modified epoxy resin (b) preferably contains an alicyclic hydrocarbon resin having at least one functional group selected from the group consisting of an ester group, a hydroxyl group, and a carboxyl group.
  • amine curing agent (c) As the curing agent for curing the epoxy resin contained in the anticorrosion coating composition of the present invention, it is preferable to use an amine-based curing agent (c). By using the amine curing agent (c) in combination with the above two types of epoxy resins, the flexibility of the resulting anticorrosion coating film can be improved, and the anticorrosion coating film and the object to be coated, or the anticorrosion coating film and the top coating Adhesion with the film can be further improved.
  • the amine-based curing agent (c) used in the anticorrosion coating composition of the present invention plays a role of causing the coating film to cure at room temperature, a so-called curing agent.
  • Such an amine curing agent (c) has an amino group that undergoes an addition reaction with the epoxy group in the bisphenol type epoxy resin (a) and the alicyclic hydrocarbon resin-modified epoxy resin (b). Then, curing of the anticorrosion coating composition is started.
  • Such an anticorrosion coating composition is suitably used for applications that are applied in a room temperature environment such as painting of the outer plate of a ship.
  • Examples of the amine curing agent (c) include known polyamine compounds and modified products thereof.
  • Examples of the polyamine compound include aliphatic polyamines, alicyclic polyamines, and aromatic polyamines.
  • Examples of the modified product of the polyamine compound include a dimer acid-modified amine-based curing agent (c ′) obtained by reacting a dimer acid and a polyamine compound. Only one amine curing agent may be used alone, or two or more amine curing agents may be used in combination.
  • Examples of the aliphatic polyamine suitably used in the anticorrosion coating composition of the present invention include ethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyoxypropylenediamine, polyoxypropylenetriamine and the like. Can be mentioned.
  • Cyclohexane metaxylenediamine, bis (4-amino-3-methylcyclohexyl) methane, polycyclohexylpolyamine, norbornenediamine, furfurylamine, tetrahydrofurfurylamine, methylenebis (furanmethaneamine), phenalkamine, 3,9- And bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane adduct.
  • dimer acid-modified amine curing agent (c ′) obtained by reacting a dimer acid and a polyamine compound as the amine curing agent (c).
  • dimer acid-modified amine curing agent (c ') in addition to steel materials such as non-treated steel materials, blast-treated steel materials, acid-treated steel materials, steel materials such as galvanized steel materials and stainless steel materials, aluminum (alloy) materials, copper
  • the adhesion of the anticorrosion coating to non-ferrous metal materials having a wide range of properties such as (alloy) materials, brass materials, and fiber reinforced plastics (FRP) can be further improved.
  • dimer acid-modified amine curing agents (c ′) examples include, for example, trade names of racamide TD-966 (manufactured by DIC Corporation), ancamide 2050 (manufactured by Air Products), Adeka Hardener. EH-355 (manufactured by ADEKA Corporation).
  • An example of a commercially available amine-based curing agent (c) other than the dimer acid-modified amine-based curing agent (c ′) is, for example, sunmide 308D-65T (trade name, manufactured by Air Products).
  • the hydrogen equivalent is preferably 0.5 or more and 1.2 or less. If it is less than 0.5, the amine group is insufficient, and if it exceeds 1.2, the epoxy group is insufficient. In any case, the coating density or anticorrosion performance (especially anticorrosion performance) can be reduced by reducing the crosslinking density.
  • the solid content ratio (c) / ⁇ (a) + (b) of the amine curing agent (c) with respect to the total of the bisphenol type epoxy resin (a) and the alicyclic hydrocarbon resin-modified epoxy resin (b) ⁇ Is preferably 15/100 or more and 50/100 or less, more preferably 20/100 or more and 40/100 or less. If it is less than 15/100, the amine group is insufficient, and if it exceeds 50/100, the epoxy group is insufficient. In any case, the coating density or anticorrosion performance (particularly anticorrosion performance) can be reduced by reducing the crosslinking density.
  • the anticorrosion coating composition of the present invention comprises a component containing a bisphenol type epoxy resin (a) and an alicyclic hydrocarbon resin-modified epoxy resin (b), and a component containing an amine curing agent (c).
  • a two-component paint is preferred.
  • the anticorrosion coating composition of the present invention preferably contains a silane coupling agent (d).
  • a silane coupling agent (d) a compound having both an organic functional group having an affinity for an organic polymer such as an epoxy resin and an inorganic functional group having an affinity for an inorganic material such as a pigment is used. It is preferable.
  • silane coupling agent (d) it is possible to improve the adhesiveness of the interface where the organic polymer and the inorganic material are in contact with each other, and to improve the adhesion of the coating film.
  • organic functional group showing affinity for the organic polymer those having polarity in the functional group are preferable, and examples of such a polar functional group include an amino group, a carboxyl group, a hydroxyl group, an epoxy group, and a glycidyl group. Preferably, it is an epoxy group.
  • the silane coupling agent (d) preferably has one or more polar functional groups.
  • silane coupling agent containing an epoxy group examples include (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, and ⁇ -glycidoxy.
  • examples thereof include propylmethyldiethoxysilane and ⁇ -glycidoxypropyltriethoxysilane.
  • Examples of commercially available epoxy group-containing silane coupling agents include, for example, KBM-303 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a trade name of (3,4-epoxycyclohexyl) ethyltrimethoxysilane; (3,4-epoxycyclohexyl) ethyltrimethoxysilane A-186 (manufactured by Nippon Unicar Co., Ltd.); ⁇ -glycidoxypropyltrimethoxysilane KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.); ⁇ - A-187 glycidoxypropyltrimethoxysilane (manufactured by Nihon Unicar Co., Ltd.); KBM-402 ⁇ -glycidoxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.); ⁇ -glycidoxyprop
  • the solid content of the silane coupling agent (d) is preferably 0.3% by mass or more and 3% by mass or less in the solid content of the anticorrosion coating composition.
  • the anticorrosion coating composition obtained can be more excellent in adhesion to the coating material and the top coating film of the anticorrosion coating film, and has excellent anticorrosion performance. You can get things.
  • the mass of the solid content of the “anticorrosive coating composition” refers to the bisphenol type epoxy resin (a), the alicyclic hydrocarbon resin-modified epoxy resin (b), the amine type curing agent (c), and the silane. It means the total amount (total amount of solid content) with the coupling agent (d), and means the total mass of the solid content of all components other than the other additives described later.
  • the anticorrosion coating composition of the present invention may contain other additives other than those described above.
  • Other additives include, for example, pigments, solvents, water binders, anti-sagging agents, anti-color separation agents, anti-settling agents, antifoaming agents, coating film consumption regulators, UV absorbers, surface modifiers, and viscosity modifiers. Agents, leveling agents, pigment dispersants and the like.
  • pigment one or more selected from the group consisting of a color pigment, an extender pigment, and a rust preventive pigment can be used.
  • the color pigment include inorganic color pigments such as titanium oxide, yellow iron oxide, carbon, and petal, and organic color pigments such as cyanine blue and cyanine green.
  • extender pigments include barium sulfate, precipitated barium sulfate, clay, talc, mica, calcium carbonate, silica, and glass flakes.
  • the rust preventive pigment include molybdic acid, phosphoric acid, phosphorous acid, boric acid, and ferrite pigments.
  • solvents examples include hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane, white spirit; dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Ethers such as monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; ethyl isobutyl ketone , Ketones such as methyl isobutyl ketone; n-butanol, propyl Examples include alcohols such as alcohol.
  • a solvent may be
  • Anti-sagging agents include organic clay Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonate salts, polyethylene wax, amide wax, hydrogenated castor oil wax, poly Examples thereof include amide waxes, synthetic fine silica, oxidized polyethylene waxes, and mixtures of two or more thereof.
  • Examples of the anti-sagging agent are, for example, trade names of Disparon 305 (manufactured by Enomoto Kasei Co., Ltd.), Dispalon 6900-20X (manufactured by Enomoto Kasei Co., Ltd.), Disparon 6650 (manufactured by Enomoto Kasei Co., Ltd.), Disparon 6700 (manufactured by Enomoto Kasei Co., Ltd.), Talen VA-750B (manufactured by Kyoeisha Chemical Co., Ltd.), and Talen VA-780 (manufactured by Kyoeisha Chemical Co., Ltd.).
  • the article to which the anticorrosive coating composition of the present invention is applied is not particularly limited, and is particularly preferably used on the surface of a structure that is at least partially disposed in water (in seawater).
  • Examples of such objects to be coated include ships; harbor facilities; oil fences; water intake facilities such as power plants; piping for cooling conduits; bridges; buoys; industrial water systems; And so on.
  • the material of the coating is non-treated steel, blasted steel, acid-treated steel, galvanized steel, stainless steel, etc., aluminum (alloy) material, copper (alloy) material, brass material, fiber reinforced plastic (FRP: Nonferrous metal materials such as Fiber (Reinforced Plastics). These steel materials and non-ferrous metal materials may have weld lines.
  • the anticorrosion coating composition of the present invention since the anticorrosion coating composition of the present invention has excellent adhesion to a brass material, it is suitably used for a marine propeller shaft portion that is often made of a brass material.
  • the anticorrosion coating film formed using the anticorrosion coating composition of the present invention is excellent in adhesion to the article to be coated and the top coating film, the anticorrosion coating film exhibits high anticorrosion properties over a long period of time even in a harsh environment.
  • Such an anticorrosive coating film can be formed by volatilizing and removing the solvent at room temperature or under heating as necessary after applying the anticorrosion coating composition on the surface of the object to be coated according to a conventional method. .
  • the anticorrosion coating film preferably has a film thickness of 10 ⁇ m or more and 500 ⁇ m or less. If it is less than 10 ⁇ m, not only is it too thin to apply uniformly, but also good corrosion resistance cannot be obtained. On the other hand, when the thickness exceeds 500 ⁇ m, not only the coating film becomes too thick and the coating cost becomes high, but also the internal stress of the coating film becomes too large and the coating film may be peeled off.
  • the coating method of the anticorrosion coating composition is not particularly limited, and may be a conventionally known method such as a dipping method, a spray method, brush coating, a roller, electrostatic coating, or electrodeposition coating.
  • the anticorrosion coating composition may be directly applied to the surface of the object to be coated, or the anticorrosion coating composition may be applied after applying a shop primer to the surface of the object to be coated as necessary.
  • an anti-corrosion coating composition containing a hydrolyzed initial condensation product of tetraalkoxysilicate, acidic solvent-dispersed colloidal silica, and zinc powder; a melting point higher than zinc and lower than iron
  • Anticorrosion paint in which the above particles are 95% by volume or more of the total amount of zinc powder, the zinc powder content is 20 to 60 parts by volume per 100 parts by volume of the dried coating film, and the coating film has heat resistance of 600 ° C. or more. It is preferable to use an anticorrosive coating composition having a composition; or a composition similar to these.
  • Top coat film It is preferable to form a top coat by applying a top coat on the anticorrosion coat coated as described above.
  • the top coat film can be formed using the same method as the coating method of the anticorrosive coating composition described above.
  • Top coatings include epoxy resin paint, chlorinated rubber resin paint, vinyl chloride resin paint, alkyd resin paint, silicone alkyd resin paint, acrylic resin paint, urethane resin paint, fluororesin paint, polyester resin Paints, silicone resin paints, epoxy acrylic resin paints, and various antifouling paints can be used.
  • the composite coating film formed using the anticorrosion coating composition of the present invention comprises a step of forming an anticorrosion coating film by coating the anticorrosion coating composition on an object to be coated, and an overcoating on at least a part of the anticorrosion coating film. It is preferable to form by the method including the step of forming a coating film.
  • the composite coating film formed in this way has high adhesion between the anticorrosion coating film, the object to be coated (base) and the top coating film, and exhibits high anticorrosion performance over a long period even in a harsh environment.
  • the anticorrosive coating composition of the present invention is all of the ship bottom, propeller, water line, outer shell, deck, upper structure, hold, and ballast tank. There is an advantage that it can be applied to the region. Of the surface of the ship, at least the ship bottom and the water line part, and preferably the propeller part, contact with seawater during the operation of the ship, so that the antifouling paint composition is applied as a top coat applied on the anticorrosion coating. It is preferable to use and form an antifouling coating film.
  • preferable antifouling paint compositions include, for example, hydrolyzable antifouling paint compositions containing an antifouling agent, and non-eluting paint compositions containing silicone rubber.
  • Hydrolyzable antifouling paint compositions include resins containing metal ester groups (metals are divalent such as Cu and Zu, the same shall apply hereinafter), resins containing silylacryl groups, metal ester groups and silyl Including resin containing acrylic group, resin containing metal acrylic group and silicon-containing group, resin containing silylacryl group and silicon-containing group, or resin containing metal acrylic group, silylacryl group and silicon-containing group A hydrolyzable antifouling paint composition can be mentioned.
  • the non-eluting antifouling paint is composed of a condensation curable silicone rubber composition and a dry curable silicone graft acrylic resin as shown in, for example, Japanese Patent No. 4043540, and macroscopically separated into each resin.
  • microscopically microdomains formed by gathering similar components together appear at random on the surface of the coating, and a large amount of components constitutes a continuous phase and a minor amount of components constitutes a dispersed phase.
  • An antifouling coating composition that forms a sea-island structure may be used.
  • Each of the above antifouling paints is a component that is usually blended in marine antifouling paints, such as antifouling agents, plasticizers, hydrolysis regulators, pigments, solvents, viscosity modifiers, silicone oils, other additives, etc. May be included.
  • the top coat film can be formed by applying at least one top coat selected from the group consisting of:
  • the anticorrosion coating composition of the present invention can be a coating that can easily manage the film thickness by adjusting the concentration of the color pigment in the coating. That is, it is easily determined whether or not the anticorrosion coating film has reached the target film thickness by coating the anticorrosion coating composition while visually confirming the change in color difference between the coating film being coated and the object to be coated. be able to. Since the color difference does not change whether the coating is wet or after drying, the change in color difference between the coating and the primer layer is visually observed while the anticorrosion coating during coating is wet. It can be determined whether or not the anticorrosion coating film being coated has reached a prescribed film thickness.
  • Such an anticorrosion coating composition capable of controlling the film thickness is particularly effective when a large structure is applied, such as when an outer skin of a ship is applied.
  • the conditions for controlling the film thickness will be described in detail below.
  • Including 0.01% by volume or more and 3% by volume or less of a color pigment based on the solid content of the anticorrosion coating composition and the following conditions: (1) The color difference between the anticorrosive coating composition and the article to be coated is 20 or more, (2) The color difference between the coating film having the target dry film thickness and the coating film having a film thickness of less than 80% of the target dry film thickness is 2 or more, (3) The color difference between the coating film having the target dry film thickness and the coating film having a film thickness exceeding 120% of the target dry film thickness is less than 1, It is preferable to adjust the content of the color pigment in the anticorrosion coating composition so as to satisfy the above condition.
  • the dry film thickness of an anticorrosion coating film can be controlled to a target value easily (typically visually) and correctly.
  • the color difference can be measured by a generally known method using a color difference meter such as an SM color computer [Model: SM-7CH (manufactured by Suga Test Instruments Co., Ltd.)].
  • the color difference between the anticorrosive coating composition and the object to be coated is preferably 20 or more.
  • the color difference between the anticorrosive coating composition and the object to be coated is set to 35 or more. Is more preferable.
  • the color difference between the anticorrosive coating composition and the object to be coated is less than 20, as the film thickness of the anticorrosive coating composition approaches the target film thickness, it becomes difficult to visually determine the color difference from the object to be coated, and a desired film There is a tendency to apply thicker than the thickness.
  • the hue range of the anticorrosive coating composition is that when the hue of the object to be coated is 0 on the Munsell's 100 hue ring and the counterclockwise display is 0 to +50 and the clockwise direction is 0 to -50. Those having a hue close to complementary colors such that the hue range is -20 to -50 or +50 to +20 are preferred. Since the color difference increases as the hues of the upper and lower layers are closer to complementary colors, the hue range of the upper anticorrosive coating composition is more preferably set to ⁇ 40 to ⁇ 50, or +50 to +40.
  • the color difference between the coating film having the target dry film thickness and the coating film having a film thickness of less than 80% of the target dry film thickness is preferably 2 or more.
  • a coating film having a film thickness of less than 80% of the target dry film thickness is a film immediately before the completion of coating, but even when there is no color difference of 2 or more with respect to the color tone of the film having the target dry film thickness It appears to the human eye as having reached the target dry film thickness. For this reason, there exists a tendency for the film thickness of the part to become partially thinner than a target dry film thickness.
  • the upper limit of the color difference is preferably 10, and more preferably 5.
  • a coating film having a film thickness exceeding 120% of the target dry film thickness is a coating film immediately after the completion of coating.
  • the color difference between the coating film having the target dry film thickness and the coating film having a film thickness exceeding 120% of the target dry film thickness is preferably as small as possible, preferably less than 1, more preferably 0.5. Is less than.
  • the color difference is 1 or more, the color difference is different even between the coating films that have reached the target dry film thickness, and the color unevenness tends to appear remarkably after coating.
  • the color difference to be satisfied by the anticorrosion coating composition among the above conditions (1) to (3) (1) can be read as (1 ') below.
  • (1 ′) The color difference between the anticorrosive coating composition and the primer is 20 or more.
  • the dry film thickness of the anticorrosion coating can be controlled easily (typically visually) to the target value accurately.
  • Example 1 A bisphenol-type epoxy resin, an alicyclic hydrocarbon resin-modified epoxy resin, a solvent (xylene and isobutanol), a silane coupling agent, a pigment, and an additive are mixed at a blending ratio shown in Table 1,
  • An epoxy liquid (liquid A) was prepared by dispersing the composition with a high-speed disperser so that the dispersed particle size became 80 ⁇ m or less.
  • an amine curing agent (Liquid B) was prepared by mixing an amine curing agent and a solvent at a ratio shown in Table 1.
  • the anticorrosive coating composition of the present Example was obtained by mixing the epoxy liquid (A liquid) and the amine curing agent (B liquid).
  • the timing for mixing the epoxy liquid (A liquid) and the amine curing agent (B liquid) was 15 minutes before coating.
  • the above dispersed particle size is a value measured according to Japanese Industrial Standard (JIS K 5600 2-5) using a grind gauge.
  • the unit of numerical values shown in Table 1 is parts by mass.
  • Examples 2 to 16, Comparative Examples 1 to 3 The anticorrosive coating compositions of Examples 2 to 16 and Comparative Examples 1 to 3 were mixed by mixing the respective components in the same procedure as in Example 1 except that the respective components were blended in the ratio as shown in Table 1. Got.
  • Amine-based curing agent (c) sunmide 308D-65T (manufactured by Air Products), solid content concentration 65%
  • Dimer acid-modified amine curing agent (c-1) Adeka Hardener EH-355 (manufactured by ADEKA Corporation), solid content concentration 68%
  • Titanium oxide Titanium CR-50 (Ishihara Sangyo Co., Ltd.)
  • Talc Talc SP-42 (manufactured by Maruo Calcium Co., Ltd.)
  • Sag stopper Disparon 6900-20X (manufactured by Enomoto Kasei Co., Ltd.).
  • the anticorrosion coating film formed by applying the anticorrosion coating composition of each Example and each Comparative Example was evaluated for adhesion to an object to be coated, adhesion to a shop primer, and adhesion to a top coating film. .
  • Each evaluation method is as follows.
  • Adhesion with the object to be coated (cross-cut adhesion test)
  • the adhesion between the object to be coated and the anticorrosive coating film was evaluated as follows. First, two base plates made of galvanized steel sheet, aluminum, stainless steel, brass, FRP, and iron were prepared for each of the examples and the comparative examples. And after apply
  • a cross-cut adhesion test was performed on one of the two test plates on which the anticorrosion coating film was formed in accordance with JIS K5600.55.6. Specifically, a 25 square grid is created by cutting a test plate with a knife until it reaches the base plate with a gap of 3 mm, and an adhesive tape is bonded onto the grid, The adhesive tape was peeled off in a direction forming an angle of 45 ° with respect to the surface. Thereafter, the squares from which the anticorrosive coating film was peeled were counted, and the ratio (%) of the squares to which all the squares were peeled was calculated. The numerical values scored according to the following criteria are shown in the “Initial” column of “Adhesiveness to substrate” in Table 2.
  • Evaluation score 5 0% peeling rate of grid on grid Evaluation score 4: More than 0% and 5% or less peeling rate of grid of grid Evaluation score 3: Stripping rate of grid on grid is over 5% and 15% or less, Evaluation score 2: Stripping rate of grid on grid is more than 15% and less than 25%, Evaluation score 1: More than 25% peeling rate of grid on grid.
  • test plate was immersed in water at 40 ° C. for 3 months, and then a cross-cut adhesion test was performed under the same conditions as described above.
  • the numerical values scored according to the same criteria as above are shown in the column “After 40 ° C. hot water immersion” in “Adhesion to substrate” in Table 2.
  • An anticorrosion coating film was formed on the shop primer layer thus formed by applying the anticorrosion coating composition shown in each of the examples and comparative examples to obtain a test plate.
  • the adhesion between the anticorrosion coating film and the shop primer was evaluated by conducting a cross-cut adhesion test on one of the two test plates on which the anticorrosion coating film was formed under the same conditions as described above.
  • the numerical values scored according to the same criteria as described above are shown in the “Initial” column of “Shop primer adhesion” in Table 2.
  • test plate was immersed in water at 40 ° C. for 3 months, and then a cross-cut adhesion test was performed under the same conditions as described above.
  • the numerical values scored according to the same criteria as described above are shown in the column “After immersion at 40 ° C.” in “Shop primer adhesion” in Table 2.
  • Adhesion of top coat film (cross-cut adhesion test) The adhesion between the anticorrosion coating and the top coating was evaluated as follows. First, a sandblasted steel sheet was prepared as an object to be coated, and the anticorrosive coating compositions of the examples and comparative examples were spray-coated on the surface of the steel sheet so as to have a dry film thickness of 30 ⁇ m ⁇ 10 ⁇ m. Then, the anticorrosion coating film was formed by making it dry at 23 degreeC for 7 days.
  • An epoxy resin paint, urethane resin paint, or acrylic resin paint is applied onto the anticorrosion coating film and dried at 23 ° C. for 7 days, so that the dry coating film has a thickness of 40 ⁇ m ⁇ 10 ⁇ m. Formed. Further, a hydrolyzable antifouling paint was applied on the anticorrosive paint film and dried at 23 ° C. for 7 days to form an overcoat paint film having a dry film thickness of 80 ⁇ m ⁇ 10 ⁇ m.
  • a silicone intermediate coating is applied on the anticorrosion coating so that the dry film thickness is 100 ⁇ m ⁇ 10 ⁇ m, and after 24 hours, the dry film thickness is 150 ⁇ m ⁇
  • a silicone-based top coating was applied to a thickness of 10 ⁇ m and dried at 23 ° C. for 7 days to form a top coating film. Then, a cross-cut adhesion test was performed on the top coat film thus obtained under the same conditions as described above.
  • “Topcoat Adhesiveness” in Table 2 the values obtained by scoring the adhesiveness of each paint based on the same criteria as described above are shown.
  • Epoxy paint Product name Nippe Epoxy Finish M (manufactured by Nippon Paint Marine Co., Ltd.), [2] Urethane paint: Product name Polyuremite Rack M (manufactured by Nippon Paint Marine Co., Ltd.), [3] Acrylic paint: Product name Nippon A-Marine Finish (manufactured by Nippon Paint Marine Co., Ltd.) [4] Hydrolyzable antifouling paint: Product name Propera Ichiban (manufactured by Nippon Paint Marine Co., Ltd.) [5] Non-eluting silicone antifouling paint: (intermediate coating) product name Ecorosilk Thai coat (manufactured by Nippon Paint Marine Co., Ltd.), (top coating) product name Ecorosilk (manufactured by Nippon Paint Marine Co., Ltd.).
  • the anticorrosion coating composition of each example and each comparative example was applied to a test plate (6 types of galvanized steel plate, aluminum, stainless steel, brass, FRP, and iron) and dried at 23 ° C. for 7 days to obtain a dry film thickness. A 170 ⁇ m anticorrosion coating was formed. The surface of the test plate was cut with a cut knife with a cutter knife, and then salt water was sprayed on the test plate for 1000 hours using a salt spray test apparatus according to JISK5600-7-1. Then, the external appearance of the anticorrosion coating film was evaluated by observing the surface of the cut part. The evaluation was carried out based on the ASTM D-714-56A method for the blistering property around the cut of the crosscut, and the numerical value obtained by scoring according to the following criteria is shown in the “Appearance” column of Table 2.
  • Evaluation score is 10, 8F: Evaluation score of 8, 6F: Evaluation score 6, 8MD, 6M, and 4F: Evaluation score of 4, 6MD and 4M: Evaluation score of 3, 8D, 6D, 4MD, 2F, and 2M: 2 evaluation points, 4D and 2MD: 1 evaluation score, 2D: Evaluation score 0.
  • the width of the coating film peeled off when the knife was inserted into the cross cut portion was measured as a creep width (mm) and shown in the “creep width” column of Table 2. In addition, it has shown that it is excellent in corrosion resistance, so that creep width is short.
  • the anticorrosion coating obtained by the anticorrosion coating composition of the examples is excellent in adhesion and anticorrosion properties with the article to be coated and shop primer composed of a wide range of materials, and on the anticorrosion coating. It turns out that it is excellent also in the interlayer adhesion with the top coat film to paint.
  • the anticorrosion coating obtained by the anticorrosion coating composition of the comparative example may be inferior in adhesion and anticorrosion to an object to be coated composed of a non-ferrous material, and is coated on the anticorrosion coating. It can be seen that the adhesion with the top coat film may not be good.
  • the adhesion between the coating object, shop primer and top coat film is different because the anticorrosion coating composition of each example is a bisphenol type epoxy resin (a) and an alicyclic hydrocarbon resin modified epoxy. Since the two types of epoxy resins and the resin (b) are used in combination, the anticorrosive coating composition of each comparative example is a mixture of only one of these epoxy resins, This is probably because the effect of improving the anticorrosion property was not obtained.

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Abstract

Provided is an anti-corrosive coating composition which contains (a) a bisphenol epoxy resin, (b) an alicyclic hydrocarbon resin-modified epoxy resin, and (c) an amine-based curing agent. This anti-corrosive coating composition has excellent adhesion to a material to be coated and an overcoat film, and exhibits high anti-corrosion performance over a long period of time even in a harsh environment. The alicyclic hydrocarbon resin-modified epoxy resin (b) is preferably a dicyclopentadiene epoxy resin (b'), and the dicyclopentadiene epoxy resin (b') preferably has an epoxy equivalent of 245/g or more but 280/g or less and a softening point of 54˚C or more but 85˚C or less.

Description

防食塗料組成物および塗膜形成方法Anticorrosion coating composition and coating film forming method
　本発明は、防食塗料組成物に関し、より詳しくは、被塗物および上塗り塗膜との付着性に優れ、優れた防食性を有する防食塗料組成物に関する。また本発明は、当該防食塗料組成物を用いた塗膜形成方法に関する。 The present invention relates to an anticorrosion coating composition, and more particularly to an anticorrosion coating composition having excellent anticorrosion properties and excellent adhesion to an object to be coated and a top coat film. Moreover, this invention relates to the coating-film formation method using the said anticorrosion coating composition.
　船舶、橋梁、タンク、プラント等の構造物は、臨海部、河口部、水中などに設置され、極めて厳しい腐食環境下に置かれる場合が多い。かかる腐食環境に耐えるために、これらの構造物の表面には、防食塗装を施すのが一般的である。防食塗料としては、従来種々の配合組成が提案されている〔たとえば、特許文献１（特開平１０－２１１４６４号公報）、特許文献２（特開平１０－２５９３５１号公報）および特許文献３（特開平０８－０９２３４９号公報）〕。 Structures such as ships, bridges, tanks, and plants are often installed in coastal areas, estuaries, underwater, etc., and are often placed in extremely severe corrosive environments. In order to withstand such a corrosive environment, the surface of these structures is generally subjected to anticorrosion coating. Various anti-corrosion paints have been proposed in the past (for example, Patent Document 1 (Japanese Patent Laid-Open No. 10-211464), Patent Document 2 (Japanese Patent Laid-Open No. 10-259351) and Patent Document 3 (Japanese Patent Laid-Open No. Hei 10-214951). No. 08-092349).
特開平１０－２１１４６４号公報Japanese Patent Laid-Open No. 10-211464 特開平１０－２５９３５１号公報Japanese Patent Laid-Open No. 10-259351 特開平０８－０９２３４９号公報Japanese Patent Laid-Open No. 08-092349
　通常、防食塗料から形成された防食塗膜上には、被塗物またはその部位が置かれる環境に応じて、各種上塗り塗料を塗装して上塗り塗膜を形成する。このような複合塗膜が優れた防食性を発揮するために、防食塗膜は、被塗物表面への下地付着性および上塗り塗膜との層間付着性に優れる必要がある。 Usually, on the anticorrosion coating formed from the anticorrosion coating, various top coatings are applied to form an overcoating according to the environment in which the article to be coated or its part is placed. In order for such a composite coating film to exhibit excellent anticorrosion properties, the anticorrosion coating film needs to have excellent adhesion to the substrate surface and interlaminar adhesion to the top coating film.
　そこで本発明は、被塗物および上塗り塗膜の両方に対する付着性に優れ、過酷な環境下でも長期間にわたって高い防食性能を発揮する塗膜を形成することができる防食塗料組成物を提供することを目的とする。また、本発明の他の目的は、当該防食塗料組成物から形成される防食塗膜および当該防食塗膜を有する複合塗膜ならびにその形成方法を提供することである。 Therefore, the present invention provides an anticorrosion coating composition that is excellent in adhesion to both an object to be coated and a top coating film, and can form a coating film that exhibits high anticorrosion performance over a long period of time even in a harsh environment. With the goal. Moreover, the other objective of this invention is to provide the anticorrosion coating film formed from the said anticorrosion coating composition, the composite coating film which has the said anticorrosion coating film, and its formation method.
　本発明は、ビスフェノール型エポキシ樹脂（ａ）と、脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）と、アミン系硬化剤（ｃ）とを含む防食塗料組成物を提供する。 The present invention provides an anticorrosion coating composition comprising a bisphenol type epoxy resin (a), an alicyclic hydrocarbon resin-modified epoxy resin (b), and an amine curing agent (c).
　脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）は、ジシクロペンタジエン型エポキシ樹脂（ｂ’）であることが好ましい。 The alicyclic hydrocarbon resin-modified epoxy resin (b) is preferably a dicyclopentadiene type epoxy resin (b ′).
　ジシクロペンタジエン型エポキシ樹脂（ｂ’）は、そのエポキシ当量が２４５以上２８０以下であり、その軟化点が５４℃以上８５℃以下であることが好ましい。 The dicyclopentadiene type epoxy resin (b ′) preferably has an epoxy equivalent of 245 or more and 280 or less and a softening point of 54 ° C. or more and 85 ° C. or less.
　ビスフェノール型エポキシ樹脂（ａ）に対する脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）の固形分比率（ｂ）／（ａ）は、質量比で５／１００以上６５／１００以下であることが好ましい。 The solid content ratio (b) / (a) of the alicyclic hydrocarbon resin-modified epoxy resin (b) to the bisphenol-type epoxy resin (a) is preferably 5/100 or more and 65/100 or less by mass ratio. .
　ビスフェノール型エポキシ樹脂（ａ）と脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）との合計に対するアミン系硬化剤（ｃ）の固形分比率（ｃ）／｛（ａ）＋（ｂ）｝は、質量比で１５／１００以上５０／１００以下であることが好ましい。 The solid content ratio (c) / {(a) + (b)} of the amine curing agent (c) with respect to the total of the bisphenol type epoxy resin (a) and the alicyclic hydrocarbon resin-modified epoxy resin (b) is The mass ratio is preferably 15/100 or more and 50/100 or less.
　アミン系硬化剤（ｃ）は、ダイマー酸変性アミン系硬化剤（ｃ’）であることが好ましい。 The amine curing agent (c) is preferably a dimer acid-modified amine curing agent (c ′).
　本発明の防食塗料組成物はシランカップリング剤（ｄ）をさらに含むことができる。シランカップリング剤（ｄ）の固形分含有量は、防食塗料組成物の固形分中０．３質量％以上３質量％以下であることが好ましい。 The anticorrosion coating composition of the present invention can further contain a silane coupling agent (d). The solid content of the silane coupling agent (d) is preferably 0.3% by mass or more and 3% by mass or less in the solid content of the anticorrosive coating composition.
　また本発明は、上記の防食塗料組成物を被塗物に塗装することにより防食塗膜を形成するステップと、少なくとも一部の防食塗膜上に上塗り塗膜を形成するステップとを含む、塗膜形成方法を提供する。被塗物の好適な例は船舶である。この場合、本発明の塗膜形成方法は、船舶の船底部、プロペラ部、水線部、外舷部、甲板部、上部構造部、ホールド部、およびバラストタンク部に防食塗料組成物を塗装することにより防食塗膜を形成するステップと、少なくとも船底部および水線部の防食塗膜上に防汚塗料組成物を塗装することにより防汚塗膜を形成するステップと、外舷部、甲板部、上部構造部、ホールド部、およびバラストタンク部に形成された防食塗膜上に、エポキシ樹脂系塗料、塩化ゴム樹脂系塗料、塩化ビニル樹脂系塗料、アルキッド樹脂系塗料、シリコーンアルキッド樹脂系塗料、アクリル樹脂系塗料、ウレタン樹脂系塗料、フッ素樹脂系塗料、ポリエステル樹脂系塗料、シリコーン樹脂系塗料、およびエポキシアクリル樹脂系塗料からなる群より選択された少なくとも１種の上塗り塗料を塗装することにより、上塗り塗膜を形成するステップとを含むことができる。 The present invention also includes a step of forming an anticorrosion coating film by applying the above-mentioned anticorrosion coating composition to an object to be coated, and a step of forming an overcoat coating film on at least a part of the anticorrosion coating film. A film forming method is provided. A suitable example of the object to be coated is a ship. In this case, the coating film forming method of the present invention applies the anticorrosion coating composition to the ship bottom, propeller, water line, outer shell, deck, upper structure, hold, and ballast tank. A step of forming an anti-fouling coating film, a step of forming an anti-fouling coating composition by coating the anti-fouling coating composition on at least the bottom and water line anti-corrosion coatings, an outer shell part, a deck part On the anti-corrosion coating formed on the superstructure part, hold part and ballast tank part, epoxy resin paint, chlorinated rubber resin paint, vinyl chloride resin paint, alkyd resin paint, silicone alkyd resin paint, Selected from the group consisting of acrylic resin paints, urethane resin paints, fluororesin paints, polyester resin paints, silicone resin paints, and epoxy acrylic resin paints Even without by painting one top coating may include forming a top coating film.
　本発明の防食塗料組成物は、被塗物および上塗り塗膜との付着性に優れ、過酷な環境下でも長期間にわたって高い防食性能を発揮する防食塗膜を形成することができる。 The anticorrosive coating composition of the present invention is excellent in adhesion to an object to be coated and a top coat film, and can form an anticorrosion coating film that exhibits high anticorrosion performance over a long period of time even in a harsh environment.
　＜防食塗料組成物＞
　本発明の防食塗料組成物は、ビスフェノール型エポキシ樹脂（ａ）と、脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）と、アミン系硬化剤（ｃ）とを含むことを特徴とする。以下、本発明の防食塗料組成物に含有される各成分を説明する。 <Anti-corrosion paint composition>
The anticorrosive coating composition of the present invention comprises a bisphenol type epoxy resin (a), an alicyclic hydrocarbon resin-modified epoxy resin (b), and an amine-based curing agent (c). Hereinafter, each component contained in the anticorrosion coating composition of the present invention will be described.
　［ビスフェノール型エポキシ樹脂（ａ）］
　本発明の防食塗料組成物に用いられるビスフェノール型エポキシ樹脂（ａ）は、一般的なビスフェノール型エポキシ樹脂であることができ、ビスフェノールＡ型であってもビスフェノールＦ型であってもよい。 [Bisphenol type epoxy resin (a)]
The bisphenol type epoxy resin (a) used in the anticorrosive coating composition of the present invention can be a general bisphenol type epoxy resin, and may be a bisphenol A type or a bisphenol F type.
　本発明で用いることができるビスフェノール型エポキシ樹脂の市販品の例を挙げれば、たとえば、いずれも商品名で、エピコート♯８２８（ビスフェノールＡ型液状エポキシ樹脂、エポキシ当量１８４～１９４、分子量約３８０、油化シェル社製）；エピコート♯８３４－９０Ｘ（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量２３０～２７０、分子量約４７０、油化シェル社製）；エピコート♯１００１（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量４５０～５００、分子量約９００、油化シェル社製）；エピコート♯１００４（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量８７５～９７５、分子量約１６００、油化シェル社製）；エピコート♯１００７（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量１７５０～２２００、分子量約２９００、油化シェル社製）；エピコート♯８０７（ビスフェノールＦ型液状エポキシ樹脂、エポキシ当量１６０～１７５、分子量約３３０、油化シェル社製）；ｊＥＲ１００１－７０Ｘ（ビスフェノールＡ型エポキシ樹脂、エポキシ当量４５０～５００、分子量約９００、ジャパンエポキシレジン株式会社製）；ｊＥＲ８３４－９０Ｘ（ビスフェノールＡ型エポキシ樹脂、エポキシ当量２３０～２７０、分子量約４７０、ジャパンエポキシレジン株式会社製）等である。本発明に用いられるビスフェノール型エポキシ樹脂は、上記のようなビスフェノール型エポキシ樹脂に限定されるものではなく、一般に市販されているその他のビスフェノール型エポキシ樹脂等も使用することができる。 Examples of commercial products of bisphenol type epoxy resins that can be used in the present invention include, for example, Epicoat # 828 (bisphenol A type liquid epoxy resin, epoxy equivalent of 184 to 194, molecular weight of about 380, oil Epicoat # 834-90X (bisphenol A type solid epoxy resin, epoxy equivalent 230-270, molecular weight about 470, manufactured by Yuka Shell Co.); Epicoat # 1001 (bisphenol A type solid epoxy resin, epoxy equivalent 450) Epicoat # 1004 (bisphenol A type solid epoxy resin, epoxy equivalent 875 to 975, molecular weight about 1600, made by Yuka Shell Co.); Epicoat # 1007 (bisphenol A type solid) Epoxy resin, epoxy equivalent 1 50-2200, molecular weight of about 2900, manufactured by Yuka Shell); Epicoat # 807 (bisphenol F type liquid epoxy resin, epoxy equivalent of 160-175, molecular weight of about 330, manufactured by Yuka Shell); jER1001-70X (bisphenol A type) Epoxy resin, epoxy equivalent 450-500, molecular weight about 900, manufactured by Japan Epoxy Resins Co., Ltd.); jER834-90X (bisphenol A type epoxy resin, epoxy equivalent 230-270, molecular weight about 470, manufactured by Japan Epoxy Resins Co., Ltd.), etc. is there. The bisphenol type epoxy resin used in the present invention is not limited to the bisphenol type epoxy resin as described above, and other commercially available bisphenol type epoxy resins and the like can also be used.
　ビスフェノール型エポキシ樹脂（ａ）は、他の成分の粘度などに応じて適当な粘度のものを選択することができ、また、その形状は固形であっても液状であってもよい。たとえば、防食塗料組成物の粘度を高める場合には固形のビスフェノール型エポキシ樹脂を用い、粘度を低下させるためには、液状のビスフェノール型エポキシ樹脂を用いることが好ましい。 As the bisphenol type epoxy resin (a), one having an appropriate viscosity can be selected according to the viscosity of other components, and the shape thereof may be solid or liquid. For example, it is preferable to use a solid bisphenol-type epoxy resin when increasing the viscosity of the anticorrosive coating composition, and to use a liquid bisphenol-type epoxy resin to reduce the viscosity.
　ビスフェノール型エポキシ樹脂（ａ）は、そのエポキシ当量が１００以上３０００以下であることが好ましく、より好ましくは１５０以上１０００以下である。１００未満であると、架橋密度が高くなることにより防食塗膜の可とう性が低下する場合がある。一方、３０００を超えると、硬化性に劣ったり（十分な架橋密度が得られなかったり）、防食塗膜の強靱性に劣ったりする場合がある。 The epoxy equivalent of the bisphenol type epoxy resin (a) is preferably 100 or more and 3000 or less, more preferably 150 or more and 1000 or less. If it is less than 100, the flexibility of the anticorrosion coating film may be lowered due to an increase in the crosslinking density. On the other hand, when it exceeds 3000, curability may be inferior (sufficient crosslinking density may not be obtained) or the toughness of the anticorrosive coating film may be inferior.
　ビスフェノール型エポキシ樹脂（ａ）は、数平均分子量が２００以上５０００以下のものが好ましく、より好ましくは３００以上２０００以下である。２００未満であると塗膜物性に劣る場合があり、５０００を超えると塗装に適切な粘度に調整するために、多量の溶剤を添加する必要が生じるなど、塗装作業性に劣る場合がある。ここでの数平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ：Gel Permeation Chromatography）により測定されるポリスチレン換算値である。 The number average molecular weight of the bisphenol type epoxy resin (a) is preferably 200 or more and 5000 or less, more preferably 300 or more and 2000 or less. If it is less than 200, the physical properties of the coating film may be inferior, and if it exceeds 5000, the workability may be inferior, such as the need to add a large amount of solvent in order to adjust the viscosity to an appropriate level for coating. The number average molecular weight here is a polystyrene equivalent value measured by gel permeation chromatography (GPC: Gel Permeation Chromatography).
　ビスフェノール型エポキシ樹脂は、１種のみを単独で用いてもよいし、２種以上を併用してもよい。 Bisphenol type epoxy resin may be used alone or in combination of two or more.
　［脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）］
　本発明の防食塗料組成物に用いられる脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）は、少なくとも一部に下記一般式（１）で表されるノルボルネン骨格（ｍは１～２０の整数）の構成単位を有する変性エポキシ樹脂であることが好ましい。下記一般式（１）で示される構成単位を含む脂環族系炭化水素樹脂変性エポキシ樹脂を防食塗料組成物に配合することにより、被塗物および上塗り塗膜との付着性が向上し、さらに塗膜の耐水性が向上する。その結果、防食性能を高めることができる。 [Aliphatic hydrocarbon-modified epoxy resin (b)]
The alicyclic hydrocarbon resin-modified epoxy resin (b) used in the anticorrosion coating composition of the present invention is at least partially a norbornene skeleton represented by the following general formula (1) (m is an integer of 1 to 20) A modified epoxy resin having a structural unit of By adding an alicyclic hydrocarbon resin-modified epoxy resin containing a structural unit represented by the following general formula (1) to the anticorrosion coating composition, adhesion to the coating object and the top coating film is improved, The water resistance of the coating is improved. As a result, anticorrosion performance can be improved.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　上記一般式（１）において、ｍは好ましくは１以上１０以下の整数である。
　一般式（１）で表される構成単位の中でも特に好ましい構成単位として、たとえば下記一般式（２）で表されるジシクロペンタジエン由来の構造単位を挙げることができる。ジシクロペンタジエン由来の構造単位は、吸湿性が低くかつ軟化点が高い。このため、ジシクロペンタジエン由来の構成単位を含むことにより、脂環族系炭化水素樹脂変性エポキシ樹脂の吸湿性を低下させるとともに、適度に軟化点を高めることができ、もって優れた塗膜の防食性能を保持しつつ、塗膜強度を高めることができる。 In the general formula (1), m is preferably an integer of 1 or more and 10 or less.
Among the structural units represented by the general formula (1), particularly preferred structural units include structural units derived from dicyclopentadiene represented by the following general formula (2). The structural unit derived from dicyclopentadiene has low hygroscopicity and high softening point. For this reason, by including a structural unit derived from dicyclopentadiene, the hygroscopicity of the alicyclic hydrocarbon resin-modified epoxy resin can be reduced, and the softening point can be appropriately increased, thereby providing excellent anticorrosion of the coating film. The coating film strength can be increased while maintaining the performance.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一般式（２）で表されるジシクロペンタジエン由来の構成単位を含む、ジシクロペンタジエン型エポキシ樹脂（ｂ’）の市販品の例を挙げれば、たとえば、いずれも商品名で、エピクロンＨＰ７２００Ｌ（エポキシ当量２４５～２５０、軟化点５４～５８、ＤＩＣ株式会社製）；エピクロンＨＰ７２００（エポキシ当量２５５～２６０、軟化点５９～６３、ＤＩＣ株式会社製）；エピクロンＨＰ７２００Ｈ（エポキシ当量２７５～２８０、軟化点８０～８５、ＤＩＣ株式会社製）；エピクロンＨＰ７２００ＨＨ（エポキシ当量２７５～２８０、軟化点８７～９２℃、ＤＩＣ株式会社製）；ＸＤ－１０００－Ｌ（エポキシ当量２４０～２５５、軟化点６０～７０℃、日本化薬株式会社製）；ＸＤ－１０００－２Ｌ（エポキシ当量２３５～２５０、軟化点５３～６３℃、日本化薬株式会社製）；Ｔａｃｔｉｘ５５６（エポキシ当量２１５～２３５、軟化点７９℃、Ｈｕｎｔｓｍａｎ　Ｉｎｃ社製）などである。 If the example of the commercial item of the dicyclopentadiene type epoxy resin (b ') containing the structural unit derived from the dicyclopentadiene represented by General formula (2) is given, for example, all are a brand name, Epicron HP7200L (epoxy) Equicron 245-250, softening point 54-58, manufactured by DIC Corporation); Epicron HP7200 (epoxy equivalent 255-260, softening point 59-63, manufactured by DIC Corporation); Epicron HP7200H (epoxy equivalent 275-280, softening point 80) -85, manufactured by DIC Corporation); Epicron HP7200HH (epoxy equivalent 275-280, softening point 87-92 ° C, manufactured by DIC Corporation); XD-1000-L (epoxy equivalent 240-255, softening point 60-70 ° C, Nippon Kayaku Co., Ltd.); XD-1000-2L (epoxy equivalent 235-25) , Softening point 53 ~ 63 ° C., manufactured by Nippon Kayaku Co., Ltd.); Tactix556 (epoxy equivalent 215-235, softening point 79 ° C., manufactured by Huntsman Inc Co., Ltd.) and the like.
　これらジシクロペンタジエン型エポキシ樹脂（ｂ’）は、柔軟性を有するシクロペンタン環を有することにより塗膜に可とう性を付与するとともに、シクロペンタン環が高い疎水性を有することにより塗膜の吸湿性を低下させることができ、もって防食塗料の幅広い材料への付着性、および防食性を付与することができる。また、さらにジシクロペンタジエン型エポキシ樹脂（ｂ’）の分子量を低下させることにより、ビスフェノール型エポキシ樹脂（ａ）との相溶性を高めることもできる。上記ジシクロペンタジエン型エポキシ樹脂は、１種のみを単独で用いてもよいし、２種以上を併用してもよい。 These dicyclopentadiene type epoxy resins (b ′) give flexibility to the coating film by having a flexible cyclopentane ring and also absorb moisture of the coating film by having a high hydrophobicity of the cyclopentane ring. Therefore, the adhesion of the anticorrosion paint to a wide range of materials and the anticorrosion can be imparted. Further, by reducing the molecular weight of the dicyclopentadiene type epoxy resin (b ′), the compatibility with the bisphenol type epoxy resin (a) can be increased. The said dicyclopentadiene type epoxy resin may be used individually by 1 type, and may use 2 or more types together.
　ジシクロペンタジエン型エポキシ樹脂（ｂ’）は、そのエポキシ当量が２３０以上２８０以下であることが好ましく、２４５以上２８０以下であることがより好ましく、さらに好ましくは２５０以上２７５以下である。２３０未満であると、架橋密度が高くなることにより防食塗膜の可とう性が低下する傾向にある。一方、２８０を超えると、硬化性に劣ったり、防食塗膜の強靱性に劣ったりする場合がある。上記のエポキシ当量は、ＪＩＳ　Ｋ　７２３６に基づいて測定した値が採用される。 The epoxy equivalent of the dicyclopentadiene type epoxy resin (b ′) is preferably 230 or more and 280 or less, more preferably 245 or more and 280 or less, and further preferably 250 or more and 275 or less. If it is less than 230, the flexibility of the anticorrosive coating film tends to decrease due to the increase in the crosslinking density. On the other hand, if it exceeds 280, the curability may be inferior or the toughness of the anticorrosive coating film may be inferior. As the epoxy equivalent, a value measured based on JIS K 7236 is adopted.
　また、ジシクロペンタジエン型エポキシ樹脂（ｂ’）の軟化点は、５４℃以上８５℃以下であることが好ましい。５４℃未満であると、防食塗膜上にさらに上塗り塗膜を形成するときに、防食塗膜の耐熱性が十分でないことにより、防食塗膜の塑性変形が生じてしまう虞がある。８５℃を超えると、被塗物との付着性が低下したり、得られる塗膜の平滑性が低下したりする場合がある。上記のエポキシ樹脂の軟化点は、熱機械分析装置（製品名：ＴＭＡ（株式会社リガク製））を用いて測定を行なった値を採用するものとする。 The softening point of the dicyclopentadiene type epoxy resin (b ′) is preferably 54 ° C. or higher and 85 ° C. or lower. If the temperature is lower than 54 ° C., when the top coating film is further formed on the anticorrosion coating film, the anticorrosion coating film may not be sufficiently heat-resistant, so that the anticorrosion coating film may be plastically deformed. When it exceeds 85 degreeC, the adhesiveness with to-be-coated object may fall, or the smoothness of the coating film obtained may fall. The softening point of said epoxy resin shall employ | adopt the value measured using the thermomechanical analyzer (Product name: TMA (made by Rigaku Corporation)).
　本発明の防食塗料組成物は、ビスフェノール型エポキシ樹脂（ａ）とジシクロペンタジエン型エポキシ樹脂（ｂ’）のような脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）とを併用することにより、被塗物との付着性を向上させるとともに、防食塗膜の上に形成される上塗り塗膜との付着性をも向上させることができるものである。特にジシクロペンタジエン型エポキシ樹脂（ｂ’）は、ビスフェノール型エポキシ樹脂（ａ）との相溶性が良好であることに加え、ジシクロペンタジエン由来の構造単位が分岐構造を有するため、溶剤揮発後であって硬化する前の塗膜中で結晶化が生じにくく、しかも、硬化後の塗膜中でも上記の分岐構造により塗膜に柔軟性を付与することができる。これらが良好な付着性をもたらす主要因と考えられる。このように付着性を良好にすることにより、これまで付着性を確保するのが難しかった真鍮などの素材にも防食塗料組成物を適用することができる。 The anticorrosive coating composition of the present invention comprises a bisphenol type epoxy resin (a) and an alicyclic hydrocarbon resin-modified epoxy resin (b) such as a dicyclopentadiene type epoxy resin (b ′) in combination. While improving the adhesiveness with a to-be-coated object, the adhesiveness with the top coat film formed on an anticorrosion coating film can also be improved. In particular, the dicyclopentadiene type epoxy resin (b ′) has good compatibility with the bisphenol type epoxy resin (a), and the structural unit derived from dicyclopentadiene has a branched structure. Thus, crystallization is unlikely to occur in the coating film before curing, and flexibility can be imparted to the coating film by the above branched structure even in the coating film after curing. These are considered to be the main factors that give good adhesion. Thus, by making adhesiveness favorable, anticorrosion coating composition can be applied also to raw materials, such as brass, for which it was difficult to ensure adhesiveness until now.
　ビスフェノール型エポキシ樹脂（ａ）に対する脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）の固形分比率（ｂ）／（ａ）は、質量比で５／１００以上６５／１００以下であることが好ましく、より好ましくは１０／１００以上３５／１００以下である。５／１００未満であると、防食性能を十分に得られない場合があり、６５／１００を超えると、防食塗膜が硬くなりすぎて被塗物への付着力が低下し、防食塗膜が剥離しやすくなる。 The solid content ratio (b) / (a) of the alicyclic hydrocarbon resin-modified epoxy resin (b) to the bisphenol-type epoxy resin (a) is preferably 5/100 or more and 65/100 or less by mass ratio. More preferably, it is 10/100 or more and 35/100 or less. If it is less than 5/100, the anticorrosion performance may not be sufficiently obtained. If it exceeds 65/100, the anticorrosion coating film becomes too hard, and the adhesion to the article to be coated is reduced. Easy to peel.
　脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）は、エステル基、水酸基、およびカルボキシル基からなる群から選択される少なくとも１つの官能基を有する脂環族系炭化水素樹脂を含むことが好ましい。このような官能基を有する脂環族系炭化水素樹脂変性エポキシ樹脂を配合することにより、被塗物および上塗り塗膜との付着性をより向上させることができる場合がある。 The alicyclic hydrocarbon resin-modified epoxy resin (b) preferably contains an alicyclic hydrocarbon resin having at least one functional group selected from the group consisting of an ester group, a hydroxyl group, and a carboxyl group. By blending an alicyclic hydrocarbon resin-modified epoxy resin having such a functional group, the adhesion to the article to be coated and the top coat film may be further improved.
　［アミン系硬化剤（ｃ）］
　本発明の防食塗料組成物に含まれるエポキシ樹脂を硬化するための硬化剤としては、アミン系硬化剤（ｃ）を用いることが好ましい。アミン系硬化剤（ｃ）を上記の２種のエポキシ樹脂と併用することにより、得られる防食塗膜の可とう性を改善できるとともに、防食塗膜と被塗物、あるいは防食塗膜と上塗り塗膜との付着性をより向上させることができる。 [Amine curing agent (c)]
As the curing agent for curing the epoxy resin contained in the anticorrosion coating composition of the present invention, it is preferable to use an amine-based curing agent (c). By using the amine curing agent (c) in combination with the above two types of epoxy resins, the flexibility of the resulting anticorrosion coating film can be improved, and the anticorrosion coating film and the object to be coated, or the anticorrosion coating film and the top coating Adhesion with the film can be further improved.
　本発明の防食塗料組成物に用いるアミン系硬化剤（ｃ）は、常温での塗膜の硬化を進行させる役割、いわゆる硬化剤としての役割を担うものである。このようなアミン系硬化剤（ｃ）は、そのアミノ基が、ビスフェノール型エポキシ樹脂（ａ）および脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）中のエポキシ基に対して付加反応することにより、防食塗料組成物の硬化を開始させる。このような防食塗料組成物は、船舶の外板の塗装などの常温環境下で塗装される用途に好適に用いられる。 The amine-based curing agent (c) used in the anticorrosion coating composition of the present invention plays a role of causing the coating film to cure at room temperature, a so-called curing agent. Such an amine curing agent (c) has an amino group that undergoes an addition reaction with the epoxy group in the bisphenol type epoxy resin (a) and the alicyclic hydrocarbon resin-modified epoxy resin (b). Then, curing of the anticorrosion coating composition is started. Such an anticorrosion coating composition is suitably used for applications that are applied in a room temperature environment such as painting of the outer plate of a ship.
　アミン系硬化剤（ｃ）としては、公知のポリアミン化合物、およびその変性物などを挙げることができる。ポリアミン化合物としては、脂肪族ポリアミン、脂環式ポリアミン、芳香族ポリアミンなどを挙げることができる。ポリアミン化合物の変性物としては、ダイマー酸とポリアミン化合物とを反応させたダイマー酸変性アミン系硬化剤（ｃ’）などを挙げることができる。アミン系硬化剤は、１種のみを単独で用いてもよく、２種以上を併用してもよい。 Examples of the amine curing agent (c) include known polyamine compounds and modified products thereof. Examples of the polyamine compound include aliphatic polyamines, alicyclic polyamines, and aromatic polyamines. Examples of the modified product of the polyamine compound include a dimer acid-modified amine-based curing agent (c ′) obtained by reacting a dimer acid and a polyamine compound. Only one amine curing agent may be used alone, or two or more amine curing agents may be used in combination.
　本発明の防食塗料組成物に好適に用いられる脂肪族ポリアミンとしては、たとえばエチレンジアミン、ジエチレントリアミン、トリエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジエチルアミノプロピルアミン、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミンなどを挙げることができる。 Examples of the aliphatic polyamine suitably used in the anticorrosion coating composition of the present invention include ethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyoxypropylenediamine, polyoxypropylenetriamine and the like. Can be mentioned.
　本発明の防食塗料組成物に好適に用いられる脂環式ポリアミンとしては、たとえばメンセンジアミン、１，２－ジアミノシクロヘキサン、イソホロンジアミン、ピペラジン、Ｎ－アミノエチルピペラジン、１，３－ビス（アミノメチル）シクロヘキサン、メタキシレンジアミン、ビス（４－アミノ－３－メチルシクロヘキシル）メタン、ポリシクロヘキシルポリアミン、ノルボルネンジアミン、フルフリールアミン、テトラハイドロフルフリールアミン、メチレンビス（フランメタンアミン）、フェナルカミン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラオキサスピロ（５．５）ウンデカンアダクトなどを挙げることができる。 Examples of the alicyclic polyamine suitably used in the anticorrosive coating composition of the present invention include mensendiamine, 1,2-diaminocyclohexane, isophoronediamine, piperazine, N-aminoethylpiperazine, 1,3-bis (aminomethyl). ) Cyclohexane, metaxylenediamine, bis (4-amino-3-methylcyclohexyl) methane, polycyclohexylpolyamine, norbornenediamine, furfurylamine, tetrahydrofurfurylamine, methylenebis (furanmethaneamine), phenalkamine, 3,9- And bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane adduct.
　本発明の防食塗料組成物に好適に用いられる芳香族ポリアミンとしては、たとえばメタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジメチルジフェニルメタン、ジアミノジフェニルスルホン、ジアミノジエチルジメチルジフェニルメタン（たとえば、４，４’－ジアミノ－３，３’－ジエチル－５，５’－ジメチルジフェニルメタン）、ジエチルトルエンジアミン、３，５－ジメチルチオトルエンジアミンなどを挙げることができる。 Examples of the aromatic polyamine suitably used in the anticorrosive coating composition of the present invention include metaphenylenediamine, diaminodiphenylmethane, diaminodimethyldiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane (for example, 4,4′-diamino-3, 3′-diethyl-5,5′-dimethyldiphenylmethane), diethyltoluenediamine, 3,5-dimethylthiotoluenediamine, and the like.
　上記のように、アミン系硬化剤（ｃ）として、ダイマー酸とポリアミン化合物とを反応させた上記ダイマー酸変性アミン系硬化剤（ｃ’）を用いることも好ましい。ダイマー酸変性アミン系硬化剤（ｃ’）を用いることにより、非処理鋼材、ブラスト処理鋼材、酸処理鋼材等の鋼材に加え、亜鉛メッキ鋼材、ステンレス鋼材等の鋼材、アルミニウム（合金）材、銅（合金）材、真鍮材、繊維強化プラスティック（ＦＲＰ：Fiber Reinforced Plastics）等の幅広い性質を有する非鉄金属材等に対する防食塗膜の付着性をさらに向上させることができる。 As described above, it is also preferable to use the dimer acid-modified amine curing agent (c ′) obtained by reacting a dimer acid and a polyamine compound as the amine curing agent (c). By using dimer acid-modified amine curing agent (c '), in addition to steel materials such as non-treated steel materials, blast-treated steel materials, acid-treated steel materials, steel materials such as galvanized steel materials and stainless steel materials, aluminum (alloy) materials, copper The adhesion of the anticorrosion coating to non-ferrous metal materials having a wide range of properties such as (alloy) materials, brass materials, and fiber reinforced plastics (FRP) can be further improved.
　ダイマー酸変性アミン系硬化剤（ｃ’）の市販品の例を挙げれば、たとえば、いずれも商品名で、ラッカマイドＴＤ－９６６（ＤＩＣ株式会社製）、アンカマイド２０５０（エアープロダクツ社製）、アデカハードナーＥＨ－３５５（株式会社ＡＤＥＫＡ製）である。ダイマー酸変性アミン系硬化剤（ｃ’）以外のアミン系硬化剤（ｃ）の市販品の一例は、たとえばサンマイド３０８Ｄ－６５Ｔ（商品名、エアープロダクツ社製）である。 Examples of commercially available dimer acid-modified amine curing agents (c ′) include, for example, trade names of racamide TD-966 (manufactured by DIC Corporation), ancamide 2050 (manufactured by Air Products), Adeka Hardener. EH-355 (manufactured by ADEKA Corporation). An example of a commercially available amine-based curing agent (c) other than the dimer acid-modified amine-based curing agent (c ′) is, for example, sunmide 308D-65T (trade name, manufactured by Air Products).
　防食塗料組成物中に含まれるビスフェノール型エポキシ樹脂（ａ）および脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）中のエポキシ基の活性水素当量に対するアミン系硬化剤（ｃ）のアミノ基の活性水素当量は、０．５以上１．２以下であることが好ましい。０．５未満であるとアミン基が不足し、１．２を超えるとエポキシ基が不足し、いずれも架橋密度が減少することにより塗膜強度または防食性能（特に防食性能）が低下し得る。 Activity of amino group of amine curing agent (c) with respect to active hydrogen equivalent of epoxy group in bisphenol type epoxy resin (a) and alicyclic hydrocarbon resin-modified epoxy resin (b) contained in anticorrosion coating composition The hydrogen equivalent is preferably 0.5 or more and 1.2 or less. If it is less than 0.5, the amine group is insufficient, and if it exceeds 1.2, the epoxy group is insufficient. In any case, the coating density or anticorrosion performance (especially anticorrosion performance) can be reduced by reducing the crosslinking density.
　また、ビスフェノール型エポキシ樹脂（ａ）と脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）との合計に対するアミン系硬化剤（ｃ）の固形分比率（ｃ）／｛（ａ）＋（ｂ）｝は、１５／１００以上５０／１００以下であることが好ましく、より好ましくは２０／１００以上４０／１００以下である。１５／１００未満であるとアミン基が不足し、５０／１００を超えるとエポキシ基が不足し、いずれも架橋密度が減少することにより塗膜強度または防食性能（特に防食性能）が低下し得る。 The solid content ratio (c) / {(a) + (b) of the amine curing agent (c) with respect to the total of the bisphenol type epoxy resin (a) and the alicyclic hydrocarbon resin-modified epoxy resin (b) } Is preferably 15/100 or more and 50/100 or less, more preferably 20/100 or more and 40/100 or less. If it is less than 15/100, the amine group is insufficient, and if it exceeds 50/100, the epoxy group is insufficient. In any case, the coating density or anticorrosion performance (particularly anticorrosion performance) can be reduced by reducing the crosslinking density.
　本発明の防食塗料組成物は、ビスフェノール型エポキシ樹脂（ａ）および脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）を含有する成分と、アミン系硬化剤（ｃ）を含有する成分とからなる２液の塗料であることが好ましい。 The anticorrosion coating composition of the present invention comprises a component containing a bisphenol type epoxy resin (a) and an alicyclic hydrocarbon resin-modified epoxy resin (b), and a component containing an amine curing agent (c). A two-component paint is preferred.
　［シランカップリング剤（ｄ）］
　本発明の防食塗料組成物は、シランカップリング剤（ｄ）を含有することが好ましい。シランカップリング剤（ｄ）としては、エポキシ樹脂などの有機ポリマーに対して親和性を示す有機官能基と、顔料などの無機系材料に対して親和性を示す無機官能基とを併せ持つ化合物を用いることが好ましい。かかるシランカップリング剤（ｄ）を用いることにより、有機ポリマーと無機系材料とが接する界面の接着性等を向上させることができ、塗膜の付着性を高めることができる。 [Silane coupling agent (d)]
The anticorrosion coating composition of the present invention preferably contains a silane coupling agent (d). As the silane coupling agent (d), a compound having both an organic functional group having an affinity for an organic polymer such as an epoxy resin and an inorganic functional group having an affinity for an inorganic material such as a pigment is used. It is preferable. By using such a silane coupling agent (d), it is possible to improve the adhesiveness of the interface where the organic polymer and the inorganic material are in contact with each other, and to improve the adhesion of the coating film.
　有機ポリマーに対して親和性を示す有機官能基としては、官能基内に極性を有するものが好ましく、このような極性官能基としてアミノ基、カルボキシル基、水酸基、エポキシ基、およびグリシジル基を挙げることができ、好ましくはエポキシ基である。シランカップリング剤（ｄ）は、極性官能基を１種または２種以上を有することが好ましい。 As the organic functional group showing affinity for the organic polymer, those having polarity in the functional group are preferable, and examples of such a polar functional group include an amino group, a carboxyl group, a hydroxyl group, an epoxy group, and a glycidyl group. Preferably, it is an epoxy group. The silane coupling agent (d) preferably has one or more polar functional groups.
　エポキシ基を含有するシランカップリング剤としては、（３、４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、γ－グリシドキシプロピルトリエトキシシランなどを挙げることができる。 Examples of the silane coupling agent containing an epoxy group include (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxy. Examples thereof include propylmethyldiethoxysilane and γ-glycidoxypropyltriethoxysilane.
　エポキシ基含有シランカップリング剤の市販品の例を挙げれば、たとえば、いずれも商品名で、（３、４－エポキシシクロヘキシル）エチルトリメトキシシランであるＫＢＭ－３０３（信越化学工業株式会社製）；（３、４－エポキシシクロヘキシル）エチルトリメトキシシランであるＡ－１８６（日本ユニカー株式会社製）；γ－グリシドキシプロピルトリメトキシシランであるＫＢＭ－４０３（信越化学工業株式会社製）；γ－グリシドキシプロピルトリメトキシシランであるＡ－１８７（日本ユニカー株式会社製）；γ－グリシドキシプロピルメチルジメトキシシランであるＫＢＭ－４０２（信越化学工業株式会社製）；γ－グリシドキシプロピルメチルジメトキシシランであるＡＺ－６１３７（日本ユニカー株式会社製）；γ－グリシドキシプロピルトリエトキシシランであるＫＢＥ－４０３（信越化学工業株式会社製）などである。防食塗料組成物は、１種のシランカップリング剤を含有してもよいし、２種以上のシランカップリング剤を含有してもよい。 Examples of commercially available epoxy group-containing silane coupling agents include, for example, KBM-303 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a trade name of (3,4-epoxycyclohexyl) ethyltrimethoxysilane; (3,4-epoxycyclohexyl) ethyltrimethoxysilane A-186 (manufactured by Nippon Unicar Co., Ltd.); γ-glycidoxypropyltrimethoxysilane KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.); γ- A-187 glycidoxypropyltrimethoxysilane (manufactured by Nihon Unicar Co., Ltd.); KBM-402 γ-glycidoxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.); γ-glycidoxypropylmethyl AZ-6137 which is dimethoxysilane (manufactured by Nippon Unicar Co., Ltd.); KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is doxypropyltriethoxysilane. The anticorrosion coating composition may contain one type of silane coupling agent or two or more types of silane coupling agents.
　シランカップリング剤（ｄ）の固形分含有量は、防食塗料組成物の固形分中０．３質量％以上３質量％以下であることが好ましい。かかる割合でシランカップリング剤（ｃ）を含むことにより、得られる防食塗膜の被塗物および上塗り塗膜に対する付着性をより優れたものとすることができ、防食性能により優れた防食塗料組成物を得ることができる。 The solid content of the silane coupling agent (d) is preferably 0.3% by mass or more and 3% by mass or less in the solid content of the anticorrosion coating composition. By including the silane coupling agent (c) at such a ratio, the anticorrosion coating composition obtained can be more excellent in adhesion to the coating material and the top coating film of the anticorrosion coating film, and has excellent anticorrosion performance. You can get things.
　なお、「防食塗料組成物」の固形分の質量とは、ビスフェノール型エポキシ樹脂（ａ）と、脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）と、アミン系硬化剤（ｃ）と、シランカップリング剤（ｄ）との合計量（固形分の合計量）を意味し、後述するその他の添加剤以外の全ての成分の固形分の総和の質量を意味する。 In addition, the mass of the solid content of the “anticorrosive coating composition” refers to the bisphenol type epoxy resin (a), the alicyclic hydrocarbon resin-modified epoxy resin (b), the amine type curing agent (c), and the silane. It means the total amount (total amount of solid content) with the coupling agent (d), and means the total mass of the solid content of all components other than the other additives described later.
　［その他の添加剤］
　本発明の防食塗料組成物は、上記以外のその他の添加剤を含有していてもよい。その他の添加剤としては、たとえば、顔料、溶剤、水結合剤、ダレ止め剤、色分かれ防止剤、沈降防止剤、消泡剤、塗膜消耗調整剤、紫外線吸収剤、表面調整剤、粘度調整剤、レベリング剤、顔料分散剤などを挙げることができる。 [Other additives]
The anticorrosion coating composition of the present invention may contain other additives other than those described above. Other additives include, for example, pigments, solvents, water binders, anti-sagging agents, anti-color separation agents, anti-settling agents, antifoaming agents, coating film consumption regulators, UV absorbers, surface modifiers, and viscosity modifiers. Agents, leveling agents, pigment dispersants and the like.
　（１）顔料
　顔料としては、着色顔料、体質顔料、および防錆顔料からなる群より選択される１種以上を用いることができる。着色顔料としては、酸化チタン、黄色酸化鉄、カーボン、弁柄等の無機着色顔料、シアニンブルー、シアニングリーン等の有機着色顔料を挙げることができる。体質顔料としては、たとえば、硫酸バリウム、沈降性硫酸バリウム、クレー、タルク、マイカ、炭酸カルシウム、シリカ、ガラスフレーク等を挙げることができる。防錆顔料としては、モリブデン酸系、リン酸系、亜リン酸系、ホウ酸系、フェライト系の顔料等を挙げることができる。 (1) Pigment As the pigment, one or more selected from the group consisting of a color pigment, an extender pigment, and a rust preventive pigment can be used. Examples of the color pigment include inorganic color pigments such as titanium oxide, yellow iron oxide, carbon, and petal, and organic color pigments such as cyanine blue and cyanine green. Examples of extender pigments include barium sulfate, precipitated barium sulfate, clay, talc, mica, calcium carbonate, silica, and glass flakes. Examples of the rust preventive pigment include molybdic acid, phosphoric acid, phosphorous acid, boric acid, and ferrite pigments.
　（２）溶剤
　溶剤としては、たとえば、トルエン、キシレン、エチルベンゼン、シクロペンタン、オクタン、ヘプタン、シクロヘキサン、ホワイトスピリット等の炭化水素類；ジオキサン、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル等のエーテル類；酢酸ブチル、酢酸プロピル、酢酸ベンジル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等のエステル類；エチルイソブチルケトン、メチルイソブチルケトン等のケトン類；ｎ－ブタノール、プロピルアルコール等のアルコールなどを挙げることができる。溶剤は、１種のみを単独で用いてもよく、２種以上を併用してもよい。 (2) Solvent Examples of the solvent include hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane, white spirit; dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Ethers such as monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; ethyl isobutyl ketone , Ketones such as methyl isobutyl ketone; n-butanol, propyl Examples include alcohols such as alcohol. A solvent may be used individually by 1 type and may use 2 or more types together.
　（３）ダレ止め剤
　ダレ止め剤としては、有機粘土系Ａｌ、Ｃａ、Ｚｎのステアレート塩、レシチン塩、アルキルスルホン酸塩などの塩類、ポリエチレンワックス、アマイドワックス、水添ヒマシ油ワックス系、ポリアマイドワックス系、合成微粉シリカ、酸化ポリエチレン系ワックス、およびこれらの２種以上の混合物等を挙げることができる。ダレ止め剤の例を挙げれば、たとえば、いずれも商品名で、ディスパロン３０５（楠本化成株式会社製）、ディスパロン６９００－２０Ｘ（楠本化成株式会社製）、ディスパロン６６５０（楠本化成株式会社製）、ディスパロン６７００（楠本化成株式会社製）、ターレンＶＡ－７５０Ｂ（共栄社化学株式会社製）、ターレンＶＡ－７８０（共栄社化学株式会社製）等である。 (3) Anti-sagging agents Anti-sagging agents include organic clay Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonate salts, polyethylene wax, amide wax, hydrogenated castor oil wax, poly Examples thereof include amide waxes, synthetic fine silica, oxidized polyethylene waxes, and mixtures of two or more thereof. Examples of the anti-sagging agent are, for example, trade names of Disparon 305 (manufactured by Enomoto Kasei Co., Ltd.), Dispalon 6900-20X (manufactured by Enomoto Kasei Co., Ltd.), Disparon 6650 (manufactured by Enomoto Kasei Co., Ltd.), Disparon 6700 (manufactured by Enomoto Kasei Co., Ltd.), Talen VA-750B (manufactured by Kyoeisha Chemical Co., Ltd.), and Talen VA-780 (manufactured by Kyoeisha Chemical Co., Ltd.).
　＜被塗物＞
　本発明の防食塗料組成物を適用する被塗物としては、特に限定されるものではなく、少なくとも一部が水中（海水中）に配置される構造物の表面に特に好適に用いられる。このような被塗物としては、たとえば、船舶；港湾施設；オイルフェンス；発電所等の取水設備；冷却用導水管等の配管；橋梁；浮標；工業用水系施設；海底基地等の水中構造物などを挙げることができる。 <Coating material>
The article to which the anticorrosive coating composition of the present invention is applied is not particularly limited, and is particularly preferably used on the surface of a structure that is at least partially disposed in water (in seawater). Examples of such objects to be coated include ships; harbor facilities; oil fences; water intake facilities such as power plants; piping for cooling conduits; bridges; buoys; industrial water systems; And so on.
　被塗物の材質は、非処理鋼材、ブラスト処理鋼材、酸処理鋼材、亜鉛メッキ鋼材、ステンレス鋼材等の鋼材、アルミニウム（合金）材、銅（合金）材、真鍮材、繊維強化プラスティック（ＦＲＰ：Fiber Reinforced Plastics）等の非鉄金属材等を挙げることができる。これらの鋼材および非鉄金属材には溶接線があってもよい。特に、本発明の防食塗料組成物は真鍮材への付着性が優れることから、真鍮材で作られることが多い船舶用プロペラシャフト部に好適に用いられる。 The material of the coating is non-treated steel, blasted steel, acid-treated steel, galvanized steel, stainless steel, etc., aluminum (alloy) material, copper (alloy) material, brass material, fiber reinforced plastic (FRP: Nonferrous metal materials such as Fiber (Reinforced Plastics). These steel materials and non-ferrous metal materials may have weld lines. In particular, since the anticorrosion coating composition of the present invention has excellent adhesion to a brass material, it is suitably used for a marine propeller shaft portion that is often made of a brass material.
　＜防食塗膜＞
　本発明の防食塗料組成物を用いて形成された防食塗膜は、被塗物および上塗り塗膜との付着性に優れるため、過酷な環境下でも長期間にわたって高い防食性を発揮する。このような防食塗膜は、常法にしたがって、被塗物の表面に防食塗料組成物を塗布した後に、必要に応じて常温下または加熱下で溶剤を揮散除去することにより形成することができる。 <Anti-corrosion coating>
Since the anticorrosion coating film formed using the anticorrosion coating composition of the present invention is excellent in adhesion to the article to be coated and the top coating film, the anticorrosion coating film exhibits high anticorrosion properties over a long period of time even in a harsh environment. Such an anticorrosive coating film can be formed by volatilizing and removing the solvent at room temperature or under heating as necessary after applying the anticorrosion coating composition on the surface of the object to be coated according to a conventional method. .
　防食塗膜は、その膜厚が１０μｍ以上５００μｍ以下であることが好ましい。１０μｍ未満であると、薄すぎて均一に塗布することが困難であるだけでなく、良好な防食性を得ることができない。一方、５００μｍを超えると、塗膜が厚くなりすぎて塗料コストが高くなるだけでなく、塗膜の内部応力が大きくなりすぎて、塗膜が剥離する場合がある。 The anticorrosion coating film preferably has a film thickness of 10 μm or more and 500 μm or less. If it is less than 10 μm, not only is it too thin to apply uniformly, but also good corrosion resistance cannot be obtained. On the other hand, when the thickness exceeds 500 μm, not only the coating film becomes too thick and the coating cost becomes high, but also the internal stress of the coating film becomes too large and the coating film may be peeled off.
　防食塗料組成物の塗布方法は特に限定されず、たとえば、浸漬法、スプレー法、ハケ塗り、ローラー、静電塗装、電着塗装等の従来公知の方法であってよい。なお、被塗物の表面に防食塗料組成物を直接塗装してもよいし、必要に応じて被塗物の表面にショッププライマーを塗布した上で防食塗料組成物を塗装してもよい。 The coating method of the anticorrosion coating composition is not particularly limited, and may be a conventionally known method such as a dipping method, a spray method, brush coating, a roller, electrostatic coating, or electrodeposition coating. The anticorrosion coating composition may be directly applied to the surface of the object to be coated, or the anticorrosion coating composition may be applied after applying a shop primer to the surface of the object to be coated as necessary.
　ショッププライマーとしては、テトラアルコキシシリケートの加水分解初期縮合物と、酸性の溶剤分散型コロイダルシリカと、亜鉛粉末とを含有する防食塗料組成物；亜鉛よりも高い融点を有し、かつ鉄よりも卑なる電位を有する亜鉛合金粉末を含有する防食塗料組成物；結合剤および球状の亜鉛末を含有し、亜鉛末の光透過式沈降法による平均粒子径が５～１０μｍの範囲であって、かつ２μｍ以上の粒子が亜鉛末の全量の９５体積％以上であり、亜鉛末含有量が乾燥塗膜１００容量部当たり２０～６０容量部であり、かつ塗膜が６００℃以上の耐熱性を有する防食塗料組成物；またはこれらと類似の組成を有する防食塗料組成物を用いることが好ましい。 As a shop primer, an anti-corrosion coating composition containing a hydrolyzed initial condensation product of tetraalkoxysilicate, acidic solvent-dispersed colloidal silica, and zinc powder; a melting point higher than zinc and lower than iron An anticorrosion coating composition containing a zinc alloy powder having a potential of: a binder and spherical zinc powder, an average particle diameter of 5 to 10 μm by light transmission precipitation method of zinc powder, and 2 μm Anticorrosion paint in which the above particles are 95% by volume or more of the total amount of zinc powder, the zinc powder content is 20 to 60 parts by volume per 100 parts by volume of the dried coating film, and the coating film has heat resistance of 600 ° C. or more. It is preferable to use an anticorrosive coating composition having a composition; or a composition similar to these.
　＜上塗り塗膜＞
　上記のようにして塗装した防食塗膜上に、上塗り塗料を塗布することにより上塗り塗膜を形成することが好ましい。上塗り塗膜は、上述の防食塗料組成物の塗布方法と同様の方法を用いて形成することができる。上塗り塗料としては、エポキシ樹脂系塗料、塩化ゴム樹脂系塗料、塩化ビニル樹脂系塗料、アルキッド樹脂系塗料、シリコーンアルキッド樹脂系塗料、アクリル樹脂系塗料、ウレタン樹脂系塗料、フッ素樹脂系塗料、ポリエステル樹脂系塗料、シリコーン樹脂系塗料、エポキシアクリル樹脂系塗料、および各種防汚塗料等を用いることができる。 <Top coat film>
It is preferable to form a top coat by applying a top coat on the anticorrosion coat coated as described above. The top coat film can be formed using the same method as the coating method of the anticorrosive coating composition described above. Top coatings include epoxy resin paint, chlorinated rubber resin paint, vinyl chloride resin paint, alkyd resin paint, silicone alkyd resin paint, acrylic resin paint, urethane resin paint, fluororesin paint, polyester resin Paints, silicone resin paints, epoxy acrylic resin paints, and various antifouling paints can be used.
　＜複合塗膜の形成方法＞
　本発明の防食塗料組成物を用いて形成される複合塗膜は、防食塗料組成物を被塗物に塗装することにより防食塗膜を形成するステップと、少なくとも一部の防食塗膜上に上塗り塗膜を形成するステップとを含む方法により形成されることが好ましい。このようにして形成される複合塗膜は、防食塗膜と被塗物（下地）および上塗り塗膜との付着性が高く、過酷な環境下でも長期間にわたって高い防食性能を発揮する。また、本発明の防食塗料組成物によれば、防食塗膜と上塗り塗膜との間にバインダーコートを設けなくともよく、複合塗膜の形成を簡略化することができる。 <Method for forming composite coating film>
The composite coating film formed using the anticorrosion coating composition of the present invention comprises a step of forming an anticorrosion coating film by coating the anticorrosion coating composition on an object to be coated, and an overcoating on at least a part of the anticorrosion coating film. It is preferable to form by the method including the step of forming a coating film. The composite coating film formed in this way has high adhesion between the anticorrosion coating film, the object to be coated (base) and the top coating film, and exhibits high anticorrosion performance over a long period even in a harsh environment. Moreover, according to the anticorrosion coating composition of this invention, it is not necessary to provide a binder coat between an anticorrosion coating film and a top coat film, and formation of a composite coating film can be simplified.
　被塗物が船舶である場合、本発明の防食塗料組成物は、船舶の船底部、プロペラ部、水線部、外舷部、甲板部、上部構造部、ホールド部、およびバラストタンク部の全ての部位に適用することができるという利点がある。船舶の表面のうち、少なくとも船底部および水線部、好ましくはさらにプロペラ部においては、船舶の運航中に海水に接するため、その防食塗膜上に塗布される上塗り塗料として防汚塗料組成物を用い、防汚塗膜を形成することが好ましい。 When the article to be coated is a ship, the anticorrosive coating composition of the present invention is all of the ship bottom, propeller, water line, outer shell, deck, upper structure, hold, and ballast tank. There is an advantage that it can be applied to the region. Of the surface of the ship, at least the ship bottom and the water line part, and preferably the propeller part, contact with seawater during the operation of the ship, so that the antifouling paint composition is applied as a top coat applied on the anticorrosion coating. It is preferable to use and form an antifouling coating film.
　好ましい防汚塗料組成物の例を挙げれば、たとえば、防汚剤を含む加水分解型の防汚塗料組成物、シリコーンゴムを含有する非溶出型の塗料組成物などである。加水分解型の防汚塗料組成物としては、金属エステル基を含有する樹脂（金属は、Ｃｕ、Ｚｕなどの２価のもの、以下同様）、シリルアクリル基を含有する樹脂、金属エステル基およびシリルアクリル基を含有する樹脂、金属アクリル基およびシリコン含有基を含有する樹脂、シリルアクリル基およびシリコン含有基を含有する樹脂、または、金属アクリル基、シリルアクリル基およびシリコン含有基を含有する樹脂を含む加水分解型防汚塗料組成物を挙げることができる。 Examples of preferable antifouling paint compositions include, for example, hydrolyzable antifouling paint compositions containing an antifouling agent, and non-eluting paint compositions containing silicone rubber. Hydrolyzable antifouling paint compositions include resins containing metal ester groups (metals are divalent such as Cu and Zu, the same shall apply hereinafter), resins containing silylacryl groups, metal ester groups and silyl Including resin containing acrylic group, resin containing metal acrylic group and silicon-containing group, resin containing silylacryl group and silicon-containing group, or resin containing metal acrylic group, silylacryl group and silicon-containing group A hydrolyzable antifouling paint composition can be mentioned.
　また、非溶出型の防汚塗料としては、たとえば特許第４０４３５４０号に示されるような、縮合硬化型シリコーンゴム組成物と乾燥硬化型シリコーングラフトアクリル樹脂からなり、巨視的にはそれぞれの樹脂に分離していないが、微視的には同種成分が寄り集まって形成されたミクロなドメインがアトランダムに塗膜表面に現れており、多量成分が連続相を構成し、微量成分が分散相を構成するという海島構造を形成する防汚塗料組成物を用いてもよい。このように海水に接する部分に防汚塗膜を形成することにより、フジツボ、イガイ、藻類などの生物を付着しにくくし、もって船舶の運航効率を高めることができる。上記の各防汚塗料は、通常船舶防汚塗料に配合されるような成分、たとえば防汚剤、可塑剤、加水分解調整剤、顔料、溶剤、粘度調整剤、シリコーンオイル、その他の添加剤等を含んでいてもよい。 The non-eluting antifouling paint is composed of a condensation curable silicone rubber composition and a dry curable silicone graft acrylic resin as shown in, for example, Japanese Patent No. 4043540, and macroscopically separated into each resin. However, microscopically, microdomains formed by gathering similar components together appear at random on the surface of the coating, and a large amount of components constitutes a continuous phase and a minor amount of components constitutes a dispersed phase. An antifouling coating composition that forms a sea-island structure may be used. Thus, by forming the antifouling coating on the portion in contact with seawater, it is possible to make it difficult for organisms such as barnacles, mussels, and algae to adhere, thereby increasing the operational efficiency of the ship. Each of the above antifouling paints is a component that is usually blended in marine antifouling paints, such as antifouling agents, plasticizers, hydrolysis regulators, pigments, solvents, viscosity modifiers, silicone oils, other additives, etc. May be included.
　一方、船舶の表面のうち、外舷部、甲板部、および上部構造部は海水に接しないため、その表面の防食塗膜上には、ウレタン系、エポキシ系、アクリル系、および塩素化ポリオレフィン系からなる群より選択された少なくとも１種の上塗り塗料を塗布して上塗り塗膜を形成することができる。 On the other hand, out of the ship's surface, the outer brim part, the deck part, and the upper structure part do not come into contact with seawater, so on the anticorrosive coating on the surface, urethane, epoxy, acrylic, and chlorinated polyolefin The top coat film can be formed by applying at least one top coat selected from the group consisting of:
　＜膜厚管理＞
　本発明の防食塗料組成物は、塗料中の着色顔料の濃度を調整することにより、膜厚管理を容易に行なうことができる塗料とすることができる。すなわち、塗装中の塗膜と被塗物との色差の変化を目視で確認しながら防食塗料組成物の塗装を行なうことにより、防食塗膜が目標膜厚に達したかどうかを容易に判定することができる。なお、色差は塗膜の状態がウエットであろうと乾燥後であろうと変化しないので、塗装中の防食塗膜がウエットのうちに、被塗物またはプライマー層との色差の変化を目視により観察し、塗装中の防食塗膜が規定の膜厚に達したか否かを判定することができる。 <Film thickness control>
The anticorrosion coating composition of the present invention can be a coating that can easily manage the film thickness by adjusting the concentration of the color pigment in the coating. That is, it is easily determined whether or not the anticorrosion coating film has reached the target film thickness by coating the anticorrosion coating composition while visually confirming the change in color difference between the coating film being coated and the object to be coated. be able to. Since the color difference does not change whether the coating is wet or after drying, the change in color difference between the coating and the primer layer is visually observed while the anticorrosion coating during coating is wet. It can be determined whether or not the anticorrosion coating film being coated has reached a prescribed film thickness.
　このような膜厚管理が可能な防食塗料組成物は、特に船舶の外板を塗布する場合のように、大型構造物を塗布する場合に特に有効である。以下にこのように膜厚管理するための条件を詳述する。 Such an anticorrosion coating composition capable of controlling the film thickness is particularly effective when a large structure is applied, such as when an outer skin of a ship is applied. The conditions for controlling the film thickness will be described in detail below.
　防食塗料組成物の固形分に対して０．０１体積％以上３体積％以下の着色顔料を含み、かつ、下記条件：
　（１）防食塗料組成物と被塗物との色差が２０以上、
　（２）目標乾燥膜厚の塗膜と、目標乾燥膜厚の８０％未満の膜厚の塗膜との色差が２以上、
　（３）目標乾燥膜厚の塗膜と、目標乾燥膜厚の１２０％超の膜厚の塗膜との色差が１未満、
を満たすように、防食塗料組成物中の着色顔料の含有量を調整することが好ましい。これにより、防食塗膜の乾燥膜厚を簡単（典型的には目視で）かつ正確に目標値にコントロールできる。この場合、着色顔料として少なくとも酸化チタンを用いることが好ましい。なお、色差の測定はＳＭカラーコンピュータ〔型式：ＳＭ－７ＣＨ（スガ試験機株式会社製）〕等の色差計を使用し、一般に知られた方法で行なうことができる。 Including 0.01% by volume or more and 3% by volume or less of a color pigment based on the solid content of the anticorrosion coating composition, and the following conditions:
(1) The color difference between the anticorrosive coating composition and the article to be coated is 20 or more,
(2) The color difference between the coating film having the target dry film thickness and the coating film having a film thickness of less than 80% of the target dry film thickness is 2 or more,
(3) The color difference between the coating film having the target dry film thickness and the coating film having a film thickness exceeding 120% of the target dry film thickness is less than 1,
It is preferable to adjust the content of the color pigment in the anticorrosion coating composition so as to satisfy the above condition. Thereby, the dry film thickness of an anticorrosion coating film can be controlled to a target value easily (typically visually) and correctly. In this case, it is preferable to use at least titanium oxide as the coloring pigment. The color difference can be measured by a generally known method using a color difference meter such as an SM color computer [Model: SM-7CH (manufactured by Suga Test Instruments Co., Ltd.)].
　［被塗物との色差］
　防食塗料組成物と被塗物との色差は２０以上であることが好ましく、色差の変化を目視で確認しやすくするには、防食塗料組成物と被塗物との色差を３５以上とするのがより好ましい。防食塗料組成物と被塗物との色差が２０未満であると、防食塗料組成物の膜厚が目標膜厚に近づくにつれて、被塗物との色差を目視で判断しにくくなり、所望の膜厚よりも厚めに塗布してしまう傾向がある。 [Color difference from substrate]
The color difference between the anticorrosive coating composition and the object to be coated is preferably 20 or more. In order to make it easy to visually confirm the change in the color difference, the color difference between the anticorrosive coating composition and the object to be coated is set to 35 or more. Is more preferable. When the color difference between the anticorrosive coating composition and the object to be coated is less than 20, as the film thickness of the anticorrosive coating composition approaches the target film thickness, it becomes difficult to visually determine the color difference from the object to be coated, and a desired film There is a tendency to apply thicker than the thickness.
　防食塗料組成物の色相範囲は、マンセルの１００色相環上で被塗物の色相を０とし、これに対して左回りを０～＋５０、右回りを０～－５０で表示したときに、その色相範囲が－２０～－５０、または＋５０～＋２０であるような補色に近い色相のものが好ましい。上下の層の色相が補色に近い関係であるほど色差が大きくなるので、上層の防食塗料組成物の色相範囲を－４０～－５０、または＋５０～＋４０に設定するのがより好ましい。 The hue range of the anticorrosive coating composition is that when the hue of the object to be coated is 0 on the Munsell's 100 hue ring and the counterclockwise display is 0 to +50 and the clockwise direction is 0 to -50. Those having a hue close to complementary colors such that the hue range is -20 to -50 or +50 to +20 are preferred. Since the color difference increases as the hues of the upper and lower layers are closer to complementary colors, the hue range of the upper anticorrosive coating composition is more preferably set to −40 to −50, or +50 to +40.
　［目標乾燥膜厚の８０％未満の膜厚の塗膜との色差］
　目標乾燥膜厚の塗膜と、目標乾燥膜厚の８０％未満の膜厚の塗膜との色差は２以上であることが好ましい。目標乾燥膜厚の８０％未満の膜厚の塗膜とは、塗装完了直前の塗膜であるが、その時点でも目標乾燥膜厚の塗膜の色調に対して２以上の色差を有しない場合、人の目には目標乾燥膜厚に達したものとして映る。このため、その部分の膜厚が目標乾燥膜厚よりも部分的に薄くなってしまう傾向がある。 [Color difference with coating film with film thickness of less than 80% of target dry film thickness]
The color difference between the coating film having the target dry film thickness and the coating film having a film thickness of less than 80% of the target dry film thickness is preferably 2 or more. A coating film having a film thickness of less than 80% of the target dry film thickness is a film immediately before the completion of coating, but even when there is no color difference of 2 or more with respect to the color tone of the film having the target dry film thickness It appears to the human eye as having reached the target dry film thickness. For this reason, there exists a tendency for the film thickness of the part to become partially thinner than a target dry film thickness.
　ただし、目標乾燥膜厚の塗膜と、目標乾燥膜厚の８０％未満の膜厚の塗膜との色差が大きすぎると、目標乾燥膜厚に達したか否かを判定しやすい反面、僅かな膜厚差でも塗膜の色むらが顕著になる傾向がある。このため色差の上限は１０であるのが好ましく、より好ましくは５である。 However, if the color difference between the coating film having the target dry film thickness and the coating film having a film thickness of less than 80% of the target dry film thickness is too large, it is easy to determine whether or not the target dry film thickness has been reached. Even with a difference in film thickness, uneven color of the coating film tends to be remarkable. For this reason, the upper limit of the color difference is preferably 10, and more preferably 5.
　［目標乾燥膜厚の１２０％超の膜厚の塗膜との色差］
　目標乾燥膜厚の１２０％超の膜厚の塗膜は、塗装完了直後の塗膜である。このため、目標乾燥膜厚の塗膜と目標乾燥膜厚の１２０％超の膜厚の塗膜との色差はできるだけ小さくすることが好ましく、１未満であることが好ましく、より好ましくは０．５未満である。色差が１以上であると、目標乾燥膜厚に達した塗膜の間でも色差が異なり、塗装後に色むらが顕著に表れる傾向がある。 [Color difference with coating film with film thickness exceeding 120% of target dry film thickness]
A coating film having a film thickness exceeding 120% of the target dry film thickness is a coating film immediately after the completion of coating. For this reason, the color difference between the coating film having the target dry film thickness and the coating film having a film thickness exceeding 120% of the target dry film thickness is preferably as small as possible, preferably less than 1, more preferably 0.5. Is less than. When the color difference is 1 or more, the color difference is different even between the coating films that have reached the target dry film thickness, and the color unevenness tends to appear remarkably after coating.
　なお、被塗物の上にプライマーを塗布し、そのプライマー層の上に防食塗料組成物を塗布する場合、防食塗料組成物が満たすべき色差の上述の条件（１）～（３）のうちの（１）は、下記の（１’）に読み替えられる。
（１’）防食塗料組成物とプライマーとの色差が２０以上。 In addition, when a primer is applied on an object to be coated and an anticorrosion coating composition is applied on the primer layer, the color difference to be satisfied by the anticorrosion coating composition among the above conditions (1) to (3) (1) can be read as (1 ') below.
(1 ′) The color difference between the anticorrosive coating composition and the primer is 20 or more.
　このような条件を満たすことにより、プライマー層を形成する場合にも、防食塗膜の乾燥膜厚を簡単（典型的には目視で）かつ正確に目標値にコントロールできる。 By satisfying such conditions, even when the primer layer is formed, the dry film thickness of the anticorrosion coating can be controlled easily (typically visually) to the target value accurately.
　以下、実施例および比較例を挙げて本発明をより詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
　＜実施例１＞
　ビスフェノール型エポキシ樹脂と、脂環族系炭化水素樹脂変性エポキシ樹脂と、溶剤（キシレンおよびイソブタノール）と、シランカップリング剤と、顔料と、添加剤とを表１に示す配合比で混合し、該組成物を高速ディスパーにて分散粒度が８０μｍ以下となるように分散することにより、エポキシ液（Ａ液）を調製した。次に、アミン系硬化剤と、溶剤とを表１に示す比率で混合することによりアミン硬化剤（Ｂ液）を調製した。上記のエポキシ液（Ａ液）とアミン硬化剤（Ｂ液）とを混合することにより、本実施例の防食塗料組成物を得た。エポキシ液（Ａ液）とアミン硬化剤（Ｂ液）とを混合するタイミングは、塗装する１５分前とした。なお、上記の分散粒度は、グラインドゲージを用いて日本工業規格（ＪＩＳ　Ｋ　５６００　２－５）に従い測定した値である。表１に示される数値の単位は質量部である。 <Example 1>
A bisphenol-type epoxy resin, an alicyclic hydrocarbon resin-modified epoxy resin, a solvent (xylene and isobutanol), a silane coupling agent, a pigment, and an additive are mixed at a blending ratio shown in Table 1, An epoxy liquid (liquid A) was prepared by dispersing the composition with a high-speed disperser so that the dispersed particle size became 80 μm or less. Next, an amine curing agent (Liquid B) was prepared by mixing an amine curing agent and a solvent at a ratio shown in Table 1. The anticorrosive coating composition of the present Example was obtained by mixing the epoxy liquid (A liquid) and the amine curing agent (B liquid). The timing for mixing the epoxy liquid (A liquid) and the amine curing agent (B liquid) was 15 minutes before coating. The above dispersed particle size is a value measured according to Japanese Industrial Standard (JIS K 5600 2-5) using a grind gauge. The unit of numerical values shown in Table 1 is parts by mass.
　＜実施例２～１６、比較例１～３＞
　表１に示されるような比率で各成分を配合したこと以外は、実施例１と同様の手順で各成分を混合することにより、実施例２～１６および比較例１～３の防食塗料組成物を得た。 <Examples 2 to 16, Comparative Examples 1 to 3>
The anticorrosive coating compositions of Examples 2 to 16 and Comparative Examples 1 to 3 were mixed by mixing the respective components in the same procedure as in Example 1 except that the respective components were blended in the ratio as shown in Table 1. Got.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　〔１〕ビスフェノール型エポキシ樹脂（ａ－１）：ｊＥＲ１００１－７０Ｘ（ジャパンエポキシレジン株式会社製）、
　〔２〕ビスフェノール型エポキシ樹脂（ａ－２）：ｊＥＲ８３４－９０Ｘ（ジャパンエポキシレジン株式会社製）、
　〔３〕脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ－１）：ＥＰＩＣＬＯＮ　ＨＰ－７２００Ｈ（ＤＩＣ株式会社）、エポキシ当量２７０以上２８０以下、軟化点８０℃以上８５℃以下、
　〔４〕脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ－２）：ＥＰＩＣＬＯＮ　ＨＰ－７２００ＨＨ（ＤＩＣ株式会社）、エポキシ当量２７０以上２８０以下、軟化点８７℃以上９２℃以下、
　〔５〕脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ－３）：Ｔａｃｔｉｘ　５５６（ハンツマン社製）、エポキシ当量２１５以上２３５以下、軟化点７９℃以下、
　〔６〕アミン系硬化剤（ｃ）：サンマイド３０８Ｄ－６５Ｔ（エアープロダクツ株式会社製）、固形分濃度６５％、
　〔７〕ダイマー酸変性アミン系硬化剤（ｃ－１）：アデカハードナーＥＨ－３５５（ＡＤＥＫＡ株式会社製）、固形分濃度６８％、
　〔８〕シランカップリング剤（ｄ）：ＫＢＭ－４０３（信越化学株式会社製）、
　〔９〕酸化チタン：チタンＣＲ－５０（石原産業株式会社製）、
　〔１０〕タルク：タルクＳＰ－４２（丸尾カルシウム株式会社製）、
　〔１１〕ダレ止め剤：ディスパロン６９００－２０Ｘ（楠本化成株式会社製）。 [1] Bisphenol type epoxy resin (a-1): jER1001-70X (manufactured by Japan Epoxy Resin Co., Ltd.)
[2] Bisphenol type epoxy resin (a-2): jER834-90X (manufactured by Japan Epoxy Resin Co., Ltd.)
[3] Alicyclic hydrocarbon resin-modified epoxy resin (b-1): EPICLON HP-7200H (DIC Corporation), epoxy equivalent of 270 to 280, softening point of 80 ° C to 85 ° C,
[4] Alicyclic hydrocarbon resin-modified epoxy resin (b-2): EPICLON HP-7200HH (DIC Corporation), epoxy equivalent of 270 to 280, softening point of 87 ° C to 92 ° C,
[5] Alicyclic hydrocarbon resin-modified epoxy resin (b-3): Tactix 556 (manufactured by Huntsman), epoxy equivalent of 215 to 235, softening point of 79 ° C. or less,
[6] Amine-based curing agent (c): sunmide 308D-65T (manufactured by Air Products), solid content concentration 65%,
[7] Dimer acid-modified amine curing agent (c-1): Adeka Hardener EH-355 (manufactured by ADEKA Corporation), solid content concentration 68%,
[8] Silane coupling agent (d): KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)
[9] Titanium oxide: Titanium CR-50 (Ishihara Sangyo Co., Ltd.),
[10] Talc: Talc SP-42 (manufactured by Maruo Calcium Co., Ltd.)
[11] Sag stopper: Disparon 6900-20X (manufactured by Enomoto Kasei Co., Ltd.).
　＜付着性の評価＞
　各実施例および各比較例の防食塗料組成物を塗布して形成される防食塗膜について、被塗物との付着性、ショッププライマーとの付着性、および上塗り塗膜との付着性を評価した。各評価方法は以下の通りである。 <Evaluation of adhesion>
The anticorrosion coating film formed by applying the anticorrosion coating composition of each Example and each Comparative Example was evaluated for adhesion to an object to be coated, adhesion to a shop primer, and adhesion to a top coating film. . Each evaluation method is as follows.
　（１）被塗物との付着性（碁盤目付着試験）
　被塗物と防食塗膜との付着性を以下のようにして評価した。まず、被塗物として、亜鉛メッキ鋼板、アルミニウム、ステンレス、真鍮、ＦＲＰ、鉄の６種類の材料からなる下地板を、各実施例および各比較例についてそれぞれ２枚ずつ用意した。そして、それぞれの下地板に対し、各実施例および各比較例の防食塗料組成物を塗布した後に、２３℃で７日間乾燥させることにより、乾燥膜厚が１７０μｍの防食塗膜を形成し試験板とした。 (1) Adhesion with the object to be coated (cross-cut adhesion test)
The adhesion between the object to be coated and the anticorrosive coating film was evaluated as follows. First, two base plates made of galvanized steel sheet, aluminum, stainless steel, brass, FRP, and iron were prepared for each of the examples and the comparative examples. And after apply | coating the anticorrosion coating composition of each Example and each comparative example with respect to each base plate, by drying for 7 days at 23 degreeC, the anticorrosion coating film whose dry film thickness is 170 micrometers is formed, and a test board It was.
　次に、防食塗膜を形成した２枚のうちの一方の試験板に対してＪＩＳ　Ｋ　５６００．５．６に準拠して碁盤目付着試験を行なった。具体的には、試験板に対し、３ｍｍの隙間間隔で下地板に達するまでナイフで切り込みを入れることにより２５マスの碁盤目を作成し、当該碁盤目上に粘着テープを貼り合わせて、塗膜面に対して４５°の角度を成す方向に粘着テープを引き剥がした。その後、防食塗膜が剥離したマス目をカウントし、全マス目に対する剥離したマス目の割合（％）を算出した。下記の基準で評点化した数値を表２の「被塗物への付着性」における「初期」の欄に示す。 Next, a cross-cut adhesion test was performed on one of the two test plates on which the anticorrosion coating film was formed in accordance with JIS K5600.55.6. Specifically, a 25 square grid is created by cutting a test plate with a knife until it reaches the base plate with a gap of 3 mm, and an adhesive tape is bonded onto the grid, The adhesive tape was peeled off in a direction forming an angle of 45 ° with respect to the surface. Thereafter, the squares from which the anticorrosive coating film was peeled were counted, and the ratio (%) of the squares to which all the squares were peeled was calculated. The numerical values scored according to the following criteria are shown in the “Initial” column of “Adhesiveness to substrate” in Table 2.
　評価点数５：碁盤のマス目の剥離率０％、
　評価点数４：碁盤のマス目の剥離率０％超５％以下、
　評価点数３：碁盤のマス目の剥離率５％超１５％以下、
　評価点数２：碁盤のマス目の剥離率１５％超２５％以下、
　評価点数１：碁盤のマス目の剥離率２５％超。 Evaluation score 5: 0% peeling rate of grid on grid
Evaluation score 4: More than 0% and 5% or less peeling rate of grid of grid
Evaluation score 3: Stripping rate of grid on grid is over 5% and 15% or less,
Evaluation score 2: Stripping rate of grid on grid is more than 15% and less than 25%,
Evaluation score 1: More than 25% peeling rate of grid on grid.
　また、もう一つの試験板について、４０℃の水中に３ヶ月浸漬した後に、上記と同様の条件で碁盤目付着試験を行なった。上記と同様の基準で評点化した数値を表２の「被塗物への付着性」における「４０℃温水浸漬後」の欄に示す。 Further, another test plate was immersed in water at 40 ° C. for 3 months, and then a cross-cut adhesion test was performed under the same conditions as described above. The numerical values scored according to the same criteria as above are shown in the column “After 40 ° C. hot water immersion” in “Adhesion to substrate” in Table 2.
　（２）ショッププライマーとの付着性（碁盤目付着試験）
　ショッププライマーと防食塗膜との付着性を以下のようにして評価した。まず、下地板としてショットブラスト鋼板を、各実施例および各比較例についてそれぞれ２枚ずつ用意した。そして、この下地板表面に１５μｍの厚みのショッププライマー層を形成した。かかるショッププライマー層は、プライマー塗料〔製品名：ニッペセラモ（日本ペイントマリン株式会社製）〕を塗布した後に、塗板を１週間屋外で暴露することにより得られた塗膜である。 (2) Adhesion with shop primer (cross-cut adhesion test)
The adhesion between the shop primer and the anticorrosion coating was evaluated as follows. First, two shot blast steel plates were prepared for each example and each comparative example as a base plate. A shop primer layer having a thickness of 15 μm was formed on the surface of the base plate. The shop primer layer is a coating film obtained by applying a primer paint [product name: NIPPE CERAMO (manufactured by Nippon Paint Marine Co., Ltd.)] and then exposing the coated plate outdoors for one week.
　このようにして形成したショッププライマー層上に、さらに各実施例および各比較例に示される防食塗料組成物を塗布することにより防食塗膜を形成し試験板とした。次に、防食塗膜を形成した２枚のうちの一方の試験板に対して上記と同様の条件で碁盤目付着試験を行なうことにより、防食塗膜とショッププライマーとの付着性を評価した。上記と同様の基準で評点化した数値を表２の「ショッププライマー付着性」における「初期」の欄に示す。 An anticorrosion coating film was formed on the shop primer layer thus formed by applying the anticorrosion coating composition shown in each of the examples and comparative examples to obtain a test plate. Next, the adhesion between the anticorrosion coating film and the shop primer was evaluated by conducting a cross-cut adhesion test on one of the two test plates on which the anticorrosion coating film was formed under the same conditions as described above. The numerical values scored according to the same criteria as described above are shown in the “Initial” column of “Shop primer adhesion” in Table 2.
　また、もう一つの試験板について、４０℃の水中に３ヶ月浸漬した後に、上記と同様の条件で碁盤目付着試験を行なった。上記と同様の基準で評点化した数値を表２の「ショッププライマー付着性」における「４０℃温水浸漬後」の欄に示す。 Further, another test plate was immersed in water at 40 ° C. for 3 months, and then a cross-cut adhesion test was performed under the same conditions as described above. The numerical values scored according to the same criteria as described above are shown in the column “After immersion at 40 ° C.” in “Shop primer adhesion” in Table 2.
　（３）上塗り塗膜の付着性（碁盤目付着試験）
　防食塗膜と上塗り塗膜との付着性を以下のようにして評価した。まず、被塗物としてサンドブラスト鋼板を用意し、この鋼板表面に３０μｍ±１０μｍの乾燥膜厚となるように各実施例および各比較例の防食塗料組成物をスプレー塗装した。その後、２３℃で７日間乾燥させることにより、防食塗膜を形成した。 (3) Adhesion of top coat film (cross-cut adhesion test)
The adhesion between the anticorrosion coating and the top coating was evaluated as follows. First, a sandblasted steel sheet was prepared as an object to be coated, and the anticorrosive coating compositions of the examples and comparative examples were spray-coated on the surface of the steel sheet so as to have a dry film thickness of 30 μm ± 10 μm. Then, the anticorrosion coating film was formed by making it dry at 23 degreeC for 7 days.
　かかる防食塗膜上に、エポキシ樹脂系塗料、ウレタン樹脂系塗料、またはアクリル樹脂系塗料を塗布し、２３℃で７日間乾燥させることにより、それぞれ乾燥膜厚が４０μｍ±１０μｍの厚みの上塗り塗膜を形成した。また、防食塗膜上に加水分解型防汚塗料を塗布し、２３℃で７日間乾燥させることにより、乾燥膜厚が８０μｍ±１０μｍの上塗り塗膜を形成した。また、非溶出型シリコーン系防汚塗料については、防食塗膜上に乾燥膜厚が１００μｍ±１０μｍとなるようにシリコーン系中塗り塗料を塗装し、２４時間経過した後に、乾燥膜厚が１５０μｍ±１０μｍとなるようにシリコーン系上塗り塗料を塗装し、２３℃で７日間乾燥させることにより上塗り塗膜を形成した。そして、このようにして得られた上塗り塗膜に対し、上記と同様の条件で碁盤目付着試験を行なった。表２の「上塗り付着性」の欄に、上記と同様の基準で各塗料の付着性を評点化した値を示す。 An epoxy resin paint, urethane resin paint, or acrylic resin paint is applied onto the anticorrosion coating film and dried at 23 ° C. for 7 days, so that the dry coating film has a thickness of 40 μm ± 10 μm. Formed. Further, a hydrolyzable antifouling paint was applied on the anticorrosive paint film and dried at 23 ° C. for 7 days to form an overcoat paint film having a dry film thickness of 80 μm ± 10 μm. For the non-eluting silicone antifouling paint, a silicone intermediate coating is applied on the anticorrosion coating so that the dry film thickness is 100 μm ± 10 μm, and after 24 hours, the dry film thickness is 150 μm ± A silicone-based top coating was applied to a thickness of 10 μm and dried at 23 ° C. for 7 days to form a top coating film. Then, a cross-cut adhesion test was performed on the top coat film thus obtained under the same conditions as described above. In the column of “Topcoat Adhesiveness” in Table 2, the values obtained by scoring the adhesiveness of each paint based on the same criteria as described above are shown.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　〔１〕エポキシ系塗料：製品名ニッペエポキシフィニッシュＭ（日本ペイントマリン株式会社製）、
　〔２〕ウレタン系塗料：製品名ポリウレマイティラックＭ（日本ペイントマリン株式会社製）、
　〔３〕アクリル系塗料：製品名ニッポンＡ－マリンフィニッシュ（日本ペイントマリン株式会社製）、
　〔４〕加水分解型防汚塗料：製品名ぷろぺら一番（日本ペイントマリン株式会社製）、
　〔５〕非溶出型シリコーン系防汚塗料：（中塗）製品名エコロシルク　タイコート（日本ペイントマリン株式会社製）、（上塗）製品名エコロシルク（日本ペイントマリン株式会社製）。 [1] Epoxy paint: Product name Nippe Epoxy Finish M (manufactured by Nippon Paint Marine Co., Ltd.),
[2] Urethane paint: Product name Polyuremite Rack M (manufactured by Nippon Paint Marine Co., Ltd.),
[3] Acrylic paint: Product name Nippon A-Marine Finish (manufactured by Nippon Paint Marine Co., Ltd.)
[4] Hydrolyzable antifouling paint: Product name Propera Ichiban (manufactured by Nippon Paint Marine Co., Ltd.)
[5] Non-eluting silicone antifouling paint: (intermediate coating) product name Ecorosilk Thai coat (manufactured by Nippon Paint Marine Co., Ltd.), (top coating) product name Ecorosilk (manufactured by Nippon Paint Marine Co., Ltd.).
　＜防食性の評価＞
　各実施例および各比較例の防食塗料組成物を試験板（亜鉛メッキ鋼板、アルミニウム、ステンレス、真鍮、ＦＲＰ、鉄の６種類）に塗布し、２３℃で７日間乾燥することにより乾燥膜厚が１７０μｍの防食塗膜をそれぞれ形成した。この試験板の表面に、カッターナイフでクロスカットの切り傷をつけた後、ＪＩＳＫ５６００－７－１に準拠した塩水噴霧試験装置を用いて、該試験板に対し塩水を１０００時間噴霧した。その後、その切り傷部分の表面を観察することにより、防食塗膜の外観を評価した。該評価は、クロスカットの切り傷周囲のフクレ性をＡＳＴＭ　Ｄ－７１４－５６Ａ法に基づいて行ない、下記の基準で評点化した数値を表２の「外観」の欄に示した。 <Evaluation of corrosion resistance>
The anticorrosion coating composition of each example and each comparative example was applied to a test plate (6 types of galvanized steel plate, aluminum, stainless steel, brass, FRP, and iron) and dried at 23 ° C. for 7 days to obtain a dry film thickness. A 170 μm anticorrosion coating was formed. The surface of the test plate was cut with a cut knife with a cutter knife, and then salt water was sprayed on the test plate for 1000 hours using a salt spray test apparatus according to JISK5600-7-1. Then, the external appearance of the anticorrosion coating film was evaluated by observing the surface of the cut part. The evaluation was carried out based on the ASTM D-714-56A method for the blistering property around the cut of the crosscut, and the numerical value obtained by scoring according to the following criteria is shown in the “Appearance” column of Table 2.
　フクレが発生していないもの　　　　　：評価点数１０、
　８Ｆ　　　　　　　　　　　　　　　　：評価点数８、
　６Ｆ　　　　　　　　　　　　　　　　：評価点数６、
　８ＭＤ、６Ｍ、および４Ｆ　　　　　　：評価点数４、
　６ＭＤおよび４Ｍ　　　　　　　　　　：評価点数３、
　８Ｄ、６Ｄ、４ＭＤ、２Ｆ、および２Ｍ：評価点数２、
　４Ｄおよび２ＭＤ　　　　　　　　　　：評価点数１、
　２Ｄ　　　　　　　　　　　　　　　　：評価点数０。 No blister has occurred: Evaluation score is 10,
8F: Evaluation score of 8,
6F: Evaluation score 6,
8MD, 6M, and 4F: Evaluation score of 4,
6MD and 4M: Evaluation score of 3,
8D, 6D, 4MD, 2F, and 2M: 2 evaluation points,
4D and 2MD: 1 evaluation score,
2D: Evaluation score 0.
　また、クロスカット部にナイフを差し込んだときに剥がれた塗膜の幅をクリープ幅（ｍｍ）として測定し、表２の「クリープ幅」の欄に示した。なお、クリープ幅が短いほど、防食性に優れていることを示している。 Further, the width of the coating film peeled off when the knife was inserted into the cross cut portion was measured as a creep width (mm) and shown in the “creep width” column of Table 2. In addition, it has shown that it is excellent in corrosion resistance, so that creep width is short.
　また、ショットブラスト鋼板に対し、プライマー塗料〔製品名：ニッペセラモ（日本ペイントマリン株式会社製）〕を塗布した後に、塗板を１週間屋外で暴露することにより、１５μｍの厚みのショッププライマー層を形成した。かかるショッププライマー層上に、各実施例および各比較例に示される防食塗料組成物を塗布することにより防食塗膜を形成し、上記と同様の方法により防食塗膜の防食性を評価した。該評価の結果を、表２の「ショッププライマー防食性」の欄に示した。 In addition, after applying a primer paint [product name: NIPPE CERAMO (manufactured by Nippon Paint Marine Co., Ltd.)] to the shot blasted steel sheet, a shop primer layer having a thickness of 15 μm was formed by exposing the coated plate outdoors for one week. . An anticorrosion coating film was formed on the shop primer layer by applying the anticorrosion coating composition shown in each Example and each Comparative Example, and the anticorrosion property of the anticorrosion coating film was evaluated by the same method as described above. The results of the evaluation are shown in the column of “Shop primer anticorrosion” in Table 2.
　表２の結果から、実施例の防食塗料組成物により得られる防食塗膜は、幅広い素材で構成される被塗物およびショッププライマーとの付着性および防食性に優れるとともに、該防食塗膜上に塗装する上塗り塗膜との層間付着性にも優れることがわかる。これに対し、比較例の防食塗料組成物により得られる防食塗膜は、非鉄素材で構成される被塗物への付着性および防食性に劣る場合があり、また、該防食塗膜上に塗装する上塗り塗膜との付着性も良好でない場合があることがわかる。 From the results in Table 2, the anticorrosion coating obtained by the anticorrosion coating composition of the examples is excellent in adhesion and anticorrosion properties with the article to be coated and shop primer composed of a wide range of materials, and on the anticorrosion coating. It turns out that it is excellent also in the interlayer adhesion with the top coat film to paint. On the other hand, the anticorrosion coating obtained by the anticorrosion coating composition of the comparative example may be inferior in adhesion and anticorrosion to an object to be coated composed of a non-ferrous material, and is coated on the anticorrosion coating. It can be seen that the adhesion with the top coat film may not be good.
　このように被塗物、ショッププライマーおよび上塗り塗膜との付着性が異なるのは、各実施例の防食塗料組成物が、ビスフェノール型エポキシ樹脂（ａ）と、脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）との２種のエポキシ樹脂を併用しているのに対し、各比較例の防食塗料組成物が、これらのエポキシ樹脂のいずれか一方のみを配合したものであるため、付着力および防食性の向上効果が得られなかったためであると考えられる。 In this way, the adhesion between the coating object, shop primer and top coat film is different because the anticorrosion coating composition of each example is a bisphenol type epoxy resin (a) and an alicyclic hydrocarbon resin modified epoxy. Since the two types of epoxy resins and the resin (b) are used in combination, the anticorrosive coating composition of each comparative example is a mixture of only one of these epoxy resins, This is probably because the effect of improving the anticorrosion property was not obtained.

Claims (9)

  1. 　ビスフェノール型エポキシ樹脂（ａ）と、
    　脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）と、
    　アミン系硬化剤（ｃ）と、
    を含む防食塗料組成物。     A bisphenol-type epoxy resin (a);
    An alicyclic hydrocarbon resin-modified epoxy resin (b);
    An amine-based curing agent (c);
    An anticorrosive paint composition comprising:
  2. 　前記脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）は、ジシクロペンタジエン型エポキシ樹脂（ｂ’）である、請求項１に記載の防食塗料組成物。 The anti-corrosion coating composition according to claim 1, wherein the alicyclic hydrocarbon resin-modified epoxy resin (b) is a dicyclopentadiene type epoxy resin (b ').
  3. 　前記ジシクロペンタジエン型エポキシ樹脂（ｂ’）は、そのエポキシ当量が２４５以上２８０以下であり、その軟化点が５４℃以上８５℃以下である、請求項２に記載の防食塗料組成物。 The anticorrosive coating composition according to claim 2, wherein the dicyclopentadiene type epoxy resin (b ') has an epoxy equivalent of 245 or more and 280 or less and a softening point of 54 ° C or more and 85 ° C or less.
  4. 　前記ビスフェノール型エポキシ樹脂（ａ）に対する前記脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）の固形分比率（ｂ）／（ａ）は、質量比で５／１００以上６５／１００以下である、請求項１に記載の防食塗料組成物。 The solid content ratio (b) / (a) of the alicyclic hydrocarbon resin-modified epoxy resin (b) to the bisphenol-type epoxy resin (a) is 5/100 or more and 65/100 or less by mass ratio. The anticorrosion coating composition according to claim 1.
  5. 　前記ビスフェノール型エポキシ樹脂（ａ）と前記脂環族系炭化水素樹脂変性エポキシ樹脂（ｂ）との合計に対する前記アミン系硬化剤（ｃ）の固形分比率（ｃ）／｛（ａ）＋（ｂ）｝は、質量比で１５／１００以上５０／１００以下である、請求項１に記載の防食塗料組成物。 Solid content ratio (c) / {(a) + (b) of the amine curing agent (c) with respect to the sum of the bisphenol type epoxy resin (a) and the alicyclic hydrocarbon resin-modified epoxy resin (b) )} Is the anticorrosion coating composition according to claim 1, which has a mass ratio of 15/100 or more and 50/100 or less.
  6. 　前記アミン系硬化剤（ｃ）は、ダイマー酸変性アミン系硬化剤（ｃ’）である、請求項１に記載の防食塗料組成物。 The anticorrosion coating composition according to claim 1, wherein the amine curing agent (c) is a dimer acid-modified amine curing agent (c ').
  7. 　シランカップリング剤（ｄ）をさらに含み、
    　前記シランカップリング剤（ｄ）の固形分含有量は、前記防食塗料組成物の固形分中０．３質量％以上３質量％以下である、請求項１に記載の防食塗料組成物。     Further comprising a silane coupling agent (d),
    The anticorrosion coating composition according to claim 1, wherein a solid content of the silane coupling agent (d) is 0.3% by mass or more and 3% by mass or less in the solid content of the anticorrosion coating composition.
  8. 　請求項１に記載の防食塗料組成物を被塗物に塗装することにより防食塗膜を形成するステップと、
    　少なくとも一部の前記防食塗膜上に上塗り塗膜を形成するステップとを含む、塗膜形成方法。     Forming an anticorrosion coating by applying the anticorrosion coating composition according to claim 1 to an object to be coated;
    Forming a top coating film on at least a part of the anticorrosion coating film.
  9. 　前記防食塗料組成物を船舶の船底部、プロペラ部、水線部、外舷部、甲板部、上部構造部、ホールド部、およびバラストタンク部に塗装することにより防食塗膜を形成するステップと、
    　少なくとも前記船底部および前記水線部の前記防食塗膜上に防汚塗料組成物を塗装することにより防汚塗膜を形成するステップと、
    　前記外舷部、前記甲板部、前記上部構造部、前記ホールド部、および前記バラストタンク部に形成された前記防食塗膜上に、エポキシ樹脂系塗料、塩化ゴム樹脂系塗料、塩化ビニル樹脂系塗料、アルキッド樹脂系塗料、シリコーンアルキッド樹脂系塗料、アクリル樹脂系塗料、ウレタン樹脂系塗料、フッ素樹脂系塗料、ポリエステル樹脂系塗料、シリコーン樹脂系塗料、およびエポキシアクリル樹脂系塗料からなる群より選択された少なくとも１種の上塗り塗料を塗装することにより、上塗り塗膜を形成するステップとを含む、請求項８に記載の塗膜形成方法。     Forming the anticorrosion coating by coating the anticorrosion coating composition on the bottom of the ship, the propeller, the water line, the outer shell, the deck, the upper structure, the hold, and the ballast tank;
    Forming an antifouling coating by coating an antifouling coating composition on at least the anticorrosion coating on the ship bottom and the water line, and
    An epoxy resin paint, a chlorinated rubber resin paint, and a vinyl chloride resin paint are formed on the anticorrosion coating formed on the outer casing, the deck, the upper structure, the hold, and the ballast tank. , Alkyd resin paint, silicone alkyd resin paint, acrylic resin paint, urethane resin paint, fluororesin paint, polyester resin paint, silicone resin paint, and epoxy acrylic resin paint The method for forming a coating film according to claim 8, further comprising: forming a top coating film by applying at least one type of top coating composition.
PCT/JP2011/060663 2011-05-09 2011-05-09 Anti-corrosive coating composition and method for forming coating film WO2012153382A1 (en)

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CN109943158A (en) * 2019-03-06 2019-06-28 湖南工程学院 Screw-thread steel antirust solution, preparation method and screw-thread steel surface treatment method
CN112143357A (en) * 2020-09-15 2020-12-29 湖北吉人水性汽车涂料有限公司 Bi-component heavy-duty anticorrosive paint based on modified chlorinated rubber
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