WO2017085970A1 - Composition de peinture anticorrosion et procédé de formation de film de revêtement séché - Google Patents

Composition de peinture anticorrosion et procédé de formation de film de revêtement séché Download PDF

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Publication number
WO2017085970A1
WO2017085970A1 PCT/JP2016/073321 JP2016073321W WO2017085970A1 WO 2017085970 A1 WO2017085970 A1 WO 2017085970A1 JP 2016073321 W JP2016073321 W JP 2016073321W WO 2017085970 A1 WO2017085970 A1 WO 2017085970A1
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Prior art keywords
coating
paint
colored
agent
mass
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PCT/JP2016/073321
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English (en)
Japanese (ja)
Inventor
弘一 鍛治
圧広 山下
亮 江原
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日本ペイントマリン株式会社
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Priority claimed from JP2015224760A external-priority patent/JP5933095B1/ja
Application filed by 日本ペイントマリン株式会社 filed Critical 日本ペイントマリン株式会社
Priority to BR112017019517-8A priority Critical patent/BR112017019517B1/pt
Priority to KR1020177024081A priority patent/KR101915924B1/ko
Priority to CN201680021791.3A priority patent/CN107960091B/zh
Priority to DE112016001076.1T priority patent/DE112016001076B4/de
Priority to SG11201706608WA priority patent/SG11201706608WA/en
Publication of WO2017085970A1 publication Critical patent/WO2017085970A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B59/00—Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
    • B63B59/04—Preventing hull fouling
    • 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
    • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B59/00—Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
    • C08K5/107—Esters; Ether-esters of monocarboxylic acids with phenols with polyphenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings

Definitions

  • the present invention relates to epoxy-based anticorrosion paint compositions.
  • the present invention also relates to an anticorrosion coating film formed from the anticorrosion coating composition, and a coated article such as a ship, a marine structure or the like provided with the anticorrosion coating film.
  • the present invention relates to a method for forming a coating film, and a paint used therefor.
  • marine structures such as bridges, tanks, and plants are coated with an anticorrosive coating on their surfaces for the purpose of imparting corrosion resistance to severe corrosive environments.
  • Antifouling coatings are often applied over anticorrosion coatings.
  • film thickness control of the dried coating is important, and if the formed dried coating does not have a sufficient thickness, the characteristics to be imparted are also given. It tends to be inadequate.
  • Patent Document 1 a non-tar epoxy resin heavy duty anti-corrosion coating is applied to the bottom of a ship, or the bottom and water line of a ship, It is described to apply a hydrolyzable antifouling paint.
  • JP-A-10-259351 Patent Document 2 discloses a non-tar epoxy resin coating composition containing a curing agent comprising a bisphenol epoxy resin, a vinyl chloride copolymer and a polyamide or a modified product thereof for heavy corrosion protection. It is described that a paint is applied to a ship or the like, and a non-organic tin-based hydrolyzable antifouling paint is applied thereon.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2002-167548 describes that an epoxy coating composition containing a specific urethane amine compound is applied as an anticorrosion coating to a ship or the like, and a top coating is applied thereon. It is done.
  • film thickness control of a coating film is not an operation which can be made easy.
  • a wet gauge is used to confirm in advance whether or not the dry film thickness to be targeted (that can obtain a desired physical property sufficiently) can be obtained in advance.
  • a method of measuring and confirming the dry film thickness based on the measurement of the coating film thickness in the middle of the work, ie in the wet state (before drying), ii) In order to confirm whether or not the film thickness of the dried coating film has reached the target film thickness, there is a method of measuring the film thickness of the dried coating film directly using an electromagnetic film thickness meter etc. .
  • film thickness control has been practically difficult particularly in the following cases.
  • coating thickness is likely to be uneven on surfaces where coating is not easy, it is often the case that the film thickness of a coating film formed on such surfaces is measured using a wet gauge, an electromagnetic film thickness meter, etc. It is difficult and complicated.
  • one-time coating means that a series of operation until it coats a paint and performs a drying process is one time, therefore, the coating film formed by one-time coating means a paint. A coating film formed by performing a drying process once after applying one or more times is repeated.
  • JP-A-10-216621 Patent Document 4
  • JP-A-2002-066445 Patent Document 5
  • a paint a paint called "film thickness judgment paint” can be used which enables a coating operator to visually observe the change in color difference of the wet coating during coating to determine whether or not the specified film thickness is reached. Forming a coating film is disclosed.
  • JP 10-211464 A Japanese Patent Application Laid-Open No. 10-259351 JP 2002-167548 A Japanese Patent Application Laid-Open No. 10-216621 Japanese Patent Laid-Open No. 2002-066445
  • Still another object of the present invention is to be able to form a coating having good adhesion to the top coating even if the time until the top coating is applied is long, in other words, it is good for the top coating
  • the coating-film formation method which can form the dry coating film which has a predetermined
  • the present invention provides the anticorrosion paint composition as shown below, as well as coatings, ships and marine structures.
  • the content of the vinyl chloride copolymer (C) is 5 to 50 parts by mass with respect to 100 parts by mass of the bisphenol A epoxy resin (A)
  • a two-component anticorrosion paint composition comprising a first agent and a second agent,
  • the first agent contains the bisphenol A epoxy resin (A) and the vinyl chloride copolymer (C)
  • the anticorrosive coating composition according to any one of [1] to [6], wherein the second agent contains the amine curing agent (B) and the monoepoxide compound (D).
  • the present invention also provides a method for forming a dried coating film and a colored anticorrosive paint as described below.
  • a method for forming a dried coating on the surface of a substrate Following process: [1] a step of setting a dry film thickness T; [2] A two-component colored anticorrosion paint comprising a first agent and a second agent, wherein the following conditions (a) to (i): (A) The coating film formed from the colored anticorrosion paint having the dry coating thickness T conceals the surface of the object to be coated, (B) A color difference ⁇ E1 between a coating formed of the colored anticorrosive paint having the dry coating thickness T and a coating formed of the colored anticorrosive coating having a dry coating thickness of 0.7 T is 2.
  • (C) containing a color pigment (D) Bisphenol A type epoxy resin (A), amine curing agent (B), vinyl chloride copolymer (C), monoepoxide compound (D), (meth) acrylate compound (E) and Contains (E)
  • the content of the vinyl chloride copolymer (C) is 5 to 50 parts by mass with respect to 100 parts by mass of the bisphenol A epoxy resin (A).
  • the content of the monoepoxide compound (D) is 2 to 50 parts by mass with respect to 100 parts by mass of the amine curing agent (B).
  • the first agent contains the bisphenol A epoxy resin (A) and the vinyl chloride copolymer (C)
  • the second agent contains the amine curing agent (B) and the monoepoxide compound (D)
  • the (meth) acrylate compound (E) contains a vinyl ester resin, Preparing or preparing a colored anticorrosive paint satisfying [3] a step of applying the colored anticorrosive paint to the surface until the surface of the object to be coated is covered with a coating film made of the colored anticorrosive paint; [4] A step of drying the coated film obtained by the step of the above [3] to obtain a dried coated film, Method, including.
  • the colored anticorrosive paint has the following condition (j): (J) The color difference ⁇ E2 between the coating formed of the colored anticorrosive paint having the dry coating thickness T and the coating formed of the colored anticorrosive coating having a dry coating thickness of 1.3 T is less than 1 Is The method according to [1], further satisfying
  • the colored anticorrosive paint has the following condition (k): (K) A color difference ⁇ E3 between the coating film formed of the colored anticorrosion paint having the dry coating thickness T and the surface of the object is 20 or more.
  • the colored anticorrosive paint further has a scale-like pigment (G) having an average particle size of 10 to 300 ⁇ m, an average thickness of 2 to 50 ⁇ m, and an aspect ratio of 2 to 100 defined as an average particle size / average thickness.
  • G scale-like pigment
  • scaly pigment (G) is at least one pigment selected from the group consisting of talc, mica and glass flakes.
  • a two-component colored anticorrosion paint comprising a first agent and a second agent, which is used to form a dried coating having a dry coating thickness T on the surface of a coated article,
  • (B) A color difference ⁇ E1 between a coating formed of the colored anticorrosive paint having the dry coating thickness T and a coating formed of the colored anticorrosive coating having a dry coating thickness of 0.7 T is 2.
  • (C) containing a color pigment (D) Bisphenol A type epoxy resin (A), amine curing agent (B), vinyl chloride copolymer (C), monoepoxide compound (D), (meth) acrylate compound (E) and Contains (E)
  • the content of the vinyl chloride copolymer (C) is 5 to 50 parts by mass with respect to 100 parts by mass of the bisphenol A epoxy resin (A).
  • the content of the monoepoxide compound (D) is 2 to 50 parts by mass with respect to 100 parts by mass of the amine curing agent (B).
  • the first agent contains the bisphenol A epoxy resin (A) and the vinyl chloride copolymer (C)
  • the second agent contains the amine curing agent (B) and the monoepoxide compound (D)
  • the (meth) acrylate compound (E) contains a vinyl ester resin, Meet the colored anticorrosive paint.
  • a scaly pigment (G) having an average particle size of 10 to 300 ⁇ m, an average thickness of 2 to 50 ⁇ m, and an aspect ratio of 2 to 100 defined as an average particle size / average thickness is further contained,
  • the present invention it is possible to form a coating having good adhesion to the top-coating even if the time until the top-coating is applied is long, in other words, good adhesion to the top-coating It is possible to provide an anticorrosion paint composition capable of extending the time until the top coat is applied while maintaining it, a coating film formed using the same, and a ship and a marine structure provided with the coating film. .
  • the anticorrosion paint composition of the present invention is useful, for example, as an anticorrosion paint to be applied to marine structures such as bridges, tanks, and plants, as well as ships.
  • a coating film having good adhesion to the top coat film can be formed even if the time until the top coat coating is applied is long, in other words, good adhesion to the top coat film
  • the epoxy-based anticorrosion paint composition which can extend the time until the topcoat paint is applied while maintaining It is possible to provide a coating film forming method capable of forming a dried coating film having a predetermined film thickness, and a colored anticorrosive paint used therefor.
  • the colored anticorrosion paint of the present invention is useful, for example, as an anticorrosion paint to be applied to marine structures such as bridges, tanks, and plants as well as ships.
  • FIG. 13 is a graph showing the relationship between the dry film thickness ( ⁇ m) and ⁇ E shown in Tables 4 to 6 (Example 13 and Comparative Example 2).
  • FIG. 16 is a graph showing the relationship between the dry film thickness ( ⁇ m) and ⁇ E shown in Tables 4 to 6 (Examples 14 and 15).
  • FIG. 16 is a graph showing the relationship between the dry film thickness ( ⁇ m) and ⁇ E shown in Tables 4 to 6 (Examples 16 to 18).
  • FIG. 16 is a graph showing the relationship between the dry film thickness ( ⁇ m) and ⁇ E shown in Tables 4 to 6 (Examples 19 to 21).
  • FIG. 16 is a graph showing the relationship between the dry film thickness ( ⁇ m) and ⁇ E shown in Tables 4 to 6 (Examples 19 to 21).
  • FIG. 18 is a graph showing the relationship between the dry film thickness ( ⁇ m) and ⁇ E shown in Tables 4 to 6 (Example 22).
  • FIG. 18 is a graph showing the relationship between the dry film thickness ( ⁇ m) and ⁇ E shown in Tables 4 to 6 (Example 23).
  • FIG. 26 is a graph showing the relationship between the dry film thickness ( ⁇ m) and ⁇ E shown in Tables 4 to 6 (Example 24).
  • FIG. 26 is a graph showing the relationship between the dry film thickness ( ⁇ m) and ⁇ E shown in Tables 4 to 6 (Examples 25 and 26).
  • the anticorrosive coating composition according to the present invention contains a bisphenol A epoxy resin (A), an amine curing agent (B), a vinyl chloride copolymer (C), and a monoepoxide compound (D). .
  • A bisphenol A epoxy resin
  • B an amine curing agent
  • C vinyl chloride copolymer
  • D monoepoxide compound
  • the anticorrosive coating composition contains, among known epoxy resins, a bisphenol A type epoxy resin (A).
  • a bisphenol A type epoxy resin (A) By using the bisphenol A type epoxy resin (A), the low temperature curability of the anticorrosion coating composition can be improved, and the base material (coated object) such as a blast steel plate, shop coated steel plate, organic zinc coated steel plate etc. Adhesion can be made favorable, and thereby, good corrosion resistance can be obtained.
  • the bisphenol A epoxy resin (A) may be used alone or in combination of two or more.
  • the anticorrosive coating composition can contain an epoxy resin other than the bisphenol A epoxy resin (A).
  • the content of bisphenol A epoxy resin (A) in the total amount of epoxy resin is preferably 50% by mass or more, 70% by mass
  • the content is more preferably 90% by mass or more, particularly preferably 95% by mass or more (for example, 100% by mass).
  • epoxy resins other than bisphenol A epoxy resin (A) for example, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin And glycidyl amine type epoxy resin, phenol novolac type epoxy resin, rubber modified epoxy resin and the like.
  • the epoxy equivalent of the bisphenol A type epoxy resin (A) is preferably 100 to 3,000, more preferably 150 to 1,000, and still more preferably 180 to 500.
  • the epoxy equivalent is 100 or more, good low temperature curability tends to be easily obtained, and the toughness of the obtained coating film tends to be good. If the epoxy equivalent exceeds 3000, the low temperature curability tends to be poor or the coating tends to be hard.
  • the number average molecular weight of the bisphenol A type epoxy resin (A) is preferably 200 to 5000, more preferably 250 to 2000, in terms of standard polystyrene measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the bisphenol A type epoxy resin (A) [solid content] is preferably contained in an amount of 10 to 60% by mass, and more preferably 15 to 55% by mass, in the solid content of the anticorrosion coating composition.
  • the content is 10% by mass or more, the corrosion resistance of the coating film tends to be good. If the content is 60% by mass or less, the coating film is not too hard, and an anticorrosion paint composition excellent in crack resistance which hardly causes defects such as cracks can be easily obtained.
  • the content of the bisphenol A epoxy resin (A) exceeds 60% by mass, the adhesion to the base and the top coat film, the interval adhesion and the like tend to be lowered.
  • Amine curing agent (B) As the amine curing agent (B), conventionally known epoxy resin curing agents can be used. Specific examples of the amine curing agent (B) include a polyamine curing agent, a modified polyamine curing agent, a polyamide curing agent, a modified polyamide curing agent and the like. The amine curing agent (B) may be used alone or in combination of two or more.
  • polyamine-based curing agents examples include aliphatic polyamines (meta-xylene diamine, isophorone diamine, diethylene triamine, triethylene tetramine, diamino diphenyl methane, etc.); alicyclic polyamines; aromatic polyamines etc.
  • the modified polyamine-based curing agent is a modified product of the above-mentioned polyamine, and is, for example, an aliphatic, alicyclic or aromatic polyamine modified by epoxide addition, Michael addition, Mannich addition, thiourea addition, acrylonitrile addition, ketone blocking, etc. Etc.
  • polyamide-based curing agent examples include polyamidoamines which are produced by condensation of dimer acid and polyamine and have reactive primary and secondary amino groups in the molecule.
  • the polyamine forming the polyamidoamine can be the above-mentioned aliphatic polyamine, alicyclic polyamine, aromatic polyamine and the like.
  • the modified polyamide-based curing agent is a modified polyamide, and examples thereof include an epoxy adduct formed by adding an epoxy compound to polyamide, a Mannich modified polyamide, and the like.
  • the amine curing agent (B) preferably contains a polyamide amine from the viewpoints of corrosion resistance, crack resistance, adhesion to a base and a top coat film, interval adhesion, and the like.
  • the content of the polyamidoamine in the amine curing agent (B) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass % Or higher and 100% by mass (the amine curing agent (B) is a polyamidoamine) are most preferable.
  • the polyamide amine is preferably an aliphatic polyamide amine which is a condensation product of a dimer acid and an aliphatic polyamine.
  • the amine equivalent of the amine curing agent (B) is usually 50 to 1000, preferably 100 to 800, more preferably 150 to 655, and still more preferably 180 to 500.
  • an anticorrosive coating composition excellent in anticorrosion, adhesion to a substrate and a top coat, interval adhesion, etc. is easily obtained.
  • the amine-based curing agent (B) [solid content] is preferably contained in an amount of 5 to 40% by mass, and more preferably 7 to 30% by mass, in the solid content of the anticorrosion coating composition.
  • content of the amine curing agent (B) is in the above range, it is advantageous in terms of corrosion resistance, crack resistance, adhesion to the base and the top coat, interval adhesion, coating workability, and the like.
  • the content ratio of the bisphenol A epoxy resin (A) (solid content) to the amine curing agent (B) (solid content) in the anticorrosion coating composition is equivalent to the equivalent ratio [bisphenol A epoxy resin (A Epoxy group / active hydrogen in amine curing agent (B)], preferably 1 / 0.5 to 1.5, more preferably 1 / 0.6 to 1.3, and further Preferably, it is 1 / 0.75 to 1.1.
  • the anticorrosion paint composition contains a vinyl chloride-based copolymer (C).
  • the vinyl chloride-based copolymer (C) refers to a copolymer containing a constituent unit derived from vinyl chloride. By containing the vinyl chloride copolymer (C), the interval adhesion, the adhesion to the base and the top coat film, the crack resistance and the like can be enhanced.
  • the vinyl chloride-based copolymer (C) may be used alone or in combination of two or more.
  • vinyl chloride-based copolymer (C) are, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-vinyl alkyl ether copolymer, vinyl chloride-acrylonitrile copolyester Polymer, vinyl chloride-diethyl maleate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-maleic anhydride copolymer, vinyl chloride-alkyl (meth) acrylate copolymer, vinyl chloride-styrene copolymer Combination, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl stearate copolymer, vinyl chloride-maleic acid (or maleic acid ester) copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-fatty acid copolymer Group vinyl copolymer and the like.
  • the content of the constituent unit derived from vinyl chloride in the vinyl chloride copolymer (C) is 50% by mass or more Preferably, it is 60% by mass or more (eg, 70% by mass or more).
  • the polymer (C) is preferably a vinyl chloride-vinyl alkyl ether copolymer.
  • the vinyl chloride-vinyl alkyl ether copolymer include a copolymer of vinyl chloride and an alkyl vinyl ether having 1 to 10, preferably 2 to 5 carbon atoms in the alkyl group.
  • vinyl chloride-vinyl isobutyl ether copolymer vinyl chloride-vinyl isopropyl ether copolymer, vinyl chloride-vinyl ethyl ether copolymer and the like. More preferably, it is a vinyl chloride-vinyl isobutyl ether copolymer.
  • the weight average molecular weight of the vinyl chloride-based copolymer (C) is usually 10000 to 100000, preferably 20000 to 50000, and more preferably 23000 to 40000 in terms of standard polystyrene measured by GPC measurement.
  • the weight average molecular weight of the vinyl chloride copolymer (C) is within the above range, the interval adhesion, the adhesion to the base and the top coat, the crack resistance, the corrosion resistance, the bisphenol A epoxy resin (A) and It is advantageous in improving the compatibility of the above and the painting workability.
  • the content of the vinyl chloride copolymer (C) [solid content] in the anticorrosion paint composition is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the bisphenol A epoxy resin (A) [solid content]. Is 10 to 45 parts by mass (eg, 10 to 40 parts by mass).
  • the content of the vinyl chloride-based copolymer (C) is 5 parts by mass or more, the interval adhesion, the adhesion to the base and the top coat, the crack resistance, the corrosion resistance, the bisphenol A epoxy resin (A) It is possible to obtain the effect of enhancing the compatibility with the above and the painting workability and the like.
  • the content of the vinyl chloride-based copolymer (C) exceeds 50 parts by mass, for example, the improvement effect of the adhesion to the interval adhesion and the top coat film may be insufficient or may be reduced. .
  • the vinyl chloride copolymer (C) [solid content] is preferably contained in an amount of 1 to 30% by mass in the solid content of the anticorrosion coating composition, and is 2 to 20% by mass (for example, 2.5 to 15% by mass). More preferably, it is included.
  • the content of the vinyl chloride copolymer (C) is in the above range, the adhesion to the interval, the adhesion to the base and the top coat, the crack resistance, the corrosion resistance, and the bisphenol A type epoxy resin (A) It is advantageous in improving the compatibility and the painting workability and the like.
  • the anticorrosive paint composition contains a monoepoxide compound (D).
  • the monoepoxide compound (D) refers to a compound having one epoxy group in the molecule. According to the anticorrosion coating composition containing the vinyl chloride copolymer (C) and the monoepoxide compound (D), the synergistic effect can further improve the interval adhesion.
  • the monoepoxide compounds (D) may be used alone or in combination of two or more.
  • the interval adhesion property is improved by the following function by containing the monoepoxide compound (D) in addition to the vinyl chloride copolymer (C). It is considered to be improved. That is, as described above, when the vinyl chloride copolymer (C) is contained, the interval adhesion of the anticorrosion paint composition can be improved, thereby maintaining good adhesion to the top coat film. After the formation of the anticorrosion coating composed of the anticorrosion coating composition can be extended the period from the application of the top coat to the coating, the vinyl chloride copolymer (C ) Can cause dehydrochlorination reaction due to exposure to light (such as ultraviolet light) or oxygen and cause chain decomposition reaction.
  • light such as ultraviolet light
  • This decomposition reaction (dehydrochlorination reaction) is considered to be promoted by active hydrogen possessed by the free amine derived from the amine curing agent (B) which may remain in the anticorrosion coating.
  • the monoepoxide compound (D) can react with the above free amine and this can be consumed, so a vinyl chloride copolymer by the above free amine can be consumed. It is considered that the dehydrochlorination reaction promotion of (C) is suppressed, and as a result, the interval adhesion is improved.
  • Preferred examples of monoepoxide compounds (D) are monoglycidyl ethers, and specific examples thereof include alkyl glycidyl ether and phenyl glycidyl ether (alkyl phenyl glycidyl ether and the like).
  • the carbon number of the alkyl moiety of the alkyl glycidyl ether and the alkyl phenyl glycidyl ether is usually 1 to 20, preferably 5 to 18, and more preferably 10 to 16.
  • the epoxy equivalent of the monoepoxide compound (D) is usually 50 to 1000, preferably 100 to 600, and more preferably 150 to 500.
  • the monoepoxide compound (D) is preferably an alkyl glycidyl ether from the viewpoint of improving interval adhesion.
  • the content of monoepoxide compound (D) [solid content] in the anticorrosion coating composition is 2 to 50 parts by mass, preferably 4 to 48 parts based on 100 parts by mass of amine curing agent (B) [solid content]. It is a part by mass (for example, 5 to 47 parts by mass).
  • the content of the monoepoxide compound (D) is 2 parts by mass or more, it is possible to obtain the effect of further improving the interval adhesion as compared with the case where the monoepoxide compound (D) is not contained.
  • the content of the monoepoxide compound (D) exceeds 50 parts by mass, the corrosion resistance and hardness of the coating may be lowered.
  • the mass ratio] is preferably 0.02 to 2.5, more preferably 0.03 to 2.0, and still more preferably 0.05 to 1.9, from the viewpoint of improving the interval adhesion. It is.
  • the content ratio of the monoepoxide compound (D) [solid content] to the amine curing agent (B) [solid content] in the anticorrosion coating composition is equivalent to the equivalent ratio [epoxy in the monoepoxide compound (D) Group / amine based on active hydrogen in the curing agent (B)], preferably 1 / 0.01 to 0.4, more preferably 1 / 0.02 to 0.3, further preferably 1 / It is 0.03 to 0.25.
  • the monoepoxide compound (D) [solid content] is preferably contained in an amount of 0.1 to 15% by mass, preferably 0.2 to 10% by mass (e.g. 0.5 to 8% by mass), in the solid content of the anticorrosion coating composition More preferably included.
  • the content of the monoepoxide compound (D) is in the above range, it is advantageous for enhancing the interval adhesion.
  • the anticorrosion paint composition can contain a (meth) acrylate compound (E) as required.
  • the (meth) acrylate compound (E) refers to a compound having one or more (meth) acryloyl groups in the molecule. By containing the (meth) acrylate compound (E), the interval adhesion, the adhesion to the base and the top coat, the corrosion resistance, the curability and the like can be enhanced.
  • As the (meth) acrylate compound (E) only one type may be used, or two or more types may be used in combination.
  • “(meth) acryloyl group” represents at least one selected from methacryloyl and acryloyl. The same applies to “(meth) acrylic”.
  • (meth) acrylate compound (E) is (meth) acrylic acid alkyl ester such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and the like .
  • the carbon number of the alkyl moiety is preferably 1 to 10, more preferably 1 to 5.
  • (meth) acrylate compound (E) examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nona ethylene glycol Di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Trimethylolpropane ethylene oxide adduct tri (meth) acrylate, trimethylolpropane propylene oxide adduct tri (meth) acrylate, glycerin tri (meth) Crylates, pentaerythritol tri (meth) acrylate, pentaerythri
  • Still another example of the (meth) acrylate compound (E) is a vinyl ester resin (epoxy (meth) acrylate) obtained by the reaction of an epoxy resin and (meth) acrylic acid.
  • the epoxy resin may be other epoxy resin as described above in the paragraph of “(1) Bisphenol A type epoxy resin (A)” besides bisphenol A type epoxy resin, but preferably bisphenol A type epoxy resin It is.
  • the (meth) acrylate compound (E) is preferably a vinyl ester resin from the viewpoints of interval adhesion, adhesion to a base and a top coat, corrosion resistance, curability, etc., and bisphenol A type vinyl It is more preferable that it is an ester resin.
  • the number average molecular weight of the vinyl ester resin is preferably 1000 to 5000, more preferably 1000 to 3000, in terms of standard polystyrene conversion value by GPC measurement. When the number average molecular weight of the vinyl ester resin is in the above range, it is advantageous in enhancing the interval adhesion, the adhesion to the base and the top coat, the corrosion resistance, the curability and the like.
  • the (meth) acrylate compound (E) [solid content] is preferably contained in an amount of 0.2 to 15% by mass in the solid content of the anticorrosion coating composition, and 0.5 to 10% by mass (e.g. 1 to 6% by mass) More preferably included.
  • the content of the (meth) acrylate compound (E) is in the above range, it is advantageous in enhancing the interval adhesion, the adhesion to the base and the top coat, the corrosion resistance, the curability, and the like.
  • the content of the (meth) acrylate compound (E) (solid content) in the anticorrosion coating composition is preferably 5 to 100 parts by mass of the bisphenol A epoxy resin (A) (solid content).
  • the amount is 25 parts by mass, more preferably 10 to 20 parts by mass (eg, 10 to 16 parts by mass).
  • the anticorrosion paint composition can contain a silane coupling agent (F) as needed.
  • a silane coupling agent (F) By containing the silane coupling agent (F), the interval adhesion, the adhesion to the base and the top coat, the corrosion resistance, the curability and the like can be enhanced.
  • the silane coupling agent (F) only one type may be used, or two or more types may be used in combination.
  • Preferred examples of the silane coupling agent (F) are alkoxysilane compounds.
  • alkoxysilane compounds include ⁇ -glycidyloxyalkyltrialkoxysilanes such as ⁇ -glycidyloxypropyltrimethoxysilane and ⁇ -glycidyloxypropyltriethoxysilane; ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltripropoxy ⁇ -aminoalkyltrialkoxysilanes such as silane; N-phenyl- ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, N- such as N-phenyl- ⁇ -aminopropyltripropoxysilane And phenyl- ⁇ -aminoalkyltrialkoxysilane and the like.
  • the silane coupling agent (F) (solid content) is preferably contained in an amount of 0.1 to 15% by mass in the solid content of the anticorrosion coating composition, and 0.2 to 10% by mass (for example, 1 to 5% by mass) More preferably, it is included.
  • the content of the silane coupling agent (F) is in the above range, it is advantageous in enhancing the interval adhesion, the adhesion to the base and the top coat, the corrosion resistance, the curability and the like.
  • the anticorrosion paint composition can contain one or more other formulation components, if necessary.
  • other formulation components for example, thermoplastic resin, solvent, pigment, anti-sagging agent (anti-settling agent), anti-coloring agent, anti-foaming / anti-abrasive agent, film-forming aid, UV absorber, anti-oxidant Agents, leveling agents, matting agents, curing accelerators, dispersing agents, viscosity modifiers, surface conditioners, plasticizers, preservatives, reactive diluents, non-reactive diluents and the like.
  • a thermoplastic resin petroleum-based resin, (meth) acrylic resin, polyester resin etc. can be used, for example. By containing a thermoplastic resin, there are cases where the physical properties of the coating can be improved.
  • solvent those generally used in the relevant field can be used, and examples thereof include toluene, xylene, isobutanol, methyl ethyl ketone, methyl isobutyl ketone and the like. Two or more mixed solvents may be used.
  • a color pigment As a pigment, a color pigment, an extender pigment, a rust preventive pigment etc. are mentioned.
  • coloring pigments are titanium oxide, carbon black, lead white, graphite, zinc sulfide, zinc oxide (zinc white), chromium oxide, yellow nickel titanium, yellow chromium titanium, yellow iron oxide, red iron oxide, black iron oxide And phthalocyanine blue, phthalocyanine green, ultramarine blue, benzimidazolone yellow, quinacridone red, azo red / yellow pigments and the like. Two or more color pigments may be used.
  • extender pigment examples include talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, silicic acid, silicate, alumina, calcium sulfate, mica-like iron oxide (MIO), glass flakes, mica (szolite mica, clarite) ⁇ Including mica etc. Two or more extender pigments may be used.
  • anticorrosive pigments are zinc molybdate, aluminum molybdate, lead cyanamide, red lead, lead suboxide, zinc chromate, zinc powder (Zn), zinc oxide (zinc white), basic lead chromate, basic It includes lead sulfate, calcium leadate, aluminum tripolyphosphate, zinc phosphate, calcium phosphate, aluminum powder (Al), hemihydrate gypsum and the like. Two or more rust preventive pigments may be used.
  • the anticorrosion paint composition according to the present invention can be prepared in the same manner as a general anticorrosion paint using an epoxy resin.
  • the anticorrosive coating composition according to the present invention is preferably a two-component coating composition.
  • the two-component anticorrosion paint composition comprises a first agent (main agent) containing at least a bisphenol A epoxy resin (A) and a second agent (curing agent) containing at least an amine curing agent (B). Become. Both the first and second agents can contain a solvent.
  • the first and second agents are usually mixed and coated on a substrate just before use.
  • the vinyl chloride copolymer (C), monoepoxide compound (D), (meth) acrylate compound (E), silane coupling agent (F) and other compounding components are as follows: It may be blended with either the first agent or the second agent, or may be blended with both. Usually, the (meth) acrylate compound (E) and the silane coupling agent (F) are blended in the first agent.
  • the vinyl chloride copolymer (C) is contained in the first agent (main agent), and the monoepoxide compound (D) is the second agent (curing agent). Contained in).
  • the interval adhesion can be enhanced as compared with the case where the vinyl chloride copolymer (C) and the monoepoxide compound (D) are both contained in the first agent.
  • Coating of the anticorrosion paint composition onto a substrate can be carried out by a general method such as brushing, roller, spray and the like.
  • the coating composition obtained by mixing the first and second agents immediately before use is applied using the above method.
  • the coating of the coating composition obtained by mixing the first agent and the second agent on a substrate is carried out within the usable time after the mixing of the first agent and the second agent.
  • the anticorrosive paint composition of the present invention typically exhibits a pot life of about 30 minutes to 8 hours. After coating, it can be dried to form an anticorrosive coating.
  • the drying temperature is usually normal temperature (about 20 to 35 ° C.), but can be performed at a temperature lower than this.
  • the object to be coated is not particularly limited as long as it requires anticorrosion, but, for example, a ship (the inner surface of a ballast tank of a ship or the bottom of a ship) In addition to outer plates, etc., it can be bridges, tanks, plants (petroleum plants etc.), marine structures such as pipes, etc.
  • the material of the surface of the substrate to be coated with the anticorrosion coating composition can be, for example, a coating film made of a coating material such as iron-based metal such as steel, non-ferrous metal, concrete, and old coating film.
  • the old coating film refers to a coating film or a part thereof which has been previously formed and used.
  • the anticorrosive coating composition according to the present invention is suitably applied to a coating method (method for producing a composite coating film) on which an undercoating film is formed on a surface of a substrate and then a top coating film is formed thereon. it can.
  • the anticorrosion paint composition according to the present invention can be used to form an undercoat film.
  • the undercoating film may be a laminated structure of a plurality of coating films, and in this case, the anticorrosion coating composition according to the present invention is used at least for the formation of the undercoating film (in contact with the topcoat film) on the outermost surface.
  • the anticorrosion coating which can become a base of the undercoating film which consists of the anticorrosion coating composition which concerns on this invention, shop coating, an organic or inorganic zinc primer coated coating film etc. can be mentioned.
  • the surface of the substrate may be blasted.
  • the film thickness of the anticorrosion coating film formed from the anticorrosion paint composition according to the present invention can be appropriately selected according to the type of the object to be coated, the application and the like, but in general, the dry film thickness is 10 to 500 ⁇ m. It is an extent.
  • the anticorrosion coating film formed from the anticorrosion coating composition which concerns on this invention may apply
  • drying may be performed to obtain a dried coating film having a desired film thickness, or by forming a plurality of dry coating films. You may obtain the dried coating film which has a desired film thickness.
  • top coat used for a top coat formed on an anticorrosion coat.
  • the top coating include oil based paints, long oil based phthalate resin paints, silicone alkyd resin paints, phenol resin paints, chlorinated rubber based resin paints, epoxy resin paints, modified epoxy resin paints, tar epoxy resin paints, vinyl chloride resin Paints, polyurethane resin paints, fluorocarbon resin paints, silicon modified resin paints, antifouling paints for preventing biological adhesion, etc.
  • the antifouling paint include acrylic resin antifouling paints and vinyl resin antifouling paints.
  • the top coat is preferably an epoxy resin paint, a polyurethane resin paint, a fluorine resin paint, an acrylic resin antifouling paint, a vinyl resin antifouling paint or the like.
  • the dry film thickness of the top coat film is usually about 10 to 300 ⁇ m.
  • the top coat may be the anticorrosion paint composition according to the present invention.
  • the anticorrosion paint composition of the present invention is a top coat
  • the anticorrosion paint composition according to the present invention for example, for repair, on the old paint film formed from the anticorrosion paint composition according to the present invention It is a case of forming the coating film which consists of things.
  • the anticorrosion paint composition according to the present invention can also be used exclusively for forming a top coat film, not a primer coat.
  • the dry film thickness of the top coat film formed from the anticorrosive coating composition according to the present invention is usually about 10 to 300 ⁇ m.
  • the anticorrosion coating film formed from the anticorrosion paint composition according to the present invention can be applied to the top coat film formed from the anticorrosion paint composition while securing good corrosion resistance and crack resistance etc. It also exhibits good adhesion to top coats formed from other top coats, and can exhibit good interval adhesion.
  • the colored anticorrosive paint (colored anticorrosive paint composition) according to the present invention can be used in the method for forming a coated film according to the present invention described in detail later.
  • the coating film forming method according to the present invention is a method for forming a dry coating film on the surface of a substrate, and the following steps: A step of setting a dry film thickness T (dry film thickness setting step), Preparing or preparing a two-component colored anticorrosion paint comprising a first agent and a second agent and satisfying the conditions (a) to (i) described later (colorable anticorrosion paint preparation step); A step (coating step) of applying a colored anticorrosion paint to the surface of the article to be coated until the surface of the substrate is covered with a paint anticorrosion paint (coating step) Step of drying) to obtain a dried coating (drying step) including.
  • a predetermined colored anticorrosive paint (colored anticorrosive paint composition) is used as a paint for forming a dried coating film.
  • This colored anticorrosion paint is a paint having a "film thickness determination function" that can determine whether or not a predetermined film thickness has been reached by visually observing the hue of the coating (wet coating) during coating. .
  • the colored anticorrosive paint according to the present invention will first be described in detail below.
  • the colored anticorrosion paint according to the present invention is a two-component anticorrosion paint composition comprising a first agent and a second agent.
  • the colored anticorrosive paint according to the present invention contains a colored pigment [condition (c)].
  • the colored anticorrosion paint comprises a bisphenol A type epoxy resin (A), an amine curing agent (B), a vinyl chloride copolymer (C), a monoepoxide compound (D) and a (meth) acrylate compound (E) And [condition (d)].
  • the first agent of the colored anticorrosion paint contains a bisphenol A epoxy resin (A) and a vinyl chloride copolymer (C) [condition (g)], and the second agent is an amine curing agent (B) And monoepoxide compound (D) [condition (h)].
  • A bisphenol A epoxy resin
  • C vinyl chloride copolymer
  • B amine curing agent
  • D monoepoxide compound
  • the first agent (main agent) of the colored anticorrosive paint contains a bisphenol A epoxy resin (A).
  • the description in "(1) Bisphenol A type epoxy resin (A)" of the above-mentioned ⁇ Anticorrosion paint composition> is cited about bisphenol A type epoxy resin (A) which the 1st agent of a coloring anticorrosion paint contains.
  • the first agent of the colored anticorrosive paint contains a vinyl chloride copolymer (C).
  • the description in "(3) vinyl chloride-based copolymer (C)" of the above-mentioned ⁇ anticorrosion paint composition> is cited for the vinyl chloride-based copolymer (C) contained in the first agent.
  • the content of the vinyl chloride copolymer (C) [solid content] in the colored anticorrosive paint is 5 to 50 parts by mass with respect to 100 parts by mass of the bisphenol A epoxy resin (A) [solid content]. e), preferably 10 to 45 parts by mass (eg, 10 to 40 parts by mass).
  • the second agent of the colored anticorrosive paint contains a monoepoxide compound (D).
  • the description in “(4) Monoepoxide compound (D)” of the above-mentioned ⁇ Anticorrosion paint composition> is cited.
  • the content of monoepoxide compound (D) [solid content] in the colored anticorrosive paint is 2 to 50 parts by mass with respect to 100 parts by mass of amine curing agent (B) [solid content] [condition (f)], Preferably, it is 4 to 48 parts by mass (for example, 5 to 47 parts by mass).
  • the colored anticorrosive paint contains a (meth) acrylate compound (E).
  • the (meth) acrylate compound (E) contains a vinyl ester resin [condition (i)], preferably bisphenol A, from the viewpoints of interval adhesion, adhesion to a substrate and a top coat, corrosion resistance, curability, etc. Type vinyl ester resin.
  • the colored anticorrosive paint can contain a silane coupling agent (F) as required.
  • the description in "(6) Silane coupling agent (F)" of the above-mentioned ⁇ anticorrosion paint composition> is quoted about a silane coupling agent (F).
  • Colored Pigment As the colored pigment contained in the colored anticorrosive paint, various kinds of conventionally known colored pigments can be used, and colored anticorrosive paints of various colors can be realized by selecting the colored pigment.
  • the type of the color pigment to be added to the color anticorrosive paint (the hue of the color anticorrosive paint) can be selected according to the color of the surface (surface to be coated) of the object to be coated. It is preferable to select the kind or combination of color pigments such that the color difference ⁇ E3 between the coating film formed from the above and the surface of the substrate is 20 or more.
  • the hue of the coating formed from the colored anticorrosive paint having the dry coating thickness T is substantially the same as the hue of the colored anticorrosive paint itself, for example, in the case of a conventional solvent-based paint that does not cause color separation. is there.
  • coloring pigment examples are not particularly limited.
  • carbon black, titanium dioxide, zircon oxide, basic lead sulfate, tin oxide, lead white, graphite, zinc sulfide, zinc oxide, chromium oxide, yellow nickel titanium, yellow chromium titanium Yellow iron oxide, red iron oxide, black iron oxide, chromium yellow, phthalocyanine blue, phthalocyanine green, ultramarine blue, quinacridones, azo red / yellow pigments and the like can be used.
  • the color pigments may be used alone or in combination of two or more.
  • carbon black and titanium dioxide are preferably used because of high coloring power, and the color pigment preferably contains titanium dioxide.
  • the coating film becomes light in color. To avoid this, it may be used in combination with other color pigments.
  • the coloring pigment content is relatively small, since it is necessary to have relatively small background hiding ability.
  • the content of the color pigment is usually 0.01 to 3% by volume, preferably 0.1 to 2% by volume, in the film-forming component. If the content of the color pigment is too small, the substrate hiding power is too small, and the change in the hue of the wet coating during the coating is also too small, so it may be determined whether the specified film thickness has been reached. It will be difficult.
  • film-forming component means all components other than the solvent contained in the colored anticorrosive paint.
  • the colored anticorrosive paint can contain pigments other than colored pigments as required.
  • pigments other than color pigments extender pigments, rust preventive pigments and the like can be mentioned.
  • specific examples of the extender pigment are talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, silicic acid, silicate, alumina, calcium sulfate, mica-like iron oxide (MIO), glass flakes, mica (szolite mica, clarite) ⁇ Including mica etc. Two or more extender pigments may be used.
  • anti-corrosive pigment examples include calcium sulfate hemihydrate, zinc molybdate, aluminum molybdate, cyanamide lead, cyanamide calcium zinc, red lead, lead oxide, zinc chromate, strontium chromate, barium chromate, zinc powder ( Zn), zinc oxide (zinc flower), basic lead chromate, basic lead sulfate, calcium lead acid, aluminum tripolyphosphate, zinc phosphate, calcium phosphate, calcium phosphite, lead trioxide, lead oxide, aluminum powder ( Al), including hemihydrate gypsum and the like. Two or more rust preventive pigments may be used.
  • the colored anticorrosive coating preferably has an average particle diameter of 10 to 300 ⁇ m and an average thickness of 2 to 50 ⁇ m, It is preferable to include a scaly (flat) pigment having an aspect ratio defined as an average particle size / average thickness of preferably 2 to 100 (hereinafter, also simply referred to as a “scaly pigment”) (G).
  • a scaly pigment having an aspect ratio defined as an average particle size / average thickness of preferably 2 to 100
  • scale-like pigment (G) and its function are demonstrated.
  • the film thickness determination paints described in Patent Documents 4 and 5 described above are all paints used for forming a coating film having a target dry film thickness (dry film thickness T) of 100 ⁇ m or more, and are included therein
  • the paint is prepared so as to satisfy the following relationship with respect to color difference by adjusting the content of the color pigment to be produced.
  • (A) The color difference between the film thickness judgment paint and the substrate is 20 or more
  • (B) The color difference between the coating film of the target dry film thickness and the coating film of the dry film thickness less than (target dry film thickness-50) m is 2 or more
  • the coating film of the target dry film thickness Film thickness + 50) Color difference of the coating film of dry film thickness more than ⁇ m is less than 1.
  • (b) is particularly important, and if the difference between the hue of the coating film approaching the target film thickness and the hue of the coating film reaching the target film thickness is not clear, the coating operator It becomes difficult to visually determine whether the wet coating film during coating has reached the target film thickness as a dry coating film or is still insufficient.
  • the film thickness judgment is easier as the color difference between the coating film approaching the target film thickness and the coating film reaching the target film thickness is larger, but a thick coating film is formed by one application. In this case, it may be difficult to make the color difference sufficiently large. More specifically, if the target dry film thickness of the coating film formed by one-time application is up to about 250 ⁇ m (the target dry film thickness in the example of Patent Document 4 is 125 ⁇ m, the implementation of Patent Document 5) The target dry film thickness in the example is a maximum of 250 ⁇ m.) According to the preparation methods described in these patent documents, the above color difference is increased to some extent, and the film thickness is determined relatively easily in forming a coating film having a desired film thickness. It was possible to do.
  • a thick film having a thickness of more than 250 ⁇ m on a substrate has been practiced to form a thick film having a thickness of more than 250 ⁇ m on a substrate.
  • the anticorrosion coating (anticorrosion coating) formed on the surface of a marine structure such as a ship or a bridge, or a steel structure such as a plant is a typical example.
  • a thick-film coating is not formed by single coating, but is formed by multiple coating (coating method in which a series of steps from coating to drying is performed multiple times to coat a dried coating). It was normal.
  • the significance of including the scale-like pigment (G) in the colored anticorrosive paint is as follows: .
  • paints anticorrosion paints, etc.
  • it is a conventional technique to include an extender pigment to enhance the coating film strength or to enhance corrosion resistance if it is an anticorrosion paint
  • it is a conventional technique and includes both an extender pigment and a color pigment
  • Film thickness determination paints are also known (the above-mentioned patent documents 4 and 5).
  • the target film thickness (the set value T of the target dry film thickness) is obtained. It is difficult to sufficiently increase the color difference between the coating film that is getting very close and the coating film that has reached the target film thickness, and whether the wet coating film has reached the target film thickness or is still insufficient in film thickness It is not always easy to determine.
  • the colored anticorrosive paint containing the scaly pigment (G) and the method for forming a coating film using the same for example, with reference to the graph of Example 13 shown in FIG.
  • the graph is not exponentially rapid monotonous decrease, but a little ⁇ E is larger between the dry film thickness 0 ⁇ m and the setting value T of the dry film thickness compared with the shape of rapid monotonous decrease It will take on a shape that seems to swell.
  • the body pigment is a component that absorbs light and blocks the transmission of light, while it becomes a thick film and the scaly pigment (G) is the surface of the coating It is considered that the direction is easily oriented (the major axis of the scale-like pigment is oriented in the plane direction of the coating film), and the light is likely to transmit the scale-like pigment (G) accordingly. It is thought that it is a cause which becomes such a graph shape.
  • the average particle diameter of the scale-like pigment (G) is preferably 10 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, still more preferably 10 to 150 ⁇ m, from the viewpoint of the sufficiency of the condition (b) and the physical properties of the paint and coating film. It is.
  • the dry film thickness T set in the dry film thickness setting step is selected from the range of 300 ⁇ m or more when the average particle diameter is less than 10 ⁇ m, it may be difficult to realize the condition (b). .
  • the average particle size is less than 10 ⁇ m, the oil absorption of the scaly pigment (G) is increased, and the viscosity of the coating is increased accordingly, so that the coating workability tends to be lowered. Even when the average particle size exceeds 300 ⁇ m, when the dry coating thickness T is selected from the range of 300 ⁇ m or more, realization of the above condition (b) tends not to be easy, and the surface smoothness of the coating is It tends to be lost.
  • the aspect ratio of the scale-like pigment (G) is preferably 2 to 100 from the viewpoint of the sufficiency of the condition (b) and the physical properties of the paint and the coating film. If the aspect ratio is high to some extent, it is easy to increase the rise of the above-mentioned graph, and therefore the aspect ratio is more preferably 3 or more, further preferably 4 or more.
  • the aspect ratio is more preferably 20 or less.
  • the average thickness of the scaly pigment (G) is preferably 2 to 50 ⁇ m.
  • the preferred range of the average thickness can be a range derived from the preferred range of the above average particle diameter and the preferred range of the above aspect ratio, and can be, for example, the range of 2 to 30 ⁇ m (for example, 2 to 20 ⁇ m).
  • the scaly pigment (G) preferably has a refractive index of 1.8 or less, more preferably 1.7 or less, and still more preferably 1.6 or less.
  • the above condition (b) is realized by reducing the refractive index and suppressing the light reflection at the interface between the binder resin (epoxy resin) and the scaly pigment (G) in the coating film to increase the light transmission amount. It can be made easy.
  • the method of measuring the refractive index is as described in the Example section.
  • the scaly pigment (G) can be an extender pigment, and specifically, it can be talc, mica (mica), clay, glass flakes, aluminum hydroxide and the like. Preferred are talc, mica (mica), clay and glass flakes, and more preferred are talc, mica (mica) and glass flakes.
  • the colored anticorrosive paint can contain one or more flaky pigments (G).
  • the colored anticorrosive paint can contain other extender pigments other than the scaly pigment (G).
  • the other extender pigment may be a flat-shaped extender pigment in which any one or more of the average particle diameter, the average thickness or the aspect ratio does not satisfy the above-mentioned predetermined range, or the particulate matter having an aspect ratio of 1 or about 1 It may be a pigment.
  • the other extender pigment may be the same material as the scale-like pigment (G) or may be a different material, and specific examples thereof include calcium carbonate in addition to those described for the scale-like pigment (G). Including magnesium carbonate, barium sulfate, silica, alumina, bentonite, silicic acid, silicate, aluminum oxide hydrate and calcium sulfate.
  • the colored anticorrosion paint can contain one or more other extender pigments.
  • the content of the scaly pigment (G) is preferably 5 to 45% by volume, more preferably 10 to 40% by volume (eg 15 to 35% by volume) in the film-forming component.
  • the content of the scaly pigment (G) is less than 5% by volume, it is difficult to obtain the above-mentioned effect by blending it, and when not using other extender pigments in combination, the coating film reinforcing effect And the coating film strength and corrosion resistance tend to be insufficient. Also, when it exceeds 45% by volume, the film forming property tends to be lowered.
  • the total content thereof is preferably 45% by volume or less of the coating film-forming component.
  • the content of the scaly pigment (G) in the total content of the scaly pigment (G) is 10 from the viewpoint of the sufficiency of the condition (b).
  • the volume ratio is preferably at least 20%, more preferably at least 20%, and still more preferably at least 30%.
  • the colored anticorrosive paint may or may not contain scale-like pigments (G). Good.
  • the colored anticorrosive paint may contain one or more other formulation components, as necessary.
  • Other components include, for example, thermoplastic resins, solvents, anti-sagging agents (anti-settling agents), anti-coloring agents, anti-foaming / anti-slip agents, film-forming assistants, UV absorbers, antioxidants, A leveling agent, a matting agent, a hardening accelerator, a dispersing agent, a viscosity regulator, a surface conditioner, a plasticizer, a preservative, a reactive diluent, a non-reactive diluent, etc. can be mentioned.
  • a thermoplastic resin petroleum-based resin, (meth) acrylic resin, polyester resin etc. can be used, for example.
  • thermoplastic resin By containing a thermoplastic resin, there are cases where the physical properties of the coating can be improved. It is preferable that the content of the other compounding components is such that it does not inhibit the clear hue and background hiding property of the color pigment and does not deteriorate the film thickness determination function of the color anticorrosive paint.
  • organic solvents can be suitably used.
  • aromatic hydrocarbons such as toluene, xylene and ethylbenzene
  • aliphatic or alicyclic hydrocarbons such as cyclopentane, octane, heptane, cyclohexane and white spirit Petroleum fractions mainly composed of aliphatic hydrocarbons and capable of exhibiting various boiling ranges having some aromatic hydrocarbons
  • dioxane, tetrahydrofuran ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol di Ethers such as butyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; butyl acetate, propyl acetate, benzyl acetate, ethylene glycol diacetate, 2- Esters such as xylethyl acetate, ethylene glycol monomethyl ether
  • the colored anticorrosive paint according to the present invention can be prepared in the same manner as a general anticorrosive paint using an epoxy resin.
  • the colored anticorrosion paint according to the present invention is a two-component type, which is a first agent (main agent) containing at least a bisphenol A epoxy resin (A) and a vinyl chloride copolymer (C), and an amine curing agent (B And a second agent (curing agent) containing at least a monoepoxide compound (D). Both the first and second agents can contain a solvent. Usually, the first agent and the second agent are mixed and coated on a substrate just before use.
  • the (meth) acrylate compound (E), the silane coupling agent (F), and other compounding components including a pigment may be compounded in any of the first agent and the second agent. It may be blended with both or both. Usually, the (meth) acrylate compound (E) and the silane coupling agent (F) are blended in the first agent.
  • the vinyl chloride-based copolymer (C) is contained in the first agent (main agent), and the monoepoxide compound (D) is contained in the second agent (curing agent).
  • the interval adhesion can be enhanced as compared with the case where the vinyl chloride copolymer (C) and the monoepoxide compound (D) are both contained in the first agent.
  • the first agent and the second agent can be prepared by mixing the blending components using a mixer such as a ball mill, a pebble mill, a roll mill, a sand grind mill, or a high speed disper.
  • a mixer such as a ball mill, a pebble mill, a roll mill, a sand grind mill, or a high speed disper.
  • the color corrosion preventive paint according to the present invention is excellent in film thickness judgment function, satisfying at least the following conditions (a) and (b), and preferably satisfying the following condition (j) Paint.
  • the “dry film thickness T” under the following conditions is, for example, a thickness selected from the range of about 10 to 500 ⁇ m, and may be selected from the range of 300 ⁇ m or more.
  • a coating film formed of a colored anticorrosion paint having a set dry film thickness T conceals the surface of the substrate
  • the color difference ⁇ E1 between the coating formed from the colored anticorrosive paint having the set dry coating thickness T and the coating formed from the colored anticorrosive coating having a dry coating thickness of 0.7 T is 2. Is 0 or more
  • the color difference ⁇ E2 between the coating formed of the colored anticorrosive paint having the set dry coating thickness T and the coating formed of the colored anticorrosive coating having the dry coating thickness of 1.3 T is less than 1 It is.
  • the color differences ⁇ E1 and ⁇ E2 and ⁇ E3 described later are generally recognized using a color difference meter (color meter) such as a tristimulus color meter SM color meter (type SM-T45, manufactured by Suga Test Instruments Co., Ltd.) It can be measured by a method.
  • the color differences ⁇ E1, ⁇ E2 and ⁇ E3 are all absolute values.
  • the condition (a) is a coating formed from a colored anticorrosive paint having a dry coating thickness T (here, the coating is a dry coating, but the base concealability of the wet coating and the dry coating is The same is applied to the concealability of the surface of the object to be coated.
  • T dry coating thickness
  • the colored anticorrosion paint according to the present invention can achieve such concealment of the surface of a substrate when forming a dry coating having a dry coating thickness T or more.
  • the hiding power of the dried coating film formed from the colored anticorrosive paint can also be evaluated by the hiding ratio in accordance with JIS K 5600-4-1: 1999.
  • the coating film formed of the colored anticorrosive paint having a dry coating thickness T preferably has a hiding ratio of 0.90 to 0.98, 0.92 to 0 More preferably, .98 (eg, 0.92 to 0.96).
  • the above condition (b) specifies the color difference ⁇ E1 between when the film thickness is the dry film thickness T set as the target and when it is 0.7 T in the dried coating film formed from the colored anticorrosive paint. It is The coating having a dry coating thickness of 0.7 T is the coating before the completion of the coating. A large color difference ⁇ E1 of 2.0 or more means that the film thickness dependency of the coating film hue in the vicinity of the completion of coating [from dry coating film thickness T (0.7 T) to dry coating film thickness T] is large. Do. As a result, it is possible to sufficiently increase the color difference between the coating film approaching the dry film thickness T considerably and the coating film reaching the dry film thickness T, so that the wet film has a target film thickness. It is possible to easily determine whether the film thickness has been reached or the film thickness is still insufficient, and it is possible to form a dry film having a dry film thickness T extremely accurately, and even a slight film thickness deficiency It can be eliminated.
  • the color difference ⁇ E1 is preferably 2.1 or more, more preferably 2.5 or more, and still more preferably 3.0 or more. However, if the color difference ⁇ E1 is too large, color unevenness easily occurs due to a slight difference in film thickness, so the color difference ⁇ E1 is preferably 10 or less, more preferably 5 or less. As described above, in the case of forming a thick film of 300 ⁇ m or more, it is preferable to use a scaly pigment (G) in order to realize the color difference ⁇ E1 of “2.0 or more”.
  • the coating film formed from the colored anticorrosive paint having the set dry coating film thickness T, and the dry coating film thickness is 0.8T
  • the color difference ⁇ E1 ′ with the coating film formed of the colored anticorrosive paint is preferably 1.0 or more, more preferably 1.1 or more, and 1.2 or more (eg, 1.5 or more). Is more preferred.
  • the color difference ⁇ E1 ′ between the coating formed from the colored anticorrosive paint having the set dry coating thickness T and the coating formed from the colored anticorrosive coating having the dry coating thickness of 0.9 T 'Is preferably 0.5 or more, more preferably 0.6 or more, and still more preferably 0.7 or more.
  • the above condition (j) specifies the color difference ⁇ E2 between when the film thickness is the dry film thickness T set as a target and when it is 1.3 T in the dried film formed from the colored anticorrosive paint. It is The coated film having a dry coating thickness of 1.3 T is a coated film after (or immediately after) the completion of the coating. When the color difference ⁇ E2 becomes 1 or more, the color difference between the coating having the dry coating thickness T and the coating exceeding the dry coating thickness T becomes large, and color unevenness easily occurs.
  • the color difference ⁇ E2 is preferably 0.5 or less, more preferably 0.4 or less (for example, 0.2 or less).
  • the color difference ⁇ E3 is preferably 20 or more [condition (k)], more preferably 25 or more, and still more preferably 30 or more. If the color difference ⁇ E3 is too small, it tends to be difficult to confirm whether the surface of the object to be coated is covered by the coating.
  • the colored anticorrosive paint satisfying the above conditions can be obtained by selecting the type (hue) of the colored pigment and adjusting the content thereof, or by adding a predetermined amount of scale-like pigment (G).
  • the set value of the dry film thickness T of the colored anticorrosive paint can be adjusted according to the content of the color pigment. That is, basically, by setting the content of the color pigment to be smaller, the set value of the dry film thickness T of the color anticorrosive paint can be made larger. In other words, since the set value of the dry coating thickness T is determined from the coating characteristics such as corrosion resistance required for the coating, the type of the object to be coated, etc.
  • the color pigment content is adjusted to be compatible.
  • the coating film forming method according to the present invention is a method for forming a dried coating film on the surface of a substrate to be coated, and the following steps: A step of setting a dry film thickness T (dry film thickness setting step), A two-component colored anticorrosion paint comprising a first agent and a second agent, which is prepared to satisfy the above conditions (a) to (i) [preferably further conditions (j) and (k)].
  • a step of preparing (coloring anticorrosive paint preparation step) A step (coating step) of applying a colored anticorrosion paint to the surface of the article to be coated until the surface of the substrate is covered with a paint anticorrosion paint (coating step) Step of drying) to obtain a dried coating (drying step) including.
  • the coating film forming method according to the present invention defines the coating film forming method in single coating, but as long as it includes the coating film forming method in single coating All coating formation methods are included in the present invention. For example, a method of obtaining a dried coating film with a desired film thickness secured by multiple coating including the coating formation method by single coating according to the present invention is also included in the present invention. Each step will be described in detail below.
  • Dry film thickness setting process This process is a process of setting dry film thickness T which is a film thickness of a target dry film formed by single application.
  • the dry film thickness T is not particularly limited, but may be selected, for example, in the range of about 10 to 500 ⁇ m and may be selected in the range of 300 ⁇ m or more.
  • the dry coating thickness T needs to be set in advance, so this step is carried out before the colored anticorrosive paint preparation step. Ru.
  • the dry film thickness T may be the film thickness of the dry film to be finally formed on the surface of the substrate, or may be the dry coating in the middle stage formed in forming the dry film. It may be the film thickness of the film.
  • An example of the former is the case of forming a final dry coating film by a single coating on the surface of a substrate, and an example of the latter is a case of forming a final dry coating film by multiple coating.
  • a dry coating film with a film thickness of 300 ⁇ m is further formed thereon, To form.
  • the film thickness of the dried coating film to be finally formed on the surface of the substrate is usually such that the desired properties to be imparted to the surface of the substrate can be sufficiently obtained by film formation (for example, Film thickness that provides sufficient corrosion resistance).
  • This step is a two-component colored anticorrosion paint comprising a first agent and a second agent, and the conditions (a) to (i) [preferably further condition (j), (K) is a step of preparing or preparing a colored anticorrosive paint according to the present invention satisfying the condition (k).
  • the details of the colored anticorrosive paint including the preparation method are as described above, and thus are omitted here.
  • This process is a process of applying a coloring anticorrosion paint on the surface until the surface of a to-be-coated-article is concealed by the coating film which consists of coloring anticorrosion paints.
  • the colored anticorrosive paint is applied to the surface of the substrate while observing the change in color difference between the coating (wet film) during coating and the surface of the substrate.
  • “To observe the change in color difference between the coating (wet coating) on the way of coating (wet coating) and the surface of the substrate” typically means that “the see-through” of the surface of the substrate has occurred on the coating surface That is, it is to observe how much the coating film (wet coating film) in the middle of coating conceals the surface of the object to be coated.
  • the hue of the wet coating is the object to be the substrate. It largely reflects the hue of the surface (that is, the "see-through” is large). Thus, the change with respect to the hue of the to-be-coated-article surface of the hue of the coating film (wet coating film) in the middle of application is visually observed. As the thickness of the coating increases, this "see-through” decreases, and the color of the surface of the object is not reflected in the color of the wet layer, that is, when the wet layer hides the surface of the object. To reach.
  • the base layer hiding property of the wet coating is almost the same as the base layer hiding property of the dried coating, so the coating thickness of the wet coating at this point (coating of the wet coating when the surface of the object is hidden)
  • the film thickness is a film thickness corresponding to the target dry film thickness T.
  • the wet coating film has covered the surface of the object to be coated.
  • a color sample provided with a dry coating film having a target dry film thickness T is prepared in advance, and the wet coating film is coated when the hue of this color sample matches the hue of the wet coating film. It can be determined that the object surface has been hidden.
  • the hue of the coating film in this region and the wet coating film It can be judged that the wet coating film has concealed the surface of the object at the point when the color matches.
  • the hue of the dry coating film having the target dry coating thickness T and the wet coating film corresponding thereto is typically the same as the hue of the colored anticorrosive paint itself, the hue of the wet coating film is It can also be judged that the wet coating film has concealed the surface of the article at a point in time when it matches the color of the colored anticorrosive paint itself.
  • the coating method of the colored anticorrosive paint is not particularly limited, and for example, conventionally known methods such as immersion method, spray method, brush coating, roller, electrostatic coating and the like can be used.
  • the coating composition obtained by mixing the first agent and the second agent immediately before use is applied using the above method.
  • Coating of the coating composition obtained by mixing the first agent and the second agent on a substrate is carried out within the pot life (useful time) after mixing the first agent and the second agent. .
  • the colored anticorrosive paint according to the present invention typically exhibits a pot life of about 30 minutes to 8 hours. After coating, it can be dried to form an anticorrosive coating.
  • the drying temperature is usually normal temperature (about 20 to 35 ° C.), but can be performed at a temperature lower than this.
  • the object to be coated is not particularly limited as long as it requires anticorrosion, but, for example, a ship (the inner surface of a ballast tank of a ship, the bottom of a ship, In addition to outer panels, etc.) Port facilities; Intake facilities such as power stations; Pipings such as water pipes for cooling; Bridges; Buoyancy; Industrial water systems; Submarine bases; Tanks; Marine structures such as plants (petroleum plants etc.) It can be a thing etc.
  • a ship the inner surface of a ballast tank of a ship, the bottom of a ship, In addition to outer panels, etc.
  • Port facilities Intake facilities such as power stations; Pipings such as water pipes for cooling; Bridges; Buoyancy; Industrial water systems; Submarine bases; Tanks; Marine structures such as plants (petroleum plants etc.) It can be a thing etc.
  • the material of the surface of the article to which the colored anticorrosive paint is applied is, for example, iron-based metal such as steel (for example, steel such as untreated steel, blast-treated steel, acid-treated steel, galvanized steel, stainless steel); Non-ferrous metals such as aluminum (alloy) materials and copper (alloy) materials; concrete; plastics; and coatings such as old coatings.
  • the old coating film refers to a coating film or a part thereof which has been previously formed and used.
  • the surface of the substrate to which the colored anticorrosion paint is applied may be pretreated, if necessary, and may have a subbing layer (coated film).
  • a subbing layer coated film
  • the shop primer layer formed from the conventionally well-known rust preventive coating composition; organic or inorganic zinc primer layer; Other anticorrosive coating films can be mentioned.
  • another anticorrosion coating is formed by, for example, forming a dry coating with a thickness of 300 ⁇ m by a single application, and further adding a dry coating with a thickness of 300 ⁇ m thereon. It can be a dry film of the first stage in the case of forming an anticorrosion coating having a film thickness of 600 ⁇ m, which is the final objective.
  • the "surface of the substrate" in the above conditions (a) and (k) means the surface of the subbing layer.
  • the other anticorrosion coating may be formed according to the method of the present invention.
  • a colored anticorrosive paint for forming the anticorrosive coating of the substrate in order to satisfy the above condition (k), it is preferable that it is a different color from the coloring anticorrosion paint for the anticorrosion coating film formed, and it is preferable that the color difference of two paints is 20 or more.
  • This step is a step of drying the coating film (wet coating film) obtained in the coating step to obtain a dried coating film.
  • the drying temperature is usually normal temperature (about 20 to 35 ° C.), but may be performed at a lower temperature or a higher temperature.
  • a top coat may be applied on the obtained dried coating to form a top coat.
  • a binder coat may be formed on the obtained dried coating, and a top coating may be applied thereon to form a top coating.
  • the top coat may be an antifouling paint applied to marine structures, ships and the like.
  • an antifouling paint the antifouling paint which uses acrylic resin which has a hydrolysable group in a side chain as binder resin can be mentioned.
  • the hydrolyzable group can be, for example, a metal ester group containing a metal atom such as divalent Cu or Zn, a trialkylsilyl ester group, or the like.
  • the dry film thickness of the top coat film is usually about 10 to 300 ⁇ m.
  • the top coat may also be the colored anticorrosive paint according to the present invention.
  • One embodiment in the case where the colored anticorrosive paint of the present invention is a top coat is formed of the colored anticorrosive paint according to the present invention on the old paint film formed from the colored anticorrosive paint according to the present invention, for example, for repair. It is a case of forming a coating film.
  • the colored anticorrosive paint according to the present invention can also be used exclusively for forming a top coat, not a primer coat.
  • the dry film thickness of the top coat film formed from the colored anticorrosive paint according to the present invention is usually about 10 to 500 ⁇ m.
  • the anticorrosive coating film formed from the colored anticorrosion paint according to the present invention is the same as that described above for the top coat film formed from the anticorrosion paint composition while ensuring good corrosion resistance and crack resistance etc. It exhibits good adhesion to top coat films formed from other top coats, and can exhibit good interval adhesion. Thereby, coating workability can be improved.
  • the method for forming a coating film using the colored anticorrosive paint according to the present invention it can be easily determined whether or not the coating film during coating has reached a predetermined film thickness.
  • the uniform coating film can be formed accurately. In this way, it is possible to effectively prevent the film thickness shortage that often occurs in the past. In addition, since excessive film thickness can be prevented, it is also possible to save paint.
  • the method for forming a coating film using the colored anticorrosive paint according to the present invention it is possible to avoid the complicated work of sequentially measuring the thickness of the coating film and checking whether or not the predetermined film thickness is reached. While being able to aim at significant efficiency-ization of coating operation, the burden reduction of the coating operator can be aimed at.
  • the coating film forming method using the colored anticorrosive paint according to the present invention can be applied to the anticorrosion coating of various structures (in particular, ships and marine structures). According to the method of the present invention, in the case of applying anticorrosion coating to the outer surface of a large structure such as a ship or the like, even a structure or a portion thereof which is difficult to be coated has a predetermined dry film thickness. The coating film can be formed accurately and simply.
  • Comparative Example 1 Preparation of Colored Anticorrosion Paint>
  • a first agent main agent
  • a second agent hardener
  • the details of each compounding component shown in Tables 1 and 2 are as follows.
  • surface is the mass part converted into solid content.
  • Tables 1 and 2 also show the volume% indication (volume% in the film forming component) of the blending amount of the color pigment and the extender pigment.
  • the film-forming component means all components other than the solvent contained in the colored anticorrosive paint.
  • the setting value T of the dried coating thickness targeted by each colored anticorrosive coating, and the hiding ratio of the dried coating of each colored coating having the dried coating thickness T (“dried coating thickness T in Tables 1 and 2 It is indicated collectively as "the concealment rate in.
  • BFA Bisphenol A epoxy resin
  • A Bisphenol A epoxy resin (solvent dilution type) manufactured by DIC Corporation, trade name "EPICLON 860-90X”, epoxy equivalent weight: 230 to 270 g / eq, number Average molecular weight (standard polystyrene conversion by GPC measurement): 470, nonvolatile matter (solid content): 90% by mass
  • E Bisphenol A Type Epoxy (Meth) Acrylate (Bisphenol A Type Vinyl Este
  • the average particle size, average thickness, aspect ratio and refractive index of an extender pigment such as scale-like pigment, and the hiding ratio of the dried coating of each colored anticorrosive coating having the dried coating thickness T was measured according to the following method.
  • [A] Average particle diameter, average thickness and aspect ratio of an extender pigment A particle image of the extender pigment is photographed using a powder image analyzer ("PITA-3" manufactured by Seishin Enterprise Co., Ltd.), and a photographed image obtained Among them, 50 particles taken in a direction perpendicular to the main surface of the particles were selected, and the major axis and the minor axis of each particle were measured. The average value of the major axes of the 50 particles was taken as the average particle size of the extender pigment, and the average value of the minor axes of the 50 particles was taken as the average thickness of the extender pigment. Also, the aspect ratio was calculated by dividing the average particle size by the average thickness.
  • the measurement conditions of the above-mentioned powder image analysis device are as follows.
  • Dispersion medium of sample liquid and its flow rate water, 0.42 ⁇ L / sec, -Types of first and second carrier liquids and their flow rates: water, 500 ⁇ L / sec, both -Observation magnification of photographed image: 10 times.
  • the amount ratio of the first agent (main agent) and the second agent (hardener) of the obtained two-component colored anticorrosion paint is shown in the "total" column in Table 1 or Table 2 (for example, in the case of Example 1)
  • First agent: second agent 80.67 parts by mass: 13.10 parts by mass
  • the mixture was sufficiently stirred and homogenized to obtain a mixed paint (anticorrosion paint composition).
  • the following evaluation test was done about the obtained mixed paint (anticorrosion paint composition). The test results are shown in Table 3.
  • this test plate was tested and evaluated according to ASTM G8-90. That is, first, a 6.3 mm diameter drill blade was used at the center of the immersion portion of the test surface (painted surface) of the test coating plate to produce a plate having a 6.3 mm diameter base exposed portion. Next, this plate was immersed in an aqueous solution of 40 ° C. containing 1% by mass each of NaCl, Na 2 SO 4 and Na 2 CO 3 to apply an electric potential of 1.5 V, and after 1 month, the coating from the exposed area was The length [creep width, mm] of the peeled portion of the film was measured. The numerical values (creep width) described in Table 3 are the average values of the results of immersion in the above three types of aqueous solutions.
  • each test board was immersed in 3% saline at 40 ° C. for 3 months.
  • the adhesion (MPa) to a primer-treated steel plate of a coating film after immersion for 3 months was measured using an adhesion tester made by Elcometer.
  • the test paint board was obtained by drying. Next, the test coating plate is exposed outdoors, and after providing intervals for a fixed period shown in Table 3, on the anticorrosion coating of the test coating plate, as a top coat (a) hydrolyzable acrylic resin antifouling paint “Ekoroflex” SPC 200 "(manufactured by Nippon Paint Marine Co., Ltd.) was applied by spray so as to have a dry coating thickness of about 150 ⁇ m.
  • "initial" in the "interval” column means that the top coat was applied immediately after the test panel began to be exposed outdoors.
  • the coated plate coated with the top coating was dried in a room for 24 hours.
  • this coated plate was immersed in actual seawater for 6 months, and immediately after removal, a cross cut method in accordance with JIS K 5600-5-6 was performed with a gap distance of 5 mm and a number of squares of 9, and topcoat adhesion was evaluated. . Evaluation criteria are as follows.
  • A The peeled area at the cut portion is 5% or less
  • B The peeling area at the cut portion is more than 5% and 15% or less
  • C Peeling area at the cut portion is more than 15% and 35% or less
  • D The peeled area at the cut portion is more than 35% and 65% or less.
  • topcoat paint is other than the antifouling paint composition
  • the anticorrosion paint composition according to the examples and comparative examples used as the undercoat paint was used
  • the top coat adhesion evaluation test was conducted in the same manner as in the above [3-1] except that the same paint as that used was used. At this time, the top coat was applied by spraying so that the dry film thickness was about 125 ⁇ m.
  • top coat adhesion as above except that the following (h) to (m) different from the above (g) were used as the top coat and the dry coat thickness of the top coat was as follows: Conducted a sex evaluation test. The results were the same as in the case of using the above-mentioned top coat (g).
  • the amount ratio of the first agent (main agent) and the second agent (hardener) of the obtained two-component colored anticorrosion paint is shown in the "total" column in Table 1 or Table 2 (for example, in the case of Example 1)
  • First agent: second agent 80.67 parts by mass: 13.10 parts by mass
  • the mixture was sufficiently stirred and homogenized to obtain a mixed paint (anticorrosion paint composition).
  • ⁇ E at a dry film thickness of 0 ⁇ m means the color difference between the anticorrosive coating film having a dry film thickness of T and the surface of the object to be coated (shop primer coating film surface). It is synonymous with color difference ⁇ E3.
  • Examples 27 to 48, Comparative Examples 3 to 9 Each component is mixed according to the formulation shown in Tables 7 to 9, and a first component (main component) containing a bisphenol A epoxy resin (A) and a second component containing an amine curing agent (B) (Curing agent) was prepared to obtain a two-component anticorrosion paint composition.
  • the details of each of the compounding ingredients shown in Tables 7 to 9 are as follows.
  • surface is the mass part converted into solid content.
  • Bisphenol A type epoxy resin (A): Bisphenol A type epoxy resin (solvent dilution type) manufactured by DIC Corporation, trade name “EPICLON 860-90X”, epoxy equivalent weight: 230 to 270 g / eq, number average molecular weight ( Standard polystyrene conversion by GPC measurement): 470, nonvolatile content (solid content): 90% by mass
  • Amine curing agent (B-1) Polyamide amine [Adimer acid modified aliphatic polyamido amine (amine component: mixture of triethylene tetramine and tetraethylene pentamine) manufactured by Air Products], trade name "Anchamide 2050", amine equivalent: 225 mg KOH / g, nonvolatile matter (solid content): 69% by mass
  • Amine curing agent (B-2): Polyamide amine (dimeric acid-modified aliphatic polyamido amine (amine component: pentaethylene hexamine) manufactured by Air Products Co
  • the amount ratio of the first agent (main agent) and the second agent (hardener) of the obtained two-component anticorrosion paint composition is shown in the “total” column in Tables 7 to 9 (for example, in the case of Example 27)
  • the first agent: the second agent 79.2 parts by mass: 11.5 parts by mass), and the mixture was sufficiently stirred and homogenized.
  • the following evaluation test was done about the obtained mixed paint (anticorrosion paint composition). The test results are shown in Tables 10-12. However, in Comparative Examples 6 to 8, the evaluation test can not be performed because the second agent (hardening agent) caused gelation.
  • this test plate was tested and evaluated according to ASTM G8-90. That is, first, a 6.3 mm diameter drill blade was used at the center of the immersion portion of the test surface (painted surface) of the test coating plate to produce a plate having a 6.3 mm diameter base exposed portion. Next, this plate was immersed in an aqueous solution of 40 ° C. containing 1% by weight each of NaCl, Na 2 SO 4 , and Na 2 CO 3 to apply a potential of 1.5 V, and after 1 month, the coating from the exposed area was The length [creep width, mm] of the peeled portion of the film was measured. The numerical values (creep width) described in Tables 10 to 12 are average values of the results of immersion in the above three types of aqueous solutions.
  • each test board was immersed in 3% saline at 40 ° C. for 3 months.
  • the adhesion (MPa) to a primer-treated steel plate of a coating film after immersion for 3 months was measured using an adhesion tester made by Elcometer.
  • the test paint board was obtained by drying. Next, the test coating plate is exposed outdoors, and after providing intervals of a fixed period shown in Tables 10 to 12, on the anticorrosion coating of the test coating plate, as a top coat (a) hydrolyzable acrylic resin antifouling paint "Ekoroflex SPC 200" (manufactured by Nippon Paint Marine Co., Ltd.) was applied by spray so as to have a dry coating thickness of about 150 ⁇ m.
  • "Initial" in the "Interval” column means that the top coat was applied immediately after the test coating plate began to be exposed outdoors.
  • the coated plate coated with the top coating was dried in a room for 24 hours.
  • this coated plate was immersed in actual seawater for 6 months, and immediately after removal, a cross cut method in accordance with JIS K 5600-5-6 was performed with a gap distance of 5 mm and a number of squares of 9, and topcoat adhesion was evaluated. . Evaluation criteria are as follows.
  • A The peeled area at the cut portion is 5% or less
  • B The peeling area at the cut portion is more than 5% and 15% or less
  • C Peeling area at the cut portion is more than 15% and 35% or less
  • D The peeled area at the cut portion is more than 35% and 65% or less.
  • topcoat paint is other than the antifouling paint composition
  • the anticorrosion paint composition according to the examples and comparative examples used as the undercoat paint was used
  • the top coat adhesion evaluation test was conducted in the same manner as in the above [3-1] except that the same paint as that used was used. At this time, the top coat was applied by spraying so that the dry film thickness was about 125 ⁇ m.
  • top coat adhesion as above except that the following (h) to (m) different from the above (g) were used as the top coat and the dry coat thickness of the top coat was as follows: Conducted a sex evaluation test. The results were the same as in the case of using the above-mentioned top coat (g).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Ocean & Marine Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne une peinture anticorrosion de type à deux composants, la composition comprenant un premier agent et un second agent, la composition contenant une résine époxyde bisphénol A (A), un agent durcisseur à base d'amine (B), un copolymère de chlorure de vinyle (C), un composé mono-époxyde (D) et un composé méthacrylate (E), la teneur du copolymère de chlorure de vinyle (C) est de 5 à 50 parties en masse pour 100 parties en masse de la résine époxyde bisphénol A (A), la teneur du composé mono-époxyde (D) est de 2 à 50 parties en masse par rapport à l'agent durcisseur à base d'amine (B), le premier agent contient la résine époxyde bisphénol A (A) et le copolymère de chlorure de vinyle (C), le second agent contient l'agent durcisseur à base d'amine (B) et le composé mono-époxyde (D) et le composé méthacrylate (E) contient une résine d'ester vinylique. L'invention se rapporte également à un film de revêtement formé au moyen de cette composition et un navire et une structure marine comprenant le film de revêtement.
PCT/JP2016/073321 2015-11-17 2016-08-08 Composition de peinture anticorrosion et procédé de formation de film de revêtement séché WO2017085970A1 (fr)

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Application Number Priority Date Filing Date Title
BR112017019517-8A BR112017019517B1 (pt) 2015-11-17 2016-08-08 Composição de tinta anticorrosiva, película de revestimento obtida a partir da mesma e navio ou estrutura marítima provido(a) de tal revestimento
KR1020177024081A KR101915924B1 (ko) 2015-11-17 2016-08-08 방식 도료 조성물 및 건조 도막의 형성 방법
CN201680021791.3A CN107960091B (zh) 2015-11-17 2016-08-08 防腐蚀涂料组合物和干燥涂膜的形成方法
DE112016001076.1T DE112016001076B4 (de) 2015-11-17 2016-08-08 Antikorrosive Farbzusammensetzung, Beschichtungsfilm und damit versehenes Schiff oder damit versehene Offshore-Konstruktion
SG11201706608WA SG11201706608WA (en) 2015-11-17 2016-08-08 Anticorrosive paint composition and method for forming dry coating film

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JP2015-224760 2015-11-17
JP2015224760A JP5933095B1 (ja) 2015-11-17 2015-11-17 防食塗料組成物、塗膜、船舶及び海洋構造物
JP2016131776 2016-07-01
JP2016-131776 2016-07-01

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CN111363420A (zh) * 2020-04-21 2020-07-03 青岛隆裕德机电科技有限公司 一种轨道车辆用锌黄底漆涂料及制备方法
WO2022130494A1 (fr) * 2020-12-15 2022-06-23 日本電信電話株式会社 Matériau de revêtement
CN115368803A (zh) * 2022-09-06 2022-11-22 安徽新大陆特种涂料有限责任公司 一种耐温耐酸内防腐涂料的生产方法

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KR102261877B1 (ko) * 2019-02-26 2021-06-07 주식회사 케이씨씨 분체도료 조성물
JP7146071B2 (ja) * 2019-04-12 2022-10-03 中国塗料株式会社 防食塗料組成物
CN110982378A (zh) * 2019-12-04 2020-04-10 广东华润涂料有限公司 水性环氧树脂基车间底漆
KR102164899B1 (ko) * 2020-07-08 2020-10-13 권오진 강재용 도료 조성물 및 이를 이용한 강재 도장방법

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WO2014032844A1 (fr) * 2012-08-29 2014-03-06 Hempel A/S Compositions de revêtement primaire anticorrosion à base de zinc comprenant des sphères de verre creuses et un pigment conducteur
WO2016042840A1 (fr) * 2014-09-16 2016-03-24 日本ペイントマリン株式会社 Procédé pour former un film de revêtement sec et revêtement utilisé dans ce procédé
JP5933095B1 (ja) * 2015-11-17 2016-06-08 日本ペイントマリン株式会社 防食塗料組成物、塗膜、船舶及び海洋構造物

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CN111363420A (zh) * 2020-04-21 2020-07-03 青岛隆裕德机电科技有限公司 一种轨道车辆用锌黄底漆涂料及制备方法
WO2022130494A1 (fr) * 2020-12-15 2022-06-23 日本電信電話株式会社 Matériau de revêtement
CN115368803A (zh) * 2022-09-06 2022-11-22 安徽新大陆特种涂料有限责任公司 一种耐温耐酸内防腐涂料的生产方法
CN115368803B (zh) * 2022-09-06 2023-07-18 安徽新大陆特种涂料有限责任公司 一种耐温耐酸内防腐涂料的生产方法

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DE112016001076B4 (de) 2019-10-31
KR101915924B1 (ko) 2018-11-06
SG11201706608WA (en) 2017-09-28
BR112017019517A2 (pt) 2018-04-24
DE112016001076T5 (de) 2018-01-04

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