WO2025017926A1 - 塗装システム - Google Patents

塗装システム Download PDF

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Publication number
WO2025017926A1
WO2025017926A1 PCT/JP2023/026668 JP2023026668W WO2025017926A1 WO 2025017926 A1 WO2025017926 A1 WO 2025017926A1 JP 2023026668 W JP2023026668 W JP 2023026668W WO 2025017926 A1 WO2025017926 A1 WO 2025017926A1
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WO
WIPO (PCT)
Prior art keywords
zinc
rich paint
coating layer
coating
paint
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2023/026668
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English (en)
French (fr)
Japanese (ja)
Inventor
貴志 三輪
聡 杉山
香織 根岸
梓 石井
真奈美 鳥本
憲宏 藤本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NTT Inc
Original Assignee
Nippon Telegraph and Telephone Corp
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Publication date
Application filed by Nippon Telegraph and Telephone Corp filed Critical Nippon Telegraph and Telephone Corp
Priority to JP2025533844A priority Critical patent/JPWO2025017926A1/ja
Priority to PCT/JP2023/026668 priority patent/WO2025017926A1/ja
Publication of WO2025017926A1 publication Critical patent/WO2025017926A1/ja
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • 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
    • B05D7/14—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 to metal, e.g. car bodies
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin

Definitions

  • This disclosure relates to a painting system.
  • Zinc-rich paint contains a large amount of zinc powder (hereafter referred to as "zinc dust") and is an excellent anti-corrosion paint that has two anti-corrosion effects: a "sacrificial corrosion protection effect” that makes use of the fact that zinc is a less noble metal than the substrate (e.g. steel) even if the coating is scratched to the metal substrate of the object being coated, and a "protective film effect” that causes the corrosive organisms (rust) of zinc to form a dense film that inhibits subsequent corrosion.
  • acrificial corrosion protection effect that makes use of the fact that zinc is a less noble metal than the substrate (e.g. steel) even if the coating is scratched to the metal substrate of the object being coated
  • a “protective film effect” that causes the corrosive organisms (rust) of zinc to form a dense film that inhibits subsequent corrosion.
  • Patent No. 6785382 International Publication No. 2022/003906
  • the sacrificial corrosion prevention effect will not be effective unless the paint is applied directly to the metal substrate and there is electrical conductivity between the zinc dust contained in the zinc-rich paint and the substrate being painted.
  • zinc-rich paint is often applied to galvanized steel as a replacement for zinc plating after the zinc plating has been worn away by corrosion. For these reasons, it is common practice to use zinc-rich paint for the first coating layer that is applied directly to the substrate being painted.
  • zinc-rich paint will exhibit excellent corrosion protection in the short term, but in the long term, corrosion of the zinc dust near the damaged area of the coating will progress, causing the coating to lose its sacrificial corrosion protection effect and resulting in a coating with many voids, resulting in a decrease in corrosion protection.
  • This disclosure has been made in consideration of the above circumstances, and the purpose of this disclosure is to improve the long-term corrosion resistance of zinc-rich paint, extend the interval between repainting metal substrates, and reduce the maintenance costs of metal substrates.
  • one aspect of the present disclosure is a coating system comprising at least one first coating layer formed on a surface of a metal substrate, and a zinc-rich paint coating layer containing zinc-rich paint formed on the first coating layer.
  • This disclosure makes it possible to improve the long-term corrosion resistance of zinc-rich paint, lengthen the interval between repainting metal substrates, and reduce the maintenance costs of metal substrates.
  • FIG. 1 shows an example of a coating structure according to an embodiment.
  • FIG. 2 is a schematic diagram for explaining corrosion of a metal substrate in a conventional coating structure.
  • FIG. 3 is a schematic diagram for explaining corrosion of a metal substrate in the coating structure of the embodiment.
  • FIG. 4 is a schematic diagram for explaining a damaged portion of the coating film in the sample.
  • FIG. 5 shows an example of a modified coating structure.
  • Figure 1 shows an example of a painting system of this embodiment.
  • the painting system of this embodiment relates to the order and combination of multiple paints that are applied to a metal substrate such as steel and then dried, and is also called the painting structure or painting specification.
  • the painting system will be referred to as the painting structure.
  • the coating structure of this embodiment comprises at least one first coating layer 2 formed on the surface of the metal substrate 1, which is the object to be coated, and a zinc-rich paint coating layer 3 containing zinc-rich paint, which is formed on the first coating layer 2.
  • the zinc-rich paint coating layer 3 is applied not as a first layer applied directly to the metal substrate 1, but as a second layer or later that is not in direct contact with the metal substrate 1.
  • the metal substrate 1 is, for example, steel (Fe).
  • the first coating layer 2 is formed (painted) directly on the surface of the metal substrate 1.
  • a resin coating layer can be used for the first coating layer 2.
  • paints using binders such as epoxy resin, modified epoxy resin, acrylic styrene resin, polyurethane resin, etc. are preferably used for the first coating layer 2. These paints have high blocking properties against corrosion-accelerating factors such as oxygen, water, and salt. Paints using other resins can also be used preferably as long as they do not contain zinc dust (zinc powder) and have high blocking properties against corrosion-accelerating factors.
  • the first coating layer 2 can be one layer or multiple layers.
  • the zinc-rich paint coating layer 3 is formed directly on the first coating layer 2 and contains zinc-rich paint.
  • Zinc-rich paint (ZRP) exhibits excellent corrosion resistance even when the coating is scratched to the metal substrate 1 due to its sacrificial anticorrosive action and protective coating action, and is therefore used in coating structures that require high corrosion resistance and long life.
  • the zinc-rich paint coating layer 3 may be a single layer or multiple layers.
  • the coating structure of this embodiment may also include at least one second coating layer 4 on the zinc-rich paint coating layer 3.
  • the second coating layer 4 may be formed by applying another paint on the zinc-rich paint coating layer 3.
  • the paint for the second coating layer 4 may be a highly weather-resistant topcoat paint such as a fluororesin or polyurethane resin.
  • the zinc-rich paint coating layer 3 is applied as the last (top) layer of the paint structure, corrosion of the zinc dust will always progress from the surface of the zinc-rich paint coating layer 3. For this reason, the progression of zinc dust corrosion can be prevented by applying at least one layer of another paint on top of the zinc-rich paint coating layer 3. For this reason, the progression of zinc dust corrosion can be limited to cases where the coating is scratched and the cross section of the zinc-rich paint coating layer 3 is exposed.
  • the zinc-rich paint coating layer 3 may contain at least one of calcium sulfate and a basic inorganic compound as an additive. In other words, it is possible to add a chemical to the zinc-rich paint to enhance the protective film effect.
  • the zinc-rich paint coating layer 3 may contain calcium sulfate as an additive (see Patent Document 1).
  • sulfate By adding sulfate to the zinc-rich paint, it is possible to increase the proportion of gordaite (NaZn 4 (SO 4 ) (OH) 6 Cl. 6H 2 O), which has a higher protective film effect among the zinc corrosion products.
  • the zinc-rich paint coating layer 3 may also contain a basic inorganic compound as an additive.
  • the basic inorganic compound includes an inorganic base or a basic oxide.
  • the basic inorganic compound includes, for example, at least one of barium carbonate, barium hydrogen phosphate, beryllium carbonate, calcium carbonate, calcium hydrogen phosphate, calcium phosphate, lithium carbonate, lithium phosphate, magnesium carbonate, basic magnesium carbonate, magnesium hydroxide, magnesium oxide, and magnesium phosphate.
  • Basic magnesium carbonate does not raise the pH too much even when added until the solution becomes saturated, does not dissolve zinc powder, which is an amphoteric metal, and has a moderate solubility in pure water (0.025 g/100 mL at 25°C). For this reason, basic magnesium carbonate can gradually supply hydroxide ions over a long period of time.
  • Patent Documents 1 and 2 zinc-rich paint containing these additives is applied directly to the metal substrate 1 as the first layer of coating.
  • This has the advantage that the additives dissolve in water and supply sulfate ions or hydroxide ions to damaged areas of the coating, further enhancing the protective coating effect of zinc.
  • the zinc-rich paint as a layer other than the first layer that is applied directly to the metal substrate 1, it is possible to minimize the disadvantage of the zinc-rich paint's reduced environmental barrier properties while retaining the advantage of increasing the protective coating effect of zinc.
  • the zinc-rich paint coating layer 3 by applying the zinc-rich paint coating layer 3 to a layer other than the first layer that is applied directly to the metal substrate 1, the disadvantage of the zinc-rich paint coating layer 3 being reduced in its environmental barrier properties is reduced, and the advantage of being able to efficiently supply the active ingredients to damaged areas of the coating is increased.
  • the zinc-rich paint of this embodiment is preferably an organic zinc-rich paint with an organic binder (e.g., epoxy resin, modified epoxy resin, acrylic styrene resin, polyurethane resin, etc.). Whereas the coating of an inorganic zinc-rich paint with an inorganic binder has a certain amount of voids from the beginning, the coating of an organic zinc-rich paint does not have voids from the beginning.
  • an organic binder e.g., epoxy resin, modified epoxy resin, acrylic styrene resin, polyurethane resin, etc.
  • the advantage that the first layer applied directly to the metal substrate 1 "does not become a coating with many voids even over a long period of time" is greater in the case of organic zinc-rich paint.
  • the paint structure of this embodiment uses a combination and order of multiple paints that are applied to a metal substrate 1 such as a steel plate and then dried, and the paints used include zinc-rich paint, which is applied to layers other than the first layer that is applied directly to the metal substrate 1.
  • zinc-rich paint exhibits excellent corrosion protection in the short term due to its sacrificial corrosion protection and protective film action.
  • the corrosion of the zinc dust near the damaged part 80 of the coating progresses, and the zinc-rich paint 81 near the damaged part 80 of the zinc-rich paint coating layer 3 loses its sacrificial corrosion protection action and becomes a coating with many voids.
  • the corrosion products of the zinc dust fill the voids to a certain extent, the coating still has many voids, and the metal substrate 1 becomes susceptible to corrosion, so the corrosion protection of the zinc-rich paint is reduced.
  • the part 82 of the metal substrate 1 that is in contact with the zinc-rich paint 81 with many voids near the damaged part 80 of the coating is susceptible to corrosion.
  • the zinc-rich paint coating layer 3 is formed other than the first layer that is applied directly to the metal substrate 1.
  • corrosion of the zinc dust near the damaged part 70 of the coating progresses over a long period of time, and the zinc-rich paint 71 near the damaged part 70 of the coating loses its sacrificial anticorrosive effect and becomes a coating with many voids.
  • the first layer that is applied directly to the metal substrate 1 becomes a coating with many voids
  • the zinc-rich paint 71 near the damaged part 70 of the zinc-rich paint coating layer 3 formed other than the first layer becomes a coating with many voids, the decrease in corrosion prevention properties is relatively small.
  • the zinc-rich paint coating layer 3 becomes more susceptible to water penetration, which has the advantage of increasing the amount of active ingredients (Zn 2+ , Ca 2+ , Mg 2+ , OH - , SO 4 2-, etc.) supplied to the damaged part 70 to produce a protective film effect. Therefore, even if the zinc-rich paint 71 near the damaged part 70 becomes a coating with many voids, there is little disadvantage, and there is the advantage of being able to supply a large amount of ingredients to generate a protective film.
  • the sacrificial anticorrosive effect of the zinc-rich paint is lost, if the coating is scratched to the metal substrate 1, the first layer in direct contact with the metal substrate 1 can be prevented from becoming a coating with many voids.
  • the protective coating effect is exerted by the zinc ions supplied by corrosion of the zinc dust of the zinc-rich paint applied to layers other than the first layer in direct contact with the metal substrate 1. This makes it possible to extend the interval for repainting metal substrates 1 such as infrastructure steel structures, and reduce the maintenance costs of the metal substrate 1.
  • a blast-treated SS400 steel plate measuring 150 x 70 x 3 mm was used as the metal substrate 1
  • a thick-film modified epoxy resin paint (Rubigol G, Kansai Paint Co., Ltd.) was used as the first coating layer 2
  • an organic zinc-rich paint (SD Zinc Mild 500, Kansai Paint Co., Ltd.) was used as the zinc-rich paint coating layer 3
  • a topcoat paint (Unitect 30SF, Kansai Paint Co., Ltd.) was used as the second coating layer 4.
  • a thick-film modified epoxy resin paint was applied to a thickness of 120 ⁇ m on an SS400 steel plate as the first layer
  • zinc-rich paint was applied to a thickness of 40 ⁇ m on top of that as the second layer
  • silicone epoxy resin paint was applied to a thickness of 55 ⁇ m on top of that as the third layer of topcoat paint.
  • Experimental Example 1 and Comparative Example 1 are samples with a paint structure in which no additives are added to the zinc-rich paint.
  • Experimental Example 2 and Comparative Example 2 are samples with a paint structure in which 2 wt% calcium sulfate (dihydrate) is added as an additive.
  • Experimental Example 3 and Comparative Example 3 are samples with a paint structure in which 4 wt% basic magnesium carbonate is added as an additive.
  • Experimental Example 4 and Comparative Example 4 are samples with a paint structure in which 2 wt% calcium sulfate (dihydrate) and 4 wt% basic magnesium carbonate are added as additives.
  • Example 1 and Comparative Example 1 First, the corrosion at the damaged paint film areas of Example 1 and Comparative Example 1 will be compared. At the 200th cycle, red rust was observed in Example 1, whereas no red rust was observed in Comparative Example 1, and the degree of corrosion was milder in Comparative Example 1. However, after 600 cycles, red rust derived from the steel flowed downward from the damaged paint film areas in both Example 1 and Comparative Example 1 (hereinafter referred to as "rust flow”), but the degree of corrosion was clearly milder in Example 1.
  • rust flow red rust derived from the steel flowed downward from the damaged paint film areas in both Example 1 and Comparative Example 1
  • Comparative Example 1 shows that in the early stages up to 200 cycles, Comparative Example 1, where the zinc-rich paint was in direct contact with the steel, provided better corrosion protection due to the sacrificial corrosion protection effect.
  • the areas where zinc dust was present in the zinc-rich paint in direct contact with the steel in Comparative Example 1 became voids containing zinc corrosion products, resulting in a disadvantage in that the environmental barrier properties of the zinc-rich paint (its ability to block the passage of water, oxygen, salt, etc.) were reduced.
  • Example 1 the sacrificial corrosion protection effect was not exhibited in the early stages, but since the zinc-rich paint was not in direct contact with the steel material, the disadvantage that the areas where zinc dust was present in the zinc-rich paint turned into voids containing zinc corrosion products was not as great as in Comparative Example 1, and it is believed that Example 1 was superior in terms of long-term corrosion protection.
  • Example 2 and Comparative Example 2 Next, the corrosion at the damaged part of the coating is compared between Example 2 and Comparative Example 2.
  • the zinc-rich paint used in Example 2 and Comparative Example 2 is a zinc-rich paint with improved corrosion resistance by adding calcium sulfate. The amount of calcium sulfate added is 2 wt%.
  • Comparative Example 2 had an increased proportion of gordite due to sulfate ions leached from the calcium sulfate, resulting in an enhanced protective coating effect.
  • Comparative Example 2 in the long term, in Comparative Example 2, the areas where calcium sulfate was present in the zinc-rich paint that was in direct contact with the steel material became voids, resulting in a disadvantage in that the environmental barrier properties of the coating were reduced.
  • Example 2 the zinc-rich paint is not in direct contact with the steel material. For this reason, the disadvantage of gaps forming in the zinc-rich paint where calcium sulfate was present is not as great as in Comparative Example 2, and it is believed that Example 2 is superior in terms of long-term corrosion prevention.
  • Example 3 and Comparative Example 3 Next, the corrosion at the damaged part of the coating is compared between Example 3 and Comparative Example 3.
  • the zinc-rich paint used in Example 3 and Comparative Example 3 has improved corrosion prevention properties due to the addition of basic magnesium carbonate.
  • the amount of basic magnesium carbonate added is 4 wt%.
  • Comparative Example 3 had the effect of lowering the corrosion rate of zinc dust and increasing the proportion of gordaite, due to an increase in pH caused by hydroxide ions leached from the basic magnesium carbonate, enhancing the protective coating effect.
  • Comparative Example 3 in the long term, in Comparative Example 3, the areas where basic magnesium carbonate was present in the zinc-rich paint that was in direct contact with the steel material became voids, resulting in the disadvantage of a reduced environmental barrier property of the coating.
  • Example 3 the zinc-rich paint is not in direct contact with the steel material. For this reason, the disadvantage of voids in the zinc-rich paint where basic magnesium carbonate was present is not as great as in Comparative Example 3, and it is believed that Example 3 was superior in terms of long-term corrosion prevention.
  • Example 4 and Comparative Example 4 Next, the corrosion at the damaged part of the coating is compared between Example 4 and Comparative Example 4. Both calcium sulfate and basic magnesium are added to the zinc-rich paint used in Example 4 and Comparative Example 4. The amount of calcium sulfate added is 2 wt%, and the amount of basic magnesium carbonate added is 4 wt%.
  • Example 4 At 200 cycles, no red rust occurred in the damaged areas of the coating in either Example 4 or Comparative Example 4. After 600 cycles, flowing rust occurred in Comparative Example 4, while light spot-like red rust occurred in Example 4, with the degree of corrosion being significantly milder in Example 4. This is because, in Comparative Example 4, corrosion in the damaged areas of the coating progressed considerably between 200 and 600 cycles, whereas in Example 4, corrosion in the damaged areas of the coating did not progress very much between 200 and 600 cycles.
  • Comparative Examples 1 to 4 where the zinc-rich paint was in direct contact with the steel, provided better corrosion protection due to the sacrificial corrosion protection effect.
  • the areas where zinc dust was present in the zinc-rich paint that was in direct contact with the steel in Comparative Examples 1 to 4 became voids containing zinc corrosion products, resulting in a disadvantage in that the environmental barrier properties of the zinc-rich paint were reduced.
  • Examples 1 to 4 the initial sacrificial corrosion protection effect was not exhibited, but since the zinc-rich paint was not in direct contact with the steel material, the disadvantage that the areas where zinc dust was present in the zinc-rich paint became voids containing zinc corrosion products was not as great as in Comparative Examples 1 to 4. For this reason, it is believed that Examples 1 to 4 were superior in terms of long-term corrosion protection.
  • Example 4 calcium sulfate and basic magnesium carbonate were added to the zinc-rich paint coating layer 3, but calcium sulfate and basic magnesium carbonate may be formed as additives in a layer other than the zinc-rich paint coating layer 3. If the coating layer containing such additives is scratched and calcium sulfate and basic magnesium carbonate are dissolved and lost from the cross section of the damaged part of the coating due to rainfall or condensation, the coating layer will become porous. For this reason, it is recommended to avoid using the coating layer containing additives as the first layer to be directly applied to the metal substrate 1.
  • Figure 5 is a diagram showing an example of a modified coating structure.
  • the coating structure shown in the figure comprises at least one first coating layer 2 (e.g., a resin coating layer containing an epoxy resin) formed on the surface of a metal substrate 1 (object to be coated), a zinc-rich paint coating layer 3 containing zinc-rich paint formed on the first coating layer, a third coating layer 5 containing calcium sulfate and basic magnesium carbonate formed on the zinc-rich paint coating layer 3, and a second coating layer 4 (topcoat coating layer) formed on the third coating layer.
  • first coating layer 2 e.g., a resin coating layer containing an epoxy resin
  • a zinc-rich paint coating layer 3 containing zinc-rich paint formed on the first coating layer
  • a third coating layer 5 containing calcium sulfate and basic magnesium carbonate formed on the zinc-rich paint coating layer 3
  • a second coating layer 4 topcoat coating layer
  • the coating structure of the modified example includes a third coating layer 5 containing calcium sulfate and basic magnesium carbonate as additives for zinc-rich paint, and the third coating layer 5 is formed on the zinc-rich paint coating layer 3.
  • the third coating layer 5 may be made of an epoxy resin paint containing calcium sulfate and basic magnesium carbonate.
  • the first coating film layer 2 and the second coating film layer 4 are the same as the first coating film layer 2 and the second coating film layer 4 in the embodiment shown in Figure 1.
  • Metal base material 2 First coating layer (resin coating layer) 3: Zinc rich paint coating layer 4: Second coating layer (top coating layer) 5: Third coating layer

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PCT/JP2023/026668 2023-07-20 2023-07-20 塗装システム Pending WO2025017926A1 (ja)

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JP2025533844A JPWO2025017926A1 (https=) 2023-07-20 2023-07-20
PCT/JP2023/026668 WO2025017926A1 (ja) 2023-07-20 2023-07-20 塗装システム

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020008753A1 (ja) * 2018-07-02 2020-01-09 日本電信電話株式会社 塗料
WO2022003906A1 (ja) * 2020-07-02 2022-01-06 日本電信電話株式会社 塗料

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020008753A1 (ja) * 2018-07-02 2020-01-09 日本電信電話株式会社 塗料
WO2022003906A1 (ja) * 2020-07-02 2022-01-06 日本電信電話株式会社 塗料

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