WO2023190795A1 - Couche de film de revêtement - Google Patents

Couche de film de revêtement Download PDF

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Publication number
WO2023190795A1
WO2023190795A1 PCT/JP2023/013033 JP2023013033W WO2023190795A1 WO 2023190795 A1 WO2023190795 A1 WO 2023190795A1 JP 2023013033 W JP2023013033 W JP 2023013033W WO 2023190795 A1 WO2023190795 A1 WO 2023190795A1
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WIPO (PCT)
Prior art keywords
oil
coating layer
group
component
amount
Prior art date
Application number
PCT/JP2023/013033
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English (en)
Japanese (ja)
Inventor
憲一 江口
愛佳 石井
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日東電工株式会社
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Publication of WO2023190795A1 publication Critical patent/WO2023190795A1/fr

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Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09D7/65—Additives macromolecular

Definitions

  • the present invention relates to a coating layer, and more specifically, the present invention relates to a coating layer that prevents snow from forming on the surface of objects such as solar panels, aircraft, railways, automobiles, wind power generators, houses, traffic lights, signboards, tunnels, snow eaves prevention boards, bridges, and road signs. It relates to a coating layer used to prevent ice from adhering.
  • oil-containing paints and coating layers have been developed in various industrial fields as a measure to prevent snow and ice from accreting on the surfaces of objects.
  • Patent Document 1 discloses an anti-icing and snow coating composition containing chemically reactive silicone rubber and silicone oil.
  • the present invention has been made in view of the above-mentioned conventional circumstances, and provides a coating layer that causes less contamination of coated objects even in low-temperature environments and has excellent icing and/or snow accumulation prevention functions. This is an issue that must be solved.
  • the coating layer is left at -20°C for 16 hours, and the oil component that bleeds onto the surface of the coating layer is collected using a cell scraper in an environment of -20°C.
  • the collected oil component is absorbed using oil-absorbing paper until no change in the mass of the oil-absorbing paper is observed.
  • Oil collection with a cell scraper and blotting with oil-blotting paper are repeated 7 times per minute.
  • the difference in mass between the oil-blotting paper before and after oil-blotting is defined as the amount of surface oil.
  • the amount of surface oil is measured three times and the average value is used. (Measurement method of icing force)
  • the coating layer was attached to a stainless steel flat plate so that the coating layer was on the surface, and the plate was left standing in a -20°C environment for 16 hours.
  • a cylindrical block of ice having a weight of 6 g and an adhering area of 4.9 cm 2 is prepared, and the bottom surface of the block of ice is brought into contact with a surface kept at a constant temperature of 10° C. for 10 seconds to adhere to the coating layer.
  • the environmental temperature was set to -20°C, and 3 hours after the ice block was attached, in an environment of -20°C, the ice block was pushed from a direction parallel to the floor surface using a load cell at a speed of 0.1 mm/sec.
  • the load applied during 40 seconds is measured with a force gauge.
  • the value obtained by dividing the measured maximum load by the adhesion area of 4.9 cm 2 is defined as the icing force.
  • the icing force was measured three times and the average value was used.
  • the coating layer of the present invention causes less contamination of the coated object even in a low-temperature environment and has an excellent function of preventing icing and/or snow accretion.
  • FIG. 1 is a sectional view showing the coating layer of the present invention together with an object to be coated.
  • FIG. 2 is a cross-sectional view showing an example of a layer structure including a coating layer of the present invention together with an object to be coated.
  • the coating layer of the present invention is a coating layer containing a resin component and at least one oil component, and the oil component has a hydrophilic group, and the coating layer is measured by the method described below.
  • the amount of surface oil is less than 40 ⁇ g/cm 2
  • the icing force of the coating layer measured by the method described below is 0.7 N/cm 2 or less.
  • the coating layer of the present invention contains a resin component and at least one oil component.
  • the resin component may be any of a moisture-curable resin that is cured by moisture, an ultraviolet-curable resin that is cured by ultraviolet irradiation, and a thermosetting resin that is cured by heating. Further, the resin component may be a resin or a thermoplastic resin that is cured by adding a curing agent that crosslinks with the resin component.
  • the resin component is not particularly limited, but includes, for example, silicone resin, polyurethane resin, polyurethane acrylic resin, vinyl chloride resin, polyester resin, elastomers, fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.), acrylic resin, Examples include EPDM (ethylene propylene diene rubber), SEBS (styrene thermoplastic elastomer), and SBR (styrene butadiene rubber).
  • any suitable silicone resin may be employed as long as the effects of the present invention are not impaired.
  • the number of silicone resins may be one, or two or more.
  • Such silicone resin may be a condensation type silicone resin or an addition type silicone resin.
  • such silicone resin may be a one-component silicone resin that is dried alone (for example, a one-component room temperature curable (RTV) resin), or a two-component silicone resin (for example, a one-component room temperature curable (RTV) resin). , two-component room temperature curable (RTV) resin).
  • silicone resin examples include one-component RTV rubber manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KE-3423, KE-347, KE-3475, KE-3495, KE-4895, KE-4896, KE-1830, KE-1884, KE-3479, KE-348, KE-4897, KE-4898, KE-1820, KE-1825, KE-1831, KE-1833, KE-1885, KE-1056, KE-1151, KE- 1842, KE-1886, KE-3424G, KE-3494, KE-3490, KE-40RTV, KE-4890, KE-3497, KE-3498, KE-3493, KE-3466, KE-3467, KE-1862, KE-1867, KE-3491, KE-3492, KE-3417, KE-3418, KE-3427, KE-3428, KE-
  • KE-1800T-A/B, KE-66, KE-1031-A/B, KE-200, KE-118) , KE-103, KE-108, KE-119, KE-109E-A/B, KE-1051J-A/B, KE-1012-A/B, KE-106, KE-1282-A/B, KE -1283-A/B, KE-1800-A/B/C, KE-1801-A/B/C, KE-1802-A/B/C, KE-1281-A/B, KE-1204-A /B, KE-1204-AL/BL, KE-1280-A/B, KE-513-A/B, KE-521-A/B, KE-1285-A/B, KE-1861-A/B , KE-12, KE-14, KE-17, KE-113, KE-24, KE-26, KE-1414, KE-1415, KE-1416,
  • KEG-2000-40A/B KEG-2000-50A/B, KEG-2000-60A/B, KEG-2000-70A/B, KEG-2001-40A/B, KEG-2001-50A/B, KE-1950-10A/B, KE-1950-20A/B, KE-1950-30A/B, KE-1950-35A/B, KE- 1950-40A/B, KE-1950-50A/B, KE-1950-60A/B, KE-1950-70A/B, KE-1935A/B, KE-1987A/B, KE-1988A/B, KE- 2019-40A/B, KE-2019-50A/B, KE-2019-60A/B, KE-2017-30A/B, KE-2017-40A/B, KE-2017-50A/B, KE-2090- 40A/B, KE-2090-50A/B, KE-2090-60A/B, KE-2090-70A/B, KE-2096-40A
  • the content of the resin component in the coating layer of the present invention is preferably 15% by mass or more, more preferably 25% by mass or more, and still more preferably 35% by mass or more. Further, the content of the resin component in the coating layer of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.
  • the coating layer of the present invention contains at least one oil component.
  • the oil component has hydrophilic groups.
  • the oil component does not exude from the coating layer of the present invention in air at a temperature of -20°C.
  • oil component for example, silicone oil, fluorine oil, hydrocarbon oil, polyether oil, ester oil, phosphorus compound oil, mineral oil, alcohol, etc. can be used.
  • silicone oil examples include silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF -56A, KF-6000, KF-6001, KF-6002, KF-6003, etc.), silicone oil manufactured by Momentive Corporation (e.g. Element14*PDMS series, TSF404 series, TSF410 series, TSF4300 series, TSF431 series, TSF433 series) , TSF437 series, TSF4420 series, TSF4421 series, etc.), silicone oil manufactured by Dow Corning Toray Co., Ltd.
  • silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. for example, KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, K
  • WACKER registered trademark
  • SILICONE FLUID AK series WACKER (registered trademark) SILICONE FLUID AP series
  • WACKER registered trademark
  • SILICONE FLUID AR series WACKER (registered trademark) SILICONE FLUID AR series
  • WACKER registered trademark
  • SILICONE FLUID AS series WACKER (registered trademark)
  • WACKER registered trademark
  • TN series WACKER (registered trademark) TN series
  • WACKER registered trademark) L series
  • WA CKER registered trademark Liquid paraffin such as AF series
  • Preferred hydrophilic groups possessed by the oil component include, for example, at least one group selected from the group consisting of carbinol groups, hydroxy groups, carboxy groups, amino groups, sulfo groups, ether groups, and ester groups. .
  • carbinol groups are more preferred from the viewpoint of exhibiting excellent icing and/or snow accretion prevention functions.
  • the number average molecular weight of the oil component is preferably 2000 or more. If the number average molecular weight of the oil component is 2,000 or more, excellent icing and/or snow accretion prevention function can be exhibited.
  • the number average molecular weight of the oil component is more preferably 2,500 or more, still more preferably 3,000 or more. Further, the number average molecular weight of the oil component is more preferably 20,000 or less, still more preferably 10,000 or less. Note that the number average molecular weight of the oil component can be measured by the method described in Examples.
  • the resin component is an addition-type silicone resin with a curing agent ratio of 0.8 or more and less than 1.4
  • the oil component is a carbinol-modified silicone oil with both ends modified
  • the number average molecular weight of the oil component is 2100 to 10000.
  • the content of the oil component in the coating layer of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. Further, in this case, the content of the oil component in the coating layer of the present invention is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.
  • the resin component is an addition type silicone resin with a curing agent ratio of 1.4 or more and 5.0 or less
  • the oil component is a carbinol-modified silicone oil with a modified type at both ends
  • the number average molecular weight of the oil component is 100 to 2000.
  • the content of the oil component in the coating layer of the present invention is preferably 3% by mass or more, more preferably 4% by mass or more, and still more preferably 5% by mass or more. Further, in this case, the content of the oil component in the coating layer of the present invention is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
  • the resin component is an addition type silicone resin with a curing agent ratio of 1.4 or more and 5.0 or less
  • the oil component is a carbinol-modified silicone oil with both terminals modified
  • the number average molecular weight of the oil component is 2,100 to 10,000.
  • the content of the oil component in the coating layer of the present invention is preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more.
  • the content of the oil component in the coating layer of the present invention is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.
  • only one type of oil component may be used, or two or more types may be used.
  • the ratio of the amount (mol) of reactive groups of the curing agent to the amount (mol) of reactive groups possessed by the resin component is preferably 1.4 or more.
  • the curing agent preferably has a hydrosilyl group.
  • the curing agent has a hydrosilyl group, and the ratio of the amount (mol) of reactive groups of the curing agent to the amount (mol) of reactive groups possessed by the resin component is 1.4 or more. It is thought that the hydrosilyl group of the curing agent and the resin component react, and further the hydrosilyl group of the curing agent and the oil component react, and the oil component is incorporated into the resin component. As a result, it is thought that the bleeding of oil components in a low-temperature environment is suppressed, and the object to be coated is not contaminated.
  • the curing agent and the oil component are combined in the coating layer of the present invention. Further, it is preferable that the curing agent and the resin component are combined.
  • Examples of the curing agent include those whose main chain is a repeating unit of diorganosiloxane and whose terminal end is a triorganosiloxane structure, and may have a branched or cyclic structure.
  • Examples of the organo group bonded to silicon at the terminal or in the repeating unit include methyl group, ethyl group, octyl group, phenyl group, etc.
  • a curing agent in which two or more of these groups are substituted with hydrogen is preferred.
  • Specific examples include hydrogen silicone and the like.
  • Specific curing agents include, for example, cat-1310s, KF-99, and KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., and HMS-151, HMS-301, and HMS-501 manufactured by Gelest.
  • the ratio of the amount of reactive groups (moles) in the curing agent to the amount (moles) of reactive groups in the resin component is more preferably 1.6 or more, and still more preferably 2.0 or more. Further, the ratio of the amount (mol) of reactive groups of the curing agent to the amount (mol) of reactive groups possessed by the resin component is preferably 6 or less, more preferably 4 or less.
  • silane coupling agent At least one silane coupling agent may be added to the resin component of the present invention.
  • the silane coupling agent include those having as a functional group at least one group selected from the group consisting of isocyanate groups, vinyl groups, epoxy groups, amino groups, and mercapto groups, acid anhydrides, and the like. .
  • silane coupling agent examples include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, and isocyanatemethyldimethoxymethylsilane. etc.
  • silane coupling agent examples include vinyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, -aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and the like.
  • the silane coupling agent is preferably used in combination with a curing agent.
  • a curing agent By combining the silane coupling agent and the curing agent, the anti-icing and/or snow accretion function of the formed coating layer and the adhesion to the substrate are improved. The reason for this is not clear, but it is speculated that in addition to the hydrosilyl group, the functional groups of the silane coupling agent react and/or interact with the functional groups of the base material, resulting in improved adhesion. .
  • the silane coupling agent reacts with the hydrosilyl group of the resin component, the hydrosilyl group of the resin component and the hydrophilic group of the oil component can prevent the oil component from seeping out from the coating layer under low temperature conditions. It is thought that this reaction can be suppressed. As a result, it is possible to provide a coating layer that has excellent adhesion to the substrate and has an excellent ability to prevent icing and/or snow accretion.
  • a resin containing the silane coupling agent in advance may be used, or an additional silane coupling agent independent of the resin may be added.
  • resins that contain a silane coupling agent in advance include KE-2098-60A/B.
  • an additional silane coupling agent may be added independently from this resin.
  • the content of the silane coupling agent in the coating layer of the present invention is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, and even more preferably 0.15 parts by mass, based on 100 parts by mass of the resin. It is more than 100%. Further, the content of the silane coupling agent in the coating layer of the present invention is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 6 parts by mass or less, based on 100 parts by mass of the resin. . In addition, only one type of silane coupling agent may be used, or two or more types may be used.
  • the coating material for forming the coating layer of the present invention can contain a solvent.
  • solvents include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, hydrocarbon solvents such as hexane, octane, decane, and isoparaffin, and ketone solvents such as acetone and methyl ethyl ketone. Examples include solvents.
  • the coating material of the present invention can further contain a curing catalyst.
  • a curing catalyst for example, platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, hexachloride platinum (IV) acid, chlorotris (triphenylphosphine) rhodium (I) Examples include metal catalysts such as.
  • the paint of the present invention can further contain fillers such as silica, talc, calcium carbonate, titanium oxide, clay, and pigments.
  • silica for example, silica manufactured by Nippon Aerosil Co., Ltd. (for example, AEROSIL50, 130, 200, 300, R972, R974, R976, RX50, RX200, RX300, RY50, RY300, R7200, R8200, R9200), etc. may be used. I can do it.
  • the coating material of the present invention may contain any other appropriate additives as long as the effects of the present invention are not impaired.
  • examples of such other additives include weathering agents, ultraviolet absorbers, and light stabilizers. Ultraviolet absorbers and light stabilizers are highly effective when used together.
  • ultraviolet absorbers include ADEKA LA-24, LA-29, LA-31, LA-31RG, LA-31G, LA-32, LA-36, LA-46, LA-F70, 1413, BASF TinuvinPS, Tinuvin99-2, Tinuvin326, Tinuvin384-2, Tinuvin900, Tinuvin928, Tinuvin970, Tinuvin1130, Tinuvin400, Tinuvin405, Ti Examples include nuvin460, Tinuvin477, Tinuvin479, UVA-903KT, UVA-935LH, and the like.
  • light stabilizers include LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, and LA- manufactured by ADEKA. 87, LA-402AF, LA-40MP, LA-40Si, BASF Tinuvin111, Tinuvin123, Tinuvin144, Tinuvin152, Tinuvin249, Tinuvin292, Tinuvin770DF, Tinuvin5 100, etc.
  • the coating material of the present invention can be obtained by mixing and/or stirring the above-mentioned components by a known method.
  • the coating layer of the present invention preferably has a surface oil amount of less than 40 ⁇ g/cm 2 as measured by the method described below.
  • the amount of surface oil is more preferably less than 30 ⁇ g/cm 2 , even more preferably less than 20 ⁇ g/cm 2 . Further, the amount of surface oil is preferably as small as possible, but may be, for example, 10 ⁇ g/cm 2 or more.
  • the coating layer is left at -20°C for 16 hours, and the oil component that bleeds onto the surface of the coating layer is collected using a cell scraper in an environment of -20°C.
  • the collected oil component is absorbed using oil-absorbing paper until no change in the mass of the oil-absorbing paper is observed.
  • Oil collection with a cell scraper and blotting with oil-blotting paper are repeated 7 times per minute.
  • the difference in mass between the oil-blotting paper before and after oil-blotting is defined as the amount of surface oil.
  • the amount of surface oil is measured three times and the average value is used.
  • the coating layer of the present invention preferably has an icing force of 0.7 N/cm 2 or less as measured by the method below.
  • the coating layer was attached to a stainless steel flat plate so that the coating layer was on the surface, and the plate was left standing in a -20°C environment for 16 hours.
  • a cylindrical block of ice having a weight of 6 g and an adhesion area of 4.9 cm 2 is prepared, and the bottom surface of the block of ice is brought into contact with a surface kept at a constant temperature of 10° C. for 10 seconds to adhere to the coating layer.
  • the environmental temperature was set to -20°C, and 3 hours after the ice block was attached, the ice block was pushed at a speed of 0.1 mm/sec with a load cell from a direction parallel to the floor surface in an environment of -20°C.
  • the load applied during 40 seconds is measured with a force gauge.
  • the value obtained by dividing the measured maximum load by the adhesion area of 4.9 cm 2 is defined as the icing force.
  • the icing force was measured three times and the average value was used.
  • 10° C. constant temperature surface refers to the surface of a device whose temperature can be changed using, for example, a Peltier element, and is used to partially melt the bottom of the ice block.
  • the icing force is 0.7 N/cm 2 or less, excellent icing and/or snow accretion prevention function can be exhibited.
  • the icing force is more preferably 0.6 N/cm 2 or less, still more preferably 0.5 N/cm 2 or less. Further, the icing force is preferably as small as possible, but may be, for example, 0.2 N/cm 2 or more, or 0.4 N/cm 2 or more.
  • another embodiment of the coating layer of the present invention is a coating layer containing a resin component and at least one oil component, and the amount of surface oil of the coating layer measured by the above method is 40 ⁇ g/
  • the icing force of the coating layer , measured by the above method, is preferably less than 0.3 N/cm 2 .
  • a first coating layer 11 can be obtained by applying the paint of the present invention to an object 10 to be coated.
  • a method for applying the paint of the present invention general methods such as brush painting, spray painting, and various types of coater painting can be used. Painting is usually done once or twice.
  • a primer is applied to the object 10 to be coated, and the primer is coated on top of the primer.
  • the paint of the present invention may be applied from.
  • the thickness of the first coating layer 11 is not particularly limited, but from the viewpoint of the quality of the dried coating film, it is preferably 2000 ⁇ m or less, and from the viewpoint of strength, it is preferably 50 ⁇ m or more.
  • coated object 10 used in the present invention examples include polyurethane resins, polyurethane acrylic resins, rubber resins, vinyl chloride resins, polyester resins, silicone resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, etc.). ), metal plates or metal foils (aluminum, copper, silver, iron, nickel, tin, stainless steel, etc.), concrete, ceramics, etc. can be used. Further, the object to be coated 10 may be in the form of a film or a sheet.
  • the coating material of the present invention After the coating material of the present invention is applied to the object to be coated 10, the coating material can be cured or dried by allowing it to stand in an environment of, for example, 20 to 180° C. for, for example, 3 minutes to 3 hours.
  • a top coat can be applied as necessary on the first coating layer 11 obtained from the paint of the present invention to form a second coating layer 12.
  • the top coat There are no particular limitations on the top coat, and for example, the same paint as the paint of the present invention can be used, but the top coat does not need to contain an oil component.
  • top coat As a method for applying the top coat, general methods such as brush painting, spray painting, and various coater coatings can be used. Painting is usually done once or twice.
  • the thickness of the second coating layer 12 is not particularly limited, but should be such that the oil component can easily permeate to the surface of the coating layer, in other words, ensuring oil permeability to the second coating layer 12. Therefore, it is preferably 500 ⁇ m or less, and from the viewpoint of strength, it is preferably 50 ⁇ m or more.
  • the curing or drying temperature and curing or drying time when applying the top coat to the first coating layer 11 are the curing or drying temperature and curing or drying time when applying the coating of the present invention to the object to be coated 10. It is similar to The curing or drying of the paint of the present invention and the curing or drying of the top coat may be performed simultaneously or separately.
  • the oil component has a hydrophilic group
  • the amount of surface oil of the coating layer measured by the following method is less than 40 ⁇ g/cm 2
  • the coating layer has an icing force of 0.7 N/cm 2 or less as measured by the following method. (Method for measuring surface oil amount)
  • the coating layer is left at -20°C for 16 hours, and the oil component that bleeds onto the surface of the coating layer is collected using a cell scraper in an environment of -20°C.
  • the collected oil component is absorbed using oil-absorbing paper until no change in the mass of the oil-absorbing paper is observed.
  • Oil collection with a cell scraper and blotting with oil-blotting paper are repeated 7 times per minute.
  • the difference in mass between the oil-blotting paper before and after oil-blotting is defined as the amount of surface oil.
  • the amount of surface oil is measured three times and the average value is used. (Measurement method of icing force)
  • the coating layer was attached to a stainless steel flat plate so that the coating layer was on the surface, and the plate was left standing in a -20°C environment for 16 hours.
  • a cylindrical block of ice having a weight of 6 g and an adhesion area of 4.9 cm 2 is prepared, and the bottom surface of the block of ice is brought into contact with a surface kept at a constant temperature of 10° C. for 10 seconds to adhere to the coating layer.
  • the environmental temperature was set to -20°C, and 3 hours after the ice block was attached, the ice block was pushed at a speed of 0.1 mm/sec with a load cell from a direction parallel to the floor surface in an environment of -20°C.
  • the load applied during 40 seconds is measured with a force gauge.
  • the value obtained by dividing the measured maximum load by the adhesion area of 4.9 cm 2 is defined as the icing force.
  • the icing force was measured three times and the average value was used.
  • ⁇ 3> The coating layer according to ⁇ 1> or ⁇ 2>, wherein the ratio of the amount (mol) of reactive groups of the curing agent to the amount (mol) of reactive groups possessed by the resin component is 1.4 or more.
  • ⁇ 4> ⁇ 1> to ⁇ 3>, wherein the hydrophilic group is at least one group selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, an amino group, a sulfo group, an ether group, and an ester group.
  • ⁇ 5> A paint for forming a coating layer according to any one of ⁇ 1> to ⁇ 4>.
  • resin component silicone resin "KE-1935" (manufactured by Shin-Etsu Chemical Co., Ltd.), first oil component (incompatible oil): carbinol-modified silicone oil "KF-6003" (manufactured by Shin-Etsu Chemical Co., Ltd.). (manufactured by Shin-Etsu Chemical Co., Ltd.) and second oil component (compatible oil): dimethylsiloxane oil "KF-96 (50cs)” (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a resin component (50 parts by mass), a first oil component (25 parts by mass), and a second oil component (25 parts by mass) were mixed under conditions of 25° C. and 101 kPa.
  • the resulting mixed solution was stirred for 60 seconds with a spatula, and further stirred for 120 seconds and defoamed for 300 seconds using a rotation/revolution mixer (CONDITIONING MIXER AR-250, manufactured by Shinky Co., Ltd.) to obtain a paint.
  • the obtained coating material was applied onto a PET film (Lumirror #75S10 manufactured by Toray Industries, Inc.) and cured by heating in a 150° C. environment for 10 minutes to form a coating layer with a thickness of about 250 ⁇ m.
  • Examples 2-3, Comparative Examples 1-3 A paint and a coating layer were obtained according to the method described in Example 1, except that the paint components and their contents were as shown in Table 1.
  • Examples 4 to 6 Comparative Example 4
  • a paint and a coating layer were obtained according to the method described in Example 1, except that the paint components and their contents were as shown in Table 2.
  • the curing agent ratio is the ratio of the amount (mol) of reactive groups of the curing agent to the amount (mol) of reactive groups possessed by the resin component.
  • the composition of the resin component was analyzed by NMR under the following measurement conditions, and the amount of reactive groups (mol) in the resin component and the amount (mol) of reactive groups in the curing agent were determined, and the curing agent ratio was calculated using the following formula. Calculated. The results are shown in Tables 1 and 2.
  • Curing agent ratio (Number of moles of hydrosilyl groups in the curing agent) / (Number of moles of carbon-carbon double bonds of vinyl groups in the resin component)
  • Measurement conditions equipment Bruker Biospin, AVANCEIII-600 with Cryo Probe observation frequency: 600MHz (1H), 79MHz (29Si) Measurement solvent: CDCl3 Measurement temperature: 300K Chemical shift standard: Measurement solvent [7.25ppm (1H)] Internal standard (TMS) [0.00ppm (29Si)]
  • the number average molecular weight of the first oil component was determined using the following measuring method and conditions. The results are shown in Tables 1 and 2.
  • the first oil component was prepared to 0.2% by mass with an eluent, left to stand for 20 hours, filtered through a 0.45 ⁇ m membrane filter, and the filtrate was subjected to GPC measurement under the following conditions.
  • Measurement conditions equipment Waters, ACQUITY APC Column: Agilent, PLgel Mixed-C + PLgel Mixed-E Column temperature: 40°C Eluent: toluene Flow rate: 0.8mL/min Injection volume: 100 ⁇ L Detector: RI Standard sample: polystyrene (PS)
  • the object of measurement is the amount of oil bled onto the surface of the coating layer at -20°C.
  • the amount of surface oil was measured using the following method, and the result was taken as a -20°C scraping test.
  • the paint layer cut into a size of 10 cm x 2 cm near the center was left at -20°C for 16 hours, and the oil that had bled onto the surface of the paint layer was removed using a cell scraper (manufactured by Kennis Co., Ltd.) under a temperature environment of -20°C. , CSS-10).
  • the oil was absorbed until no change in the mass (oil absorption amount) of the oil-absorbing paper was observed.
  • Collecting oil with a cell scraper and blotting it with oil-blotting paper was repeated 7 times per minute.
  • the difference in mass of the oil-blotting paper before and after oil-blotting was taken as the amount of surface oil.
  • the amount of surface oil was measured three times, and the average value was calculated.
  • the evaluation criteria for the -20°C scraping test are as follows. ⁇ ...Less than 40 ⁇ g/ cm2 ⁇ ...40 ⁇ g/cm2 or more
  • the object of measurement is the force required to move ice blocks attached to the coating layer in an environment of -20°C, and for convenience, in this specification, the magnitude of this force is defined as "icing force”. did.
  • the icing force was measured using the following method. First, a cylindrical block of ice was created. To make ice cubes, place a stainless steel ring (inner diameter 25 mm) on the bottom of a styrene square case type 16 (manufactured by As One), pour 6 g of pure water into it, freeze it at -20°C for more than 16 hours, and then remove the stainless steel ring after freezing. It was made by removing.
  • the coating layer was attached to a stainless steel flat plate so that the coating layer was on the surface, and the plate was left standing in a -20°C environment for 16 hours.
  • a cylindrical block of ice having a weight of 6 g and an adhering area of 4.9 cm 2 was prepared, and the bottom surface of the block of ice was brought into contact with a surface kept at a constant temperature of 10° C. for 10 seconds to adhere to the coating layer.
  • the environmental temperature was set to -20°C, and 3 hours after the ice cubes were attached, the ice cubes were placed on a load cell (DPU-50 manufactured by Imada Co., Ltd., with attachment treatment) in a -20°C environment from a direction parallel to the floor surface.
  • a type A-4 was pressed at a speed of 0.1 mm/sec, and the load applied during 40 seconds was measured with a force gauge (ZTS-50N manufactured by Imada Co., Ltd.). The value obtained by dividing the measured maximum load by the adhesion area of 4.9 cm 2 was recorded as the icing force.
  • the test was conducted three times and the average value was determined.
  • the paint of the present invention can provide a coating layer that causes less contamination of the coated object even in low-temperature environments and has excellent anti-icing and/or snow accretion functions. .
  • the coating layer of the present invention causes less contamination of the coated object even in low-temperature environments and has excellent icing and/or snow accumulation prevention functions, so it can be applied to solar panels, aircraft, railways, automobiles, and wind power generators. It can be used to prevent snow and ice from adhering to the surfaces of objects such as houses, traffic lights, signboards, tunnels, snow eaves prevention boards, bridges, and road signs.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'une couche de film de revêtement qui ne contamine pas largement une partie adhérée même dans un environnement à basse température, la couche de film de revêtement ayant une fonction exceptionnelle pour empêcher l'accrétion de glace et/ou de neige. La présente invention concerne une couche de film de revêtement contenant un composant de résine et au moins un type de composant d'huile, le composant d'huile ayant des groupes hydrophyliques, la quantité d'huile sur la surface de la couche de film de revêtement étant inférieure à 40 μg/cm 2, et la force d'accrétion de glace de la couche de film de revêtement étant inférieure ou égale à 0,7 N/cm2.
PCT/JP2023/013033 2022-03-31 2023-03-29 Couche de film de revêtement WO2023190795A1 (fr)

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PCT/JP2023/013033 WO2023190795A1 (fr) 2022-03-31 2023-03-29 Couche de film de revêtement

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04288381A (ja) * 1991-01-23 1992-10-13 Showa Electric Wire & Cable Co Ltd 耐熱塗料
JP2005512796A (ja) * 2001-12-21 2005-05-12 ロディア・シミ 鎖末端及び鎖中にＳｉ−Ｈ単位を含む水素化シリコーンオイルをベースとし、白金含有率が低い架橋性シリコーン組成物のための架橋剤
JP2016108415A (ja) * 2014-12-04 2016-06-20 日東電工株式会社 水生生物付着防止粘着テープ
WO2019235497A1 (fr) * 2018-06-04 2019-12-12 東亞合成株式会社 Composition de film hydrophobe, oléophobe et son utilisation
WO2020096071A1 (fr) * 2018-11-09 2020-05-14 日東電工株式会社 Matériau et film de revêtement
WO2020096070A1 (fr) * 2018-11-09 2020-05-14 日東電工株式会社 Corps de feuille
WO2021193973A1 (fr) * 2020-03-27 2021-09-30 日東電工株式会社 Substance de revêtement et corps multicouche

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2915778B2 (ja) * 1994-03-23 1999-07-05 信越化学工業株式会社 離型紙用シリコーン組成物
DE19957276A1 (de) * 1999-11-29 2001-10-11 Abb Research Ltd Additionsvernetzende Siliconkautschukmischungen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04288381A (ja) * 1991-01-23 1992-10-13 Showa Electric Wire & Cable Co Ltd 耐熱塗料
JP2005512796A (ja) * 2001-12-21 2005-05-12 ロディア・シミ 鎖末端及び鎖中にＳｉ−Ｈ単位を含む水素化シリコーンオイルをベースとし、白金含有率が低い架橋性シリコーン組成物のための架橋剤
JP2016108415A (ja) * 2014-12-04 2016-06-20 日東電工株式会社 水生生物付着防止粘着テープ
WO2019235497A1 (fr) * 2018-06-04 2019-12-12 東亞合成株式会社 Composition de film hydrophobe, oléophobe et son utilisation
WO2020096071A1 (fr) * 2018-11-09 2020-05-14 日東電工株式会社 Matériau et film de revêtement
WO2020096070A1 (fr) * 2018-11-09 2020-05-14 日東電工株式会社 Corps de feuille
WO2021193973A1 (fr) * 2020-03-27 2021-09-30 日東電工株式会社 Substance de revêtement et corps multicouche

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