WO2023190796A1 - Matériau de revêtement, couche de film de revêtement et stratifié - Google Patents

Matériau de revêtement, couche de film de revêtement et stratifié Download PDF

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WO2023190796A1
WO2023190796A1 PCT/JP2023/013034 JP2023013034W WO2023190796A1 WO 2023190796 A1 WO2023190796 A1 WO 2023190796A1 JP 2023013034 W JP2023013034 W JP 2023013034W WO 2023190796 A1 WO2023190796 A1 WO 2023190796A1
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group
amount
paint
mol
resin
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PCT/JP2023/013034
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English (en)
Japanese (ja)
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憲一 江口
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日東電工株式会社
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Publication of WO2023190796A1 publication Critical patent/WO2023190796A1/fr

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    • 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 paints, coating layers, and laminates, and specifically relates to objects such as solar panels, aircraft, railways, automobiles, wind power generators, houses, traffic lights, signboards, tunnels, snow eaves prevention boards, bridges, and road signs.
  • This invention relates to paints, coating layers, and laminates used to prevent snow and ice from adhering to surfaces.
  • 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 is capable of forming a coating layer that has excellent adhesion to a base material, etc., and has an excellent function of preventing icing and/or snowing.
  • the problem to be solved is to provide paint.
  • [1] Contains a resin component having a hydrosilyl group and a vinyl group, and an oil component, The amount of excess hydrosilyl group represented by the following formula exceeds 0.0015 mol/100 g, Paints containing silane coupling agents.
  • [Amount of surplus hydrosilyl group (mol/100g)] [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
  • the hydrophilic group is at least one selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group.
  • [4] A coating layer formed from the paint according to any one of [1] to [3].
  • [5] A laminate in which the coating layer described in [4] is laminated on a base material.
  • the laminate according to [5], wherein the base material includes any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
  • the paint of the present invention it is possible to form a coating layer that has excellent adhesion to substrates and the like and has an excellent function of preventing icing and/or snowing.
  • FIG. 1 is a cross-sectional view showing a coating layer formed using the paint of the present invention together with a base material.
  • FIG. 2 is a sectional view showing an example of a layer structure including a coating layer formed from the paint of the present invention together with a base material.
  • the coating material of the present invention contains a resin component having a hydrosilyl group and a vinyl group, and an oil component, has an amount of surplus hydrosilyl groups represented by the following formula exceeding 0.0015 mol/100 g, and contains a silane coupling agent.
  • Amount of surplus hydrosilyl group (mol/100g)] [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)]
  • the coating material of the present invention contains at least one resin component.
  • the resin component has a hydrosilyl group and a vinyl group.
  • examples of the resin component include a resin component containing only a resin, a resin component containing a resin and a curing agent, and the like.
  • the resin 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 may be a resin or a thermoplastic resin that is cured by adding a curing agent that crosslinks with the resin.
  • resins include, but are not limited to, silicone resins, polyurethane resins, polyurethane acrylic resins, vinyl chloride resins, polyester resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, etc.), acrylic resins, and EPDM.
  • silicone resins polyurethane resins, polyurethane acrylic resins, vinyl chloride resins, polyester resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, etc.), acrylic resins, and EPDM.
  • silicone resins silicone resins
  • polyurethane resins polyurethane acrylic resins
  • vinyl chloride resins polyester resins
  • elastomers elastomers
  • fluororesins polyamide resins
  • polyolefin resins polyethylene, polypropylene, etc.
  • acrylic resins and EPDM.
  • EPDM ethylene propylene dien
  • 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 resins examples include silicone resins having hydrosilyl groups and vinyl groups, silicone resins having vinyl groups, and the like. It is also possible to include as a resin a silicone resin having neither a hydrosilyl group nor a vinyl group.
  • 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 in the coating material of the present invention is preferably 15% by mass or more, more preferably 25% by mass or more, and even more preferably 35% by mass or more. Further, the resin content in the coating material of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.
  • the curing agent examples 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.
  • 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. That is, the curing agent preferably has a hydrosilyl group. 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.
  • Examples of embodiments in which a curing agent is used include an embodiment in which an additional curing agent independent of the resin is added.
  • the curing agent can be used, for example, to adjust the amount of hydrosilyl groups and the amount of excess hydrosilyl groups in the paint.
  • KE-2098-60A/B is a mixture of KE-2098-60A, a silicone polymer having a vinyl group, and KE-2098-60B, a silicone polymer having a hydrosilyl group, at a mass ratio of 1:1.
  • a resin containing a set of a polymer having a vinyl group and a polymer having a hydrosilyl group is used, a desired amount of excess hydrosilyl groups may be obtained without adding an additional curing agent.
  • an additional curing agent independent of this may be further added.
  • the coating material of the present invention contains at least one oil component.
  • 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
  • the oil component has a hydrophilic group.
  • the hydrophilic group include carbinol group, hydroxy group, carboxy group, carboxylic anhydride group, amino group, sulfo group, ether group, epoxy group, mercapto group, thiol group, ester group, etc. At least one group selected from the group consisting of a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group is preferred.
  • carbinol groups are more preferred from the viewpoint of exhibiting excellent icing and/or snow accretion prevention functions.
  • oil component only one type of oil component may be used, or two or more types of oil components may be used.
  • the coating material of the present invention contains at least one silane coupling agent.
  • 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 adhesion of the formed coating layer to the substrate improves when the paint contains a silane coupling agent, but in addition to the hydrosilyl group, the functional groups of the silane coupling agent improve the adhesion to the substrate. It is presumed that the adhesion is improved due to reaction and/or interaction with the functional groups of In addition, since 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, etc., 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 considered possible to provide a paint that can form a coating layer that has excellent adhesion to substrates and has excellent anti-icing and/or snow accretion functions.
  • 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 material of the present invention is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and still more preferably 0.15% by mass or more. Further, the content of the silane coupling agent in the coating material of the present invention is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass or less. In addition, only one type of silane coupling agent may be used, or two or more types may be used.
  • a coating layer formed from a paint that does not contain a silane coupling agent may not have the ability to prevent icing and/or snow accumulation.
  • the paint 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.
  • reaction control agent The coating material of the present invention may further contain a reaction control agent so that a coating film can be stably produced.
  • reaction control agents include reaction control agents manufactured by Shin-Etsu Chemical Co., Ltd. (product number: NO. 6-10) and reaction control agents manufactured by Dow Toray Industries, Inc. (product numbers: SILASTICTMRD-9, SILASTICTM RD-201). , a reaction control agent manufactured by Momentive (product number: ME75), a reaction control agent manufactured by Gelest (product numbers: VMS-005, VMS-T11), and the like.
  • the coating material of the present invention can be obtained by mixing and/or stirring the above-mentioned components by a known method.
  • the amount of hydrosilyl groups in the paint and the amount of vinyl groups in the paint can be determined, for example, by compositional analysis of the paint by NMR (nuclear magnetic resonance) measurement. Then, the amount of excess hydrosilyl groups can be determined from the amount of hydrosilyl groups in the paint and the amount of vinyl groups in the paint.
  • the amount of surplus hydrosilyl groups in the present invention exceeds 0.0015 mol/100 g, preferably exceeds 0.0030 mol/100 g, more preferably exceeds 0.0045 mol/100 g, and even more preferably exceeds 0.0060 mol/100 g.
  • the amount of surplus hydrosilyl groups in the present invention is preferably 0.1 mol/100 g or less, more preferably 0.075 mol/100 g or less, and still more preferably 0.05 mol/100 g or less.
  • the amount of surplus hydrosilyl groups is 0.0015 mol/100 g or less, the adhesion of the coating layer formed from the paint to the substrate etc. may be poor.
  • the present invention relates to a coating layer formed from the above-mentioned coating material.
  • the present invention also relates to a laminate in which the coating layer is laminated on a base material.
  • the coating layer of the present invention preferably has a surface oil amount of 40 ⁇ g/cm 2 or more as measured by the method described below. It is preferable that the surface oil amount is 40 ⁇ g/cm 2 or more because the oil component is oozed out from the coating layer under low temperature conditions and the icing and/or snow accretion prevention function is improved.
  • 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.
  • PDT adhesion Evaluation of adhesion (adhesion) was carried out with reference to JIS K-5600-5-6 (mechanical properties of coating film, adhesion). Specifically, the cross-cut test cutter guide (product name "Super Cutter Guide”, manufactured by Taiyu Kizai Co., Ltd.), cutter, polyimide adhesive tape (NO. 360UL, thickness 0.06 mm x width 50 mm, manufactured by Nitto Denko Co., Ltd.) prepared. Polyimide adhesive tape uses silicone adhesive and was selected because it has high adhesion to the silicone layer.
  • a transparent adhesive tape cut to a length of about 75 mm was pasted on the grid-cut area, and firmly rubbed with fingers to stick it. More specifically, the tape was rubbed flat with a finger at the area where it covered the grid and at least over a length exceeding 20 mm. Whether the tape was in proper contact with the paint film was determined by the color of the paint film seen through the tape.
  • Adhesion was evaluated in accordance with JIS K5600-5-6 in six grades from 0 to 5.
  • 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 formed of a coating material containing a resin component and an oil component, and the PET adhesion of the coating layer measured by the above method is: Of the six grades of evaluation according to JIS K5600-5-6, a rating of 0 to 1 is preferable.
  • a first coating layer 11 can be obtained by coating a base material 10 with the paint of the present invention. That is, a laminate including the base material 10 and the first coating layer 11 can be obtained.
  • 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 base material 10, and the paint of the present invention is applied over the primer. You may also apply paint.
  • the thickness of the first coating layer 11 is not particularly limited, but from the viewpoint of the quality of the coating film after drying, it is preferably 2000 ⁇ m or less, and from the viewpoint of strength, it is preferably 50 ⁇ m or more.
  • Examples of the base material 10 used in the present invention include polyurethane resins, polyurethane acrylic resins, rubber resins, vinyl chloride resins, polyester resins such as polyethylene terephthalate (PET) resins, polycarbonate (PC) resins, silicone resins, elastomers, Base materials such as fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.), metal plate or metal foil (aluminum, copper, silver, iron, nickel, tin, stainless steel, etc.), concrete, ceramics, etc. can be used.
  • PET polyethylene terephthalate
  • PC polycarbonate
  • silicone resins silicone resins
  • Base materials such as fluororesin, polyamide resin, polyolefin resin (polyethylene, polypropylene, etc.), metal plate or metal foil (aluminum, copper, silver, iron, nickel, tin, stainless steel, etc.), concrete, ceramics, etc. can be used.
  • the base material 10 is preferably a base material containing any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
  • the polyester resin include polyethylene terephthalate and polybutylene terephthalate
  • the polyamide resin include nylon 6, nylon 66, and polyphthalamide.
  • the metal include stainless steel, aluminum, and iron.
  • the base material 10 may be in the form of a film or a sheet.
  • the paint of the present invention After the paint of the present invention is applied to the substrate 10, the paint can be cured or dried by allowing it to stand, for example, for 3 minutes to 3 hours in an environment of 20 to 180°C.
  • 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. . That is, a laminate including the base material 10, the first coating layer 11, and the second coating layer 12 can be obtained.
  • 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 same as the curing or drying temperature and curing or drying time when applying the coating of the present invention to the base material 10. The same is true.
  • 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.
  • ⁇ 1> Contains a resin component having a hydrosilyl group and a vinyl group, and an oil component, The amount of excess hydrosilyl group represented by the following formula exceeds 0.0015 mol/100 g, Paints containing silane coupling agents.
  • [Amount of surplus hydrosilyl group (mol/100g)] [Amount of hydrosilyl groups in the paint (mol/100g)] - [Amount of vinyl groups in the paint (mol/100g)] ⁇ 2>
  • the hydrophilic group is at least one selected from the group consisting of a carbinol group, a hydroxy group, a carboxy group, a carboxylic anhydride group, an amino group, a sulfo group, an ether group, an epoxy group, a mercapto group, a thiol group, and an ester group.
  • the paint according to ⁇ 2> which is a seed group.
  • ⁇ 4> A coating layer formed from the paint according to any one of ⁇ 1> to ⁇ 3>.
  • ⁇ 5> A laminate in which the coating layer described in ⁇ 4> is laminated on a base material.
  • the base material includes any one selected from polyester resin, polyamide resin, polycarbonate resin, and metal.
  • Example 1 ⁇ Preparation of paint> As paint components, resin: KE-2098-60 and first oil component (incompatible oil): KF-6003 were prepared. In the examples, the component with the highest content among the oil components is referred to as the first oil component, and the component with the second highest content is referred to as the second oil component.
  • the resin component KE-2098-60 is a mixture of KE-2098-60A and KE-2098-60B at a mass ratio of 1:1.
  • ⁇ KF-6003 Carbinol-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the resin (42 parts by mass) and the first oil component (58 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 to 4 Comparative Examples 1 to 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.
  • the resin component KE-1950-50 is a mixture of KE-1950-50A and KE-1950-50B at a mass ratio of 1:1.
  • ⁇ KF-96 (50cs): Dimethylsiloxane oil, Shin-Etsu Chemical Co., Ltd. ⁇ 3-Isocyanatepropyltriethoxysilane: Silane coupling agent, Shin-Etsu Manufactured by Kagaku Kogyo Co., Ltd.
  • the amount of surplus hydrosilyl groups (mol/100g) is the amount obtained by subtracting the amount of vinyl groups in the paint (mol/100g) from the amount of hydrosilyl groups in the paint (mol/100g).
  • the composition of the paint was analyzed by NMR under the following measurement conditions, the amount of hydrosilyl groups in the paint (mol/100g) and the amount of vinyl groups in the paint (mol/100g) were determined, and the amount of excess hydrosilyl groups (mol/100g) was determined. 100g) was calculated using the following formula. The results are shown in Table 1.
  • 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 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.
  • 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 are as follows. ⁇ (Good)...40 ⁇ g/ cm2 or more ⁇ (Poor)...40 ⁇ g/ cm2 or more
  • PDT adhesion Evaluation of adhesion (adhesion) was carried out with reference to JIS K-5600-5-6 (mechanical properties of coating film, adhesion). Specifically, the cross-cut test cutter guide (product name "Super Cutter Guide”, manufactured by Taiyu Kizai Co., Ltd.), cutter, polyimide adhesive tape (NO. 360UL, thickness 0.06 mm x width 50 mm, manufactured by Nitto Denko Co., Ltd.) prepared. Polyimide adhesive tape uses silicone adhesive and was selected because it has high adhesion to the silicone layer.
  • a transparent adhesive tape cut to a length of about 75 mm was pasted on the grid-cut area, and firmly rubbed with fingers to stick it. More specifically, the tape was rubbed flat with a finger at the area where it covered the grid and at least over a length exceeding 20 mm. Whether the tape was in proper contact with the paint film was judged by the color of the paint film seen through the tape.
  • Adhesion was evaluated in accordance with JIS K5600-5-6 in six grades from 0 to 5.
  • the evaluation criteria are as follows. ⁇ (Good)...Out of 6 stages of evaluation, it is classified as 0-1 ⁇ (Poor)...Out of 6 stages of evaluation, it is classified as 2-5
  • 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 provides a coating layer that has excellent adhesion to substrates, etc., and has an excellent ability to prevent icing and/or snow accretion.
  • the paint of the present invention has excellent adhesion to substrates, etc., and can form a coating layer with excellent icing and/or snow accretion prevention functions. It can be used to prevent snow and ice from adhering to the surfaces of objects such as wind power generators, 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)
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  • 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'un matériau de revêtement qui présente une excellente adhérence à un matériau de base et similaire et est en mesure de former une couche de film de revêtement ayant une excellente fonction dans la prévention de l'accrétion de glace et/ou de l'accrétion de neige. La présente invention concerne un matériau de revêtement qui contient un composant huileux et un composant de résine ayant un groupe hydrosilyle et un groupe vinyle, dans lequel une quantité de groupe hydrosilyle en excès représentée par la formule ci-dessous dépasse 0,0015 mol/100 g et qui contient un agent de couplage au silane. [Quantité de groupe hydrosilyle en excès (mol/100 g)] = [quantité de groupes hydrosilyle dans le matériau de revêtement (mol/100 g)] - [quantité de groupes vinyle dans le matériau de revêtement (mol/100 g)]
PCT/JP2023/013034 2022-03-31 2023-03-29 Matériau de revêtement, couche de film de revêtement et stratifié WO2023190796A1 (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 (6)

* 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
JPH07258606A (ja) * 1994-03-23 1995-10-09 Shin Etsu Chem Co Ltd 離型紙用シリコーン組成物
JP2003515650A (ja) * 1999-11-29 2003-05-07 アーベーベー・リサーチ・リミテッド 追加的架橋性シリコーンゴム混合物
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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210323283A1 (en) * 2018-11-09 2021-10-21 Nitto Denko Corporation Sheet body
US20210403754A1 (en) * 2018-11-09 2021-12-30 Nitto Denko Corporation Coating material and film
WO2021193973A1 (fr) * 2020-03-27 2021-09-30 日東電工株式会社 Substance de revêtement et corps multicouche

Patent Citations (6)

* 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
JPH07258606A (ja) * 1994-03-23 1995-10-09 Shin Etsu Chem Co Ltd 離型紙用シリコーン組成物
JP2003515650A (ja) * 1999-11-29 2003-05-07 アーベーベー・リサーチ・リミテッド 追加的架橋性シリコーンゴム混合物
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

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