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WO2023032926A1 - Stratifié et procédé de production d'un stratifié - Google Patents

Stratifié et procédé de production d'un stratifié Download PDF

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Publication number
WO2023032926A1
WO2023032926A1 PCT/JP2022/032444 JP2022032444W WO2023032926A1 WO 2023032926 A1 WO2023032926 A1 WO 2023032926A1 JP 2022032444 W JP2022032444 W JP 2022032444W WO 2023032926 A1 WO2023032926 A1 WO 2023032926A1
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WIPO (PCT)
Prior art keywords
laminate
porous portion
organic layer
porous
polysiloxane
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PCT/JP2022/032444
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English (en)
Japanese (ja)
Inventor
浩樹 幅▲崎▼
涼太 山本
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Hokkaido University NUC
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Hokkaido University NUC
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Priority to JP2023545567A priority Critical patent/JP7762443B2/ja
Publication of WO2023032926A1 publication Critical patent/WO2023032926A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing

Definitions

  • the present invention relates to a laminate and a method for manufacturing the laminate. More particularly, the present invention relates to a laminate having one or more of synovial properties, antifouling properties, liquid repellency, and snow/ice sliding properties, and a method for producing the same.
  • SLIPS Slippery liquid infused porous surface
  • lubricants such as perfluoropolyether and silicone oil
  • SLIPS has synovial properties that allow various liquids such as water and oil to slide down easily, and exhibits many notable properties such as surface antifouling, snow/icing prevention, and corrosion resistance improvement. The following are known prior arts related to SLIPS.
  • an aluminum oxide film is provided on the surface of an aluminum member having a hierarchical structure composed of an aluminum oxide film having hierarchical etching pits and nanopores present on the surface of the etching pits, and the aluminum oxide film is composed of a fluorine-containing organic phosphorous
  • An aluminum composite for use in snow control is described having a monolayer of an acid compound and a coating layer of fluorine-containing oil over the monolayer.
  • US Pat. No. 6,200,400 discloses an article comprising a liquid-impregnated surface, said surface comprising a plurality of microscale and/or nanoscale solids spaced sufficiently closely together to stably contain the impregnating liquid therebetween. features, the surface stably containing the impregnating liquid between the solid features, the impregnating liquid filling spaces between the solid features, and the solid features despite movement of the surface. Articles are described that are held in place between. It is stated that the solid features may be pores and the impregnating liquid may be a silicone oil or a fluorocarbon.
  • Patent Document 3 comprises a lubricating fluid layer, said lubricating fluid being immiscible with biological substances, said lubricating layer forming an ultra-smooth surface on a coarse solid substrate, said lubricating fluid comprising: a slippery surface adhering to said substrate, said substrate being preferentially wetted by said lubricating fluid, said solid substrate and lubricating fluid configured and arranged to contact a biological material; Forming articles for repelling biological material are described. It is stated that the lubricating fluid may be a liquid silicone elastomer or a perfluorinated fluid and that the substrate may be a roughened surface comprising a porous material.
  • Patent Document 4 describes an article having a slippery surface, the supramolecular polymer having the general formula PxSy, where P is a covalently crosslinked polymer, S is a supramolecular block within the polymer network, x+y is 1 , y is 0 to 1) and a lubricating liquid, wherein the lubricating liquid may contain a silicone oil or a perfluorocarbon, and the supramolecular polymer and the lubricating liquid are: Articles are described that have an affinity for each other such that the lubricating liquid is absorbed into the polymeric material in sufficient quantity to form a slippery lubricating layer on the surface of the liquid swelling polymer.
  • Patent Document 5 a surface treatment film such as an anodized film having gaps such as pores and holes applied to the surface of a metal is impregnated with a fluorine-based monomer having a fluorocarbon chain, and then this surface treatment film is subjected to low-energy
  • a metal product having a fluorine-based polymer thin film formed on a metal surface is described in which a fluorine polymer thin film is formed by electron beam irradiation.
  • Patent Document 6 discloses a base material, a porous layer provided on the base material, and a lubricating liquid impregnated inside the porous layer, and the porous layer contains at least inorganic oxide fine particles and A water- and oil-repellent substrate composed of a mixture containing an inorganic binder containing one or more hydrolysates of alkoxysilane, wherein the lubricating liquid is fluorine-based oil or silicone oil.
  • a substrate is described.
  • Non-Patent Documents 1 to 4 describe polydimethylsiloxane (PDMS) and polymethylhydrosiloxane (PMHS) as surfaces for overcoming the problem of durability, which is a problem of SLIPS, by utilizing properties like solid wax. It is described that a synovial solid surface that functions as a liquid phase-like surface is produced by covalently grafting organic molecules having chemical bonds (Si—C, Si—O, CH) such as ing.
  • PDMS polydimethylsiloxane
  • PMHS polymethylhydrosiloxane
  • SLIPS which has been known so far, has little effect of physical damage due to the high fluidity of the lubricant, but the lubricant may be consumed by cleaning, evaporation, detachment, etc., and durability is an issue. rice field.
  • the aluminum composite material described in Patent Document 1, the articles described in Patent Documents 2 to 4, the metal product described in Patent Document 5, and the water- and oil-repellent substrate described in Patent Document 6 are , synovial properties to various solvents (wettability; static contact angle, contact angle hysteresis and drop falling angle), abrasion resistance, durability, corrosion resistance, ice resistance, etc. I didn't.
  • the thickness of the graft layer is only a few nanometers, so improvement in durability is limited.
  • the problem to be solved by the present invention is a laminate having improved synovial properties, abrasion resistance, antifouling properties, liquid repellency, snow/ice sliding properties, droplet falling properties, corrosion resistance, durability, etc., and its It is to provide a manufacturing method.
  • the present inventors have made intensive studies to solve the above problems, and found that a porous portion and an organic layer covering at least a part of the porous portion and filling the inside of the porous portion are provided. and the organic layer is a layer formed from one or more of amorphous fluororesin and/or polysiloxane, and the laminate easily slides down various liquids such as water and oil, similar to SLIPS. In addition to exhibiting excellent synovial properties that can be I have completed my invention.
  • a metal substrate, a porous portion provided in at least a part of the metal substrate, and at least the porous portion SLIPS is a laminate having an organic layer that partially covers and fills the interior of the porous portion, wherein the organic layer is a layer formed of one or more of amorphous fluororesin and / or polysiloxane.
  • the present invention provides the following laminate and method for producing the laminate.
  • Item 1 Having a porous portion and an organic layer covering at least a portion of the porous portion and filling the inside of the porous portion, A laminate, wherein the organic layer is a layer formed from one or more of polysiloxane and/or amorphous fluororesin.
  • Item 2 Having a metal substrate, a porous portion provided in at least a portion of the metal substrate, and an organic layer covering at least a portion of the porous portion and filling the inside of the porous portion death, A laminate, wherein the organic layer is a layer formed from one or more of polysiloxane and/or amorphous fluororesin.
  • Item 3 The polysiloxane has the following formula (1); (In Formula (1), R 1 , R 2 , X 1 and X 3 are each independently an alkyl group, an aromatic group and an unsaturated hydrocarbon group, and X 2 and X 4 are each independently an alkyl group. , an aromatic group, an unsaturated hydrocarbon group, or hydrogen, and n is an integer of 2 or more, and n X 3 and X 4 may be the same or different.) Item 3. The laminate according to item 1 or 2, which is a compound represented by. Item 4: The laminate according to any one of Items 1 to 3, wherein the organic layer is gel.
  • Item 5 The laminate according to any one of Items 1 to 4, which has one or more of synovial properties, antifouling properties, liquid repellency, and snow/ice sliding properties.
  • Item 6 Used as electric wires, steel towers, metal structures, utility poles, transformers, electric wire accessories, power transmission related equipment, signs, signboards, antennas, roofs, bags, vehicles, aircraft, guardrails, building materials, food plant members, Item 6. The laminate according to any one of items 1 to 5.
  • Item 7 A step of forming, on a metal substrate having a porous portion on at least a portion of the surface thereof, an organic layer that covers at least a portion of the porous portion and fills the inside of the porous portion, and heating the organic layer; has The organic layer is a layer formed from one or more of polysiloxane and / or amorphous fluororesin, A method for manufacturing a laminate.
  • Item 8 The method according to Item 7, comprising the step of forming a porous portion on at least part of the surface of the metal substrate.
  • the present invention provides a laminate having improved synovial properties, abrasion resistance, antifouling properties, liquid repellency, snow/ice sliding properties, droplet falling properties, corrosion resistance, durability, etc., and a method for producing the same. .
  • FIG. 4 is an SEM image of the surface morphology of the surface portion of the stainless steel substrate produced in Production Example 4.
  • FIG. 4 is an SEM image of the surface morphology of the surface portion of the titanium base material produced in Production Example 5.
  • FIG. 4 is a SEM image of the surface morphology of the iron substrate surface portion produced in Production Example 7.
  • a first aspect of the present invention has a porous portion, and an organic layer covering at least a portion of the porous portion and filling the inside of the porous portion, wherein the organic layer comprises polysiloxane and/or or a laminate, which is a layer formed from one or more amorphous fluororesins.
  • a second aspect of the present invention includes a metal substrate, a porous portion provided in at least a portion of the metal substrate, and at least a portion of the porous portion and the porous portion filled with The laminate has an organic layer containing a polysiloxane and/or an amorphous fluororesin.
  • the porous portion has an opening in the surface portion and is particularly limited as long as it can be filled with polysiloxane and / or amorphous fluororesin that forms the organic layer. not.
  • the average diameter of the pores forming the porous portion is not particularly limited as long as the polysiloxane and/or amorphous fluororesin forming the organic layer can be filled and not easily released.
  • it is 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, still more preferably 50 nm or more, for example 1 mm or less, preferably 100 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 1 ⁇ m or less, still more preferably 500 nm or less.
  • the average diameter of the pores forming the porous portion is less than 1 nm, it becomes difficult to fill the polysiloxane and/or amorphous fluororesin forming the organic layer, it takes time, special techniques are required, etc. problems may occur.
  • the average diameter exceeds 1 mm, the amount of polysiloxane and/or amorphous fluororesin used increases when forming the organic layer, which is disadvantageous in terms of cost, and there is a risk that it will easily separate after filling. be.
  • the thickness of the porous portion is not particularly limited. For example, it is 100 nm or more, preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and for example 1 mm or less, preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less. If the thickness of the porous portion is less than 100 nm, the filling amount of polysiloxane and/or amorphous fluororesin forming the organic layer is reduced, and the laminate may not exhibit the desired effects.
  • porous portion Materials and components that form the porous portion are not particularly limited as long as they can maintain the porous shape and do not change the properties of the polysiloxane and/or the amorphous fluororesin. Examples include metals, oxides, carbon, ceramics, activated carbon, polymers, and organic-inorganic composites. In the present invention, it is preferable to contain an oxide, particularly a metal oxide.
  • the porous portion may be formed, for example, by treating the surface layer of the metal substrate, or may be formed by bonding a separately formed porous member to the surface of the metal substrate. good too. In particular, the one formed by treating the surface layer of the metal substrate is preferable.
  • the porous portion can be formed from one or more kinds of porous members.
  • a porous member further provided with a porous portion may be used. Also, the porous portion may be provided on at least a portion of the nonmetallic base material.
  • a metal substrate in which a porous portion, which is a porous anodic oxide film, is formed on at least a part of the metal substrate by anodizing the metal substrate.
  • a material in which a porous portion is formed by reacting a metal substrate with a reagent capable of forming a porosity for example, various acids, various bases, etc.
  • anodic oxidation treatment In the anodic oxidation treatment, the surface of the metal substrate is oxidized directly under an electric field in an aqueous solution or an organic electrolytic solution containing a small amount of water using the metal substrate as an anode (anode) to oxidize the surface. It is a process to
  • the metal substrate used in the anodizing treatment is not particularly limited, and those described in ⁇ Metal substrate> can be used.
  • a metal substrate containing Al, Ti, Fe, Cu, Zn, or an alloy containing one or more of these is preferably used.
  • Metal substrates containing Al or Al alloys are particularly preferred.
  • the conditions of the anodizing treatment are not particularly limited as long as a porous anodized film having pores can be formed.
  • the conditions for the anodic oxidation treatment can be appropriately adjusted according to the film thickness of the anodic oxide film, the pore size of the pores, and the like.
  • electrolytes for example, for aluminum, acid aqueous solutions such as sulfuric acid, phosphoric acid, nitric acid, chromic acid, silicic acid, oxalic acid, malonic acid, citric acid, sulfamic acid, mixed acids thereof, these acids
  • An aqueous acid solution containing a salt of can be used.
  • a weakly alkaline aqueous borax solution is also available.
  • sulfuric acid, oxalic acid or phosphoric acid are preferred.
  • an aqueous base solution e.g., an aqueous solution of an alkali metal hydroxide such as sodium hydroxide
  • a solvent containing a salt e.g., a water-ethylene glycol mixed solution containing ammonium fluoride, etc.
  • the pH of the electrolytic solution is not particularly limited, and is, for example, pH 6.0 or less, preferably pH 3.0 or less.
  • the temperature of the electrolytic solution is not particularly limited, and is, for example, 0° C. or higher, preferably 10° C. or higher, and for example, 35° C. or lower, preferably 30° C. or lower.
  • the anodic oxidation voltage is not particularly limited, and is, for example, 0.1 V or higher, preferably 10 V or higher, more preferably 20 V or higher, and is, for example, 300 V or lower, preferably 240 V or lower, more preferably 200 V or lower.
  • the anodic oxidation current is not particularly limited, and is, for example, 10 A/m 2 or more, preferably 50 A/m 2 or more, and is, for example, 1000 A/m 2 or less, preferably 500 A/m 2 or less.
  • the time for the anodizing treatment is not particularly limited, and is, for example, 1 second or longer, preferably 1 minute or longer, more preferably 10 minutes or longer, still more preferably 15 minutes or longer, and for example 100 minutes or shorter, preferably 60 minutes or shorter. , more preferably 45 minutes or less.
  • the pore size of the pores of the porous portion obtained by the anodic oxidation treatment is, for example, 1 nm or more, preferably 2 nm or more, more preferably 5 nm or more, and for example, 500 nm or less, preferably 300 nm or less, more preferably 200 nm. It is below.
  • the thickness of the porous portion obtained by the anodic oxidation treatment is, for example, 100 nm or more, preferably 500 nm or more, and for example, 300 ⁇ m or less, more preferably 200 ⁇ m or less.
  • pretreatment such as cleaning treatment, degreasing treatment, etching treatment, electropolishing treatment, etc. is performed as necessary prior to anodization treatment, so that oil and fat components present on the anodization treatment surface and vapor-phase oxidation are removed. It is preferable to remove the film or the like.
  • a pore widening treatment may be performed to further enlarge the diameter of the pores (nanopores) generated by the anodizing treatment.
  • the pore widening treatment is performed by immersing the metal base material after the anodizing treatment in an acid aqueous solution such as sulfuric acid, phosphoric acid, nitric acid, chromic acid, silicic acid, oxalic acid, sulfamic acid, mixed acid of these for a certain period of time. be able to.
  • the conditions for the pore widening treatment in the present invention are, for example, the temperature of the acid aqueous solution is in the range of 10° C. or higher and 40° C.
  • the concentration of the acid aqueous solution is in the range of 1% by mass or higher and 15% by mass or lower, and the treatment time is, for example, The range is from 60 seconds to 7200 seconds.
  • the pore widening treatment is preferably carried out by immersing in an aqueous solution of phosphoric acid, sulfuric acid or oxalic acid having a concentration of 3 to 10% by mass at 15 to 35° C. for 600 to 1200 seconds.
  • the metal substrate is not particularly limited.
  • alloys containing one or more of Al, Ti, Fe, Cu, Zn, Cr, and Ni, laminates thereof, and the like are preferable.
  • Particularly preferred are Al, Al alloys, Ti, Ti alloys, iron, zinc, zinc alloys (eg, zamak, brass, etc.), iron-chromium alloys (eg, stainless steel, etc.).
  • stainless steel examples include austenitic stainless steel, austenitic ferritic duplex stainless steel, ferritic stainless steel, and martensitic stainless steel.
  • austenitic stainless steel for example, SUS200 series, 300 series, etc. indicated by JIS steel grades is preferable.
  • the shape and the like of the metal substrate are not particularly limited. It can have any shape depending on the application. For example, plate-like, line/rod-like (octagonal, hexagonal, flat, square, round, etc.), chevron (L-shaped), straight sheet pile, U-shaped sheet pile, groove (U-shaped), I-shaped, H A shape, a rail shape, a tubular shape, a shape obtained by combining one or more of these shapes, and the like can be mentioned.
  • the thickness of the plate-shaped metal substrate is not particularly limited, and can be, for example, 0.1 mm or more, preferably 0.5 mm or more and 100 mm or less.
  • the diameter of the wire/rod-shaped metal substrate is not particularly limited, and can be, for example, 0.1 mm or more, preferably 0.5 mm or more and 100 mm or less.
  • the metal substrate is preferably subjected to pretreatments such as cleaning, degreasing, etching, and electropolishing to remove oil and fat components, gas-phase oxide films, etc. present on the surface of the metal substrate.
  • pretreatments such as cleaning, degreasing, etching, and electropolishing to remove oil and fat components, gas-phase oxide films, etc. present on the surface of the metal substrate.
  • the organic layer covers at least a portion of the porous portion and fills the inside of the porous portion.
  • the organic layer is a layer formed from one or more of polysiloxane and/or amorphous fluororesin.
  • the organic layer is, for example, (1) a coating film obtained by applying one or more of polysiloxane and / or amorphous fluororesin or a dry coating film thereof, (2) the coating film of (1) or A crosslinked coating obtained by heat-treating a dried coating may also be used.
  • the polysiloxane and/or amorphous fluororesin forming the organic layer may be dissolved in a suitable organic solvent or the like.
  • the organic layer is preferably gel-like.
  • gel-like means that the polysiloxane and/or the amorphous fluororesin are partially thermally decomposed and intermolecularly crosslinked by heating the polysiloxane and/or the amorphous fluororesin, thereby increasing the viscosity. It is in a state of reduced liquidity.
  • dimethylpolysiloxane which is a type of polysiloxane
  • a thermal decomposition initiation temperature about 150° C.
  • part of the dimethylpolysiloxane is thermally decomposed and intermolecularly crosslinked. Viscosity increases and a gel-like substance is formed.
  • Polysiloxane is a resin having a --Si--O-- bond in its molecule, and is not particularly limited as long as it can form a film.
  • siloxane units (M units) represented by R a 3 SiO 0.5 siloxane units (D units) represented by R b 2 SiO, siloxane units (T units) represented by R c SiO 1.5 and SiO Polysiloxane containing one or more siloxane units (Q units) represented by 2 may also be used.
  • R a , R b and R c are each independently an alkyl group, an aromatic group or an unsaturated hydrocarbon group, and when there are a plurality of each of R a , R b and R c in the polysiloxane, the same may be different.
  • MQ resins composed of M units and Q units T resins composed of T units, MDQ resins composed of M units, D units and Q units, M units, D units, T units and Q units DT resin composed of D units and T units, MDT resin composed of M units, D units and T units, MTQ resin composed of M units, T units and Q units, and
  • QDT resins composed of D units, T units and Q units can be used.
  • the structure of polysiloxane is not particularly limited, and may be linear, cyclic, three-dimensional network structure, or the like. In the present invention, it is preferred to use linear polysiloxane.
  • polysiloxane examples include 1,1,3,3-tetramethyldisiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, and trimethylsiloxy group-blocked at both ends of the molecular chain.
  • R 1 , R 2 , X 1 and X 3 are each independently an alkyl group, an aromatic group and an unsaturated hydrocarbon group
  • X 2 and X 4 are each independently an alkyl group.
  • n is an integer of 2 or more
  • n X 3 and X 4 may be the same or different.
  • It is preferably a linear polysiloxane represented by.
  • polysiloxane in the present invention the following formula (2); R 3 SiO 1.5 (2) (In formula (2), R3 is an alkyl group, an aromatic group, or an unsaturated hydrocarbon group, and multiple R3s may be the same or different.)
  • Polysiloxane polysilsesquioxane having a three-dimensional network structure containing repeating units represented by is preferable.
  • the terminal is, for example, —SiR 3 (OR 4 ) 2 or —SiR 3 (OR 4 )O 0.5 (wherein R 3 is an alkyl group, an aromatic group or an unsaturated hydrocarbon group, and R 4 is , an alkyl group having 1 to 6 carbon atoms or H, and a plurality of R 3 and a plurality of R 4 may be the same or different.).
  • alkyl groups for R 1 , R 2 , R 3 , X 1 , X 2 , X 3 and X 4 in formulas (1) and (2) include alkyl groups having 1 to 20 carbon atoms. Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, cyclohexyl group, heptyl group, dodecyl group and stearyl group. These alkyl groups having 1 to 20 carbon atoms may have a substituent such as halogen.
  • the unsaturated hydrocarbon groups for R 1 , R 2 , R 3 , X 1 , X 2 , X 3 and X 4 in formulas (1) and (2) are unsaturated aliphatic hydrocarbon groups having 2 to 20 carbon atoms. A hydrogen group is mentioned.
  • ethenyl group (vinyl group), propenyl group (allyl group), butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, octynyl group and the like. mentioned.
  • the repeating unit number n is an integer of 1 or more. For example, it is 10 or more, preferably 20 or more, and for example, 15,000 or less, preferably 5,000 or less.
  • the polysiloxane of formula (1) has a kinematic viscosity at 25° C. of, for example, 500 mm 2 /sec or more, preferably 10,000 mm 2 /sec or more, for example 10,000,000 mm 2 /sec or less, preferably It may be 1,000,000 mm 2 /sec or less.
  • the weight average molecular weight of the polysiloxane (polysilsesquioxane) having a three-dimensional network structure containing repeating units represented by formula (2) is not particularly limited. For example, it is 400 or more, preferably 500 or more, and for example, 5,000 or less, preferably 4,000 or less.
  • a commercially available polysiloxane can be used.
  • Commercially available products include, for example, KF-96, KF-965, KF-968, KF-50, KF-54, HIVAC F-4, HIVAC F-5, KF56, KF-99, KR-242A, KR-251, KR-112, KR-255, KR-271, KR-282, KR-300, KR-311, KR-515 , KR-500, KR-401N, KR-510, KR-213, KR-4000G, KR-4000F2, KR-400, KR-401, KR-511, KR-2710, X-48-1030, X-48 -1500, X-48-1600, X-40-2667A, X-40-2756, X-40-9225, X-40-9246, X-40-9250, X-40-9227, X-40-9312 , X-40-2327, X-40-2450, X-40-9300
  • polysiloxane in the present invention for example, polymethylhydrogensiloxane (PMHS) represented by the following formula (3), for example, polydimethylsiloxane (PDMS) represented by the following formula (4), for example, the following formula It is preferable to use one or more of polymethylsilsesquioxanes having the structural unit represented by (5).
  • polysiloxane in the present invention it is preferable to use a mixture of, for example, PMHS represented by the following formula (3) and PDMS represented by, for example, the following formula (4).
  • the amorphous fluororesin is not particularly limited as long as it is an amorphous (amorphous) resin.
  • amorphous fluororesins include perfluoro(4-vinyloxy-1-butene) cyclized polymer (BVE), tetrafluoroethylene-perfluorodioxole copolymer (TFE/PDD), tetrafluoroethylene-per From the group consisting of fluoromethyl vinyl ether copolymer (TFE/MFA), tetrafluoroethylene-perfluoroethyl vinyl ether copolymer (TFE/EFA), tetrafluoroethylene-perfluoropropyl vinyl ether copolymer (TFE/PFA), etc.
  • amorphous fluororesins may be used as they are.
  • the AF series manufactured by DuPont Fluorochemicals, Mitsui
  • the Algoflon series manufactured by Solvay Special Polymers Japan
  • the Cytop series manufactured by AGC
  • the amorphous fluororesin includes, for example, the following repeating unit (6); (Wherein, s represents the number of repeating units.) It is preferable to use a perfluoro(4-vinyloxy-1-butene) cyclized polymer (BVE) having For example, CTX-809A, CTL-109AE, CTX-109AE, CTL-809M, CTL-107MK, CTX-809SP2, CT-SOLV180, CT-SOLV100E, CT-SOLV100K, etc. in Cytop series can be used.
  • BVE perfluoro(4-vinyloxy-1-butene) cyclized polymer
  • the average molecular weight of the amorphous fluororesin is not particularly limited. For example, it is 100,000 or more, preferably 120,000 or more, more preferably 150,000 or more, and for example, 500,000 or less, preferably 300,000 or less, more preferably 200,000 or less.
  • the organic layer formed from one or more of polysiloxane and/or amorphous fluororesin covers at least a portion of the porous portion and fills the inside of the porous portion.
  • the method of covering at least part of the porous portion with the organic layer and filling the interior of the porous portion with the organic layer is not particularly limited.
  • a dip coating method, a bar coating method, a die coating method, a slit coating method, a roll coating method, a spray coating method, a spin coating method, or the like can be used.
  • the dip coating method it is possible to promote the filling into the inside of the porous portion by performing it under ultrasonic waves.
  • a spray coating method it is possible to selectively coat or fill only an arbitrary portion of the porous portion with the organic layer.
  • the coating and filling amount of polysiloxane and/or amorphous fluororesin are not particularly limited. For example, it is 10 ⁇ g/cm 2 or more, preferably 50 ⁇ g/cm 2 or more.
  • Heat treatment In the present invention, an organic layer formed from one or more of polysiloxane and / or amorphous fluororesin, after covering at least a part of the porous portion and filling the inside of the porous portion, if necessary Heat treatment is preferably performed after drying (solvent removal). Heat treatment conditions are not particularly limited. The temperature may be within a range in which the polysiloxane and/or the amorphous fluororesin do not ignite or spontaneously ignite.
  • the heat treatment conditions are, for example, in air at a thermal decomposition temperature or higher, for example, 120° C. or higher, preferably 150° C. or higher, more preferably 170° C. or higher, and for example, 400° C. or lower, preferably 350° C. or lower.
  • the heating time is, for example, 1 minute or longer, preferably 10 minutes or longer, and for example, 5 hours or shorter, preferably 3 hours or shorter.
  • a heating furnace it is preferable to use a heating furnace (oven).
  • the organic layer formed from one or more of polysiloxane and/or amorphous fluororesin can be firmly integrated with the porous portion.
  • an organic layer formed from one or more of polysiloxane and/or amorphous fluororesin is filled in the porous portion and exerts an anchor effect, so that the organic layer has excellent wear resistance. may be provided over at least a portion of the porous portion.
  • the organic layer formed from one or more of polysiloxane and/or amorphous fluororesin is subjected to heat treatment to cause intermolecular cross-linking to form a three-dimensional network and gel. can be done. As a result, the organic layer and the porous portion are firmly integrated, and the detachment of the organic layer can be significantly suppressed. It is possible to express one or more of the above for a long period of time.
  • the laminate of the present invention has one or more of synovial properties, antifouling properties, liquid repellency, and snow/ice sliding properties.
  • the laminate of the present invention has a static contact angle with water of 90° or more, preferably 95° or more and 125° or less.
  • the static contact angle of the laminate of the present invention with respect to organic solvents other than water is not particularly limited. For example, it may be 90° or less.
  • the laminate of the present invention has a surface tension of 20 mN/m or more and 80 mN/m or less of a solvent (water, rapeseed oil, hexadecane, dodecane, ethylene glycol, ethanol, etc.), and the difference between the advancing contact angle and the receding contact angle is It is preferred that the contact angle hysteresis is 15° or less, preferably 10° or less. Further, the laminate of the present invention preferably has a liquid droplet falling angle of 20° or less, preferably 16° or less, for a solvent having a surface tension of 20 mN/m or more and 80 mN/m or less.
  • a solvent water, rapeseed oil, hexadecane, dodecane, ethylene glycol, ethanol, etc.
  • the laminate will have at least one of synovial properties, antifouling properties, liquid repellency, and snow/ice sliding properties. be able to. Furthermore, the laminate of the present invention exhibits little change over time (deterioration over time) in static contact angle, contact angle hysteresis, and falling angle of droplets, and exhibits synovial properties, antifouling properties, liquid repellency, and snow/ice sliding properties. Any one or more of the above can be exhibited continuously for a long period of time. As a result, for example, excellent anti-snow/anti-icing properties can be maintained for a long period of time.
  • the laminate of the present invention has little change (deterioration over time) in static contact angle, contact angle hysteresis, and droplet falling angle, and has good synovial properties, abrasion resistance, antifouling properties, liquid repellency, and snow/ice sliding properties.
  • power transmission related facilities such as electric wires, electric poles, transformers, insulators, electric wire accessories, etc.
  • Equipment and instruments steel towers, radio towers, metal structures, buildings, houses, warehouses, guardrails, protective fences; building materials such as roofing materials, exterior wall materials, window materials, staircase materials; traffic signs, curved mirrors , display equipment and devices such as traffic lights, signboards, signboards, outdoor displays; antennas for broadcasting, communication, radar, etc.; transportation vehicles such as passenger cars, freight vehicles, motorcycles, all-terrain vehicles, and snowmobiles, Construction, agriculture, work vehicles such as snowplows, transportation machinery and equipment such as railroad vehicles, aircraft, and ships; heat exchangers, coolers, refrigerators, ovens, cutters, liquid dispensers, tanks, stirring and mixing ⁇ Processing equipment such as reaction tanks and discharge nozzles ⁇ Tools (including for food); sporting goods such as skis, sleds, skates, snowshoes, stocks, outdoor activity equipment, mountaineering equipment; bags, shoes, fabrics, non-woven fabrics, etc.
  • transportation vehicles such as passenger cars, freight vehicles, motorcycles, all-terrain vehicles
  • the laminate of the present invention can be suitably used for the purpose of exhibiting excellent snow-sliding/ice-sliding properties (hard-to-snow/hard-to-ice properties) for a long period of time.
  • a method for manufacturing a laminate according to a first aspect of the present invention includes steps of preparing a porous member, forming an organic layer covering at least a portion of the porous member and filling the inside of the porous portion, and and heating the organic layer, wherein the organic layer is a layer formed of one or more of polysiloxane and/or amorphous fluororesin. A step of further forming a porous portion on the porous member may be provided.
  • a metal substrate having a porous portion on at least a portion of its surface is coated with at least a portion of the porous portion and the inside of the porous portion is filled with and heating the organic layer, wherein the organic layer is a layer formed from one or more of polysiloxane and/or amorphous fluororesin. Furthermore, a step of forming a porous portion on at least part of the surface of the metal substrate may be included.
  • the metal substrate, the porous portion (porous member), the organic layer, the polysiloxane and the amorphous fluororesin in the method for producing the laminate of the present invention are the same as ⁇ metal substrate>, ⁇ porous Part>, ⁇ Organic layer>, (Polysiloxane) and (Amorphous fluororesin).
  • the step of forming the porous portion is the same as described in the section (anodic oxidation treatment) in ⁇ porous portion>.
  • the step of forming the organic layer is the same as described in the section ⁇ Organic Layer>, and the step of heating the organic layer is the same as described in the section (Heat Treatment) in ⁇ Organic Layer>. is.
  • Example 1 Polymethylhydrogensiloxane (PMHS: KF-99, manufactured by Shin-Etsu Silicone Co., Ltd.) was used as the lubricant.
  • the metal substrate 1 having a porous portion on at least a part of the surface obtained in Production Example 2 was immersed in PMHS for 10 minutes under ultrasonic waves to impregnate the porous portion with PMHS.
  • the metal substrate 1 was taken out and left at 25° C. under atmospheric pressure with an inclination of 45° to remove excess PMHS. After that, heat treatment was performed in an oven at 200° C. for 2 hours to solidify the PMHS, and a laminate 1 was obtained.
  • Example 2 A laminate 2 was obtained in the same manner as in Example 1, except that the laminate was heat-treated in an oven at 150° C. for 2 hours.
  • Example 3 Polydimethylsiloxane (PDMS: KF-96, manufactured by Shin-Etsu Silicone Co., Ltd.) was used as a lubricant.
  • the metal substrate 1 having a porous portion on at least a part of the surface obtained in Production Example 2 was immersed in PDMS for 10 minutes under ultrasonic waves to impregnate the porous portion with PDMS.
  • the metal substrate 1 was taken out and left at 25° C. under atmospheric pressure with an inclination of 45° to remove excess PDMS. After that, heat treatment was performed in an oven at 300° C. for 2 hours to solidify the PDMS, and a laminate 3 was obtained.
  • Example 4 A laminate 4 was obtained in the same manner as in Example 3, except that the laminate was heat-treated in an oven at 280° C. for 2 hours.
  • Laminate 5 was obtained in the same manner as in Example 3, except that heat treatment was performed in an oven at 250° C. for 2 hours.
  • Amorphous fluororesin (CYTOP: manufactured by AGC, CTL-107MK) was used as the lubricant.
  • the metal substrate 1 having a porous portion on at least a part of the surface obtained in Production Example 2 was immersed in a 7% by mass solution of CYTOP under ultrasonic waves for 10 minutes to impregnate the porous portion with CYTOP.
  • the metal substrate 1 is taken out, left at 25° C. under atmospheric pressure for 10 minutes, dried, and then heat-treated in an oven at 80° C. for 30 minutes, followed by heat treatment at 180° C. for 30 minutes to solidify CYTOP. , to obtain a laminate 6.
  • Example 7 In Example 6, the metal substrate 1 having a porous portion on at least a portion of the surface obtained in Production Example 2 was used as the metal substrate 2 having a porous portion on at least a portion of the surface obtained in Production Example 3. A laminate 7 was obtained in the same manner as in Example 3, except that the material was changed.
  • PSi mixture 1 containing 2 parts of polymethylhydrogensiloxane (PMHS: KF-99 manufactured by Shin-Etsu Silicone Co., Ltd.) and 1 part of polydimethylsiloxane (PDMS: KF-96 manufactured by Shin-Etsu Silicone Co., Ltd.) as lubricants was used.
  • the metal substrate 1 having a porous portion on at least a part of the surface obtained in Production Example 2 was immersed in the PSi mixture 1 under ultrasonic waves for 10 minutes to impregnate the porous portion with the PSi mixture 1.
  • the metal substrate 1 was taken out and left at 25° C. under atmospheric pressure with an inclination of 45° to remove excess PSi mixture 1 . After that, heat treatment was performed in an oven at 200° C. for 2 hours to solidify the PSi mixture 1 and obtain a laminate 8 .
  • Example 9 In Example 8, 1 part of polymethylhydrogensiloxane (PMHS: manufactured by Shin-Etsu Silicone Co., Ltd., KF-99) and polydimethylsiloxane (PDMS: manufactured by Shin-Etsu Silicone Co., Ltd., KF-96) were used as lubricants. A laminate 9 was obtained in the same manner as in Example 8, except that the PSi mixture 2 contained in was used.
  • PMHS manufactured by Shin-Etsu Silicone Co., Ltd., KF-99
  • PDMS manufactured by Shin-Etsu Silicone Co., Ltd., KF-96
  • Example 10 A laminate 10 was obtained in the same manner as in Example 9, except that heat treatment was performed in an oven at 180° C. for 2 hours.
  • Example 11 A laminate 11 was obtained in the same manner as in Example 9, except that the laminate was heat-treated in an oven at 220° C. for 2 hours.
  • Example 12 A laminate 12 was obtained in the same manner as in Example 9, except that heat treatment was performed in an oven at 250° C. for 2 hours.
  • PSi mixture 3 containing 1 part of polymethylhydrogensiloxane (PMHS: KF-99, manufactured by Shin-Etsu Silicone Co., Ltd.) and 2 parts of polydimethylsiloxane (PDMS: KF-96, manufactured by Shin-Etsu Silicone Co., Ltd.) as lubricants was used.
  • the metal substrate 1 having a porous portion on at least a part of its surface obtained in Production Example 2 was immersed in the PSi mixture 3 under ultrasonic waves for 10 minutes to impregnate the porous portion with the PSi mixture 3.
  • the metal substrate 1 was taken out and left at 25° C. under atmospheric pressure with an inclination of 45° to remove excess PSi mixture 3 . Thereafter, heat treatment was performed in an oven at 220° C. for 2 hours to solidify the PSi mixture 3 and obtain a laminate 13 .
  • Example 14 As a lubricant, polymethylsilsesquioxane (PSQ: KR-4000G (50 mass % isoparaffin solution) manufactured by Shin-Etsu Silicone Co., Ltd.) was used.
  • PSQ polymethylsilsesquioxane
  • the metal substrate 1 having a porous portion on at least a part of the surface obtained in Production Example 2 was immersed in a 50 mass % isoparaffin solution of PSQ for 10 minutes under ultrasonic waves. After that, it was dried at room temperature (25° C.) to form a dry film, and a laminate 14 was obtained.
  • the electropolished Al substrate obtained in Production Example 1 was immersed in PMHS for 10 minutes under ultrasonic waves.
  • the electropolished Al substrate was taken out and left at 25° C. under atmospheric pressure with an inclination of 45° to remove excessive PMHS. After that, heat treatment was performed in an oven at 200° C. for 2 hours to solidify the PMHS, and a laminate 15 was obtained.
  • a droplet of 10 ⁇ L was placed on the sample on the electric tilting stage, the stage was tilted at a speed of 0.1°/s in this state, and the angle at which the droplet started to roll was obtained as the droplet falling angle.
  • Cross-sectional SEM and cross-sectional EDS analysis Observation and analysis of the cross section were performed by the following methods.
  • a cross-sectional sample was prepared using a cross-section polisher (manufactured by JEOL Ltd., SM-09010). After that, using a field emission scanning electron microscope (Sigma-500, manufactured by ZEISS) equipped with an EDS (XFlash6-30, manufactured by Bruker), observation and EDS analysis were performed at an acceleration voltage of 2 kV or less.
  • a ball-on-flat tribometer manufactured by CSM Instruments was used, SUJ2 steel balls were used, and the conditions were a load of 1.0 N, a rotation radius of 1.5 mm, and a rotation speed of 1 mm/s or 10 mm/s.
  • the ice adhesion force was measured by the shear adhesion strength test described below.
  • a cylindrical polyester container wrapped with a wire is placed on a sample fixed on a water-cooled cooling unit (WLVPU-30, manufactured by VICS), and a Peltier controller (VPE-20, manufactured by VICS) is controlled to- Cooling was performed at 20° C. for 30 minutes. Thereafter, the container was filled with pure water and cooled again at ⁇ 20° C. for 30 minutes to freeze the pure water in the container and form ice blocks on the surface of the sample.
  • WLVPU-30 water-cooled cooling unit
  • VPE-20 Peltier controller
  • the static contact angle for the solvent (water: surface tension 72.8 mN / m) of the laminates 1, 3 and 6 is 100 to 120 °, and the static contact angle for organic solvents other than water is 90. ° or less.
  • the contact angle hysteresis (the difference between the advancing contact angle and the receding contact angle) is about 10° or less for the solvents 1 to 5 for all of the laminates 1, 3 and 6, and the surface tension of the solvent It can be seen that the effect of Furthermore, regarding the droplet falling angle in 10 ⁇ L of solvent, the droplet falling angle of solvents 1 to 5 in layered product 1 is 11° or less, and the droplet falling angle of solvents 1 to 3 in layered product 3 is 5° or less. , and the drop falling angles of the solvents 1 to 5 in the laminate 6 are all 13° or less, indicating that the laminate 6 has excellent synovial properties.
  • Laminates 1, 3, 6 and 14 obtained in Examples 1, 3, 6 and 14 and polytetrafluoroethylene plates (PTFE plates) were measured for falling angles at water droplet volumes of 10 ⁇ L and 30 ⁇ L. Table 2 shows the results.
  • the water tumble angle at a water droplet amount of 30 ⁇ L for the laminates 1, 3, 6 and 14 and the water tumble angle at a water droplet amount of 10 ⁇ L for the laminates 1, 3 and 6 are smaller than the water contact angle of the PTFE plate and smooth. It was found to be excellent in water resistance. In particular, it can be seen that the laminates 1, 3 and 6 have excellent water sliding properties in terms of the falling angle of water droplets.
  • FIG. 3 shows the results of EDS analysis of cross sections of the surface portions of the laminates 1, 3 and 6 obtained in Examples 1, 3 and 6.
  • FIG. 15 to 17 obtained in Comparative Examples 1 to 3 were observed with an electron microscope.
  • a cross-sectional SEM image of the surface portion is shown in FIG. From the cross-sectional SEM image of the surface portion in FIG.
  • a lubricant layer 1 is formed. Further, from the SEM image of the porous portion in FIG. 2 and FIG. 3, the porous portions of the laminates 1, 3, and 6 are filled with a lubricant. It can be seen that the filling rate is high. On the other hand, it can be seen from FIG. 4 that the laminates 15 to 17 have a structure in which the lubricant layer 1 is formed directly on the metal layer 3. FIG.
  • FIG. 5 shows a photograph of the surface morphology, an electron microscope photograph of the surface morphology, and a cross-sectional EDS analysis result surface image of the surface of the laminate 6 and the laminate 17 after 200 rotations.
  • the laminates 1, 3 and 6 and the laminates 15 to 17 do not have a large difference in the initial coefficient of friction.
  • the laminates 15 to 17 have a coefficient of friction (dynamic friction coefficient) exceeding 0.6 at low rotation speeds, the laminates 1, 3, and 6 maintain low friction coefficients even at high rotation speeds.
  • the wear resistance is greatly improved.
  • the laminates 1, 3, and 6 have improved wear resistance because the lubricant penetrates into the porous portion and the adhesion of the liquid phase is improved. From this, it can be seen that the laminates 1, 3 and 6 are significantly improved in durability compared to the laminates 15-17.
  • the lubricant layer remains on the surface of the laminate 6 even after 200 rotations, whereas the lubricant layer peels off and the base aluminum of the laminate 17 is exposed. I know there is.
  • FIG. 6 shows a photograph of the surface morphology, an electron microscope photograph of the surface morphology, and a surface image of the cross-sectional EDS analysis of the surface portion of the laminate 9 after 100 rotations.
  • the laminates 2, 4, 9 and 10 in which the lubricant after heat treatment is gel-like are compared with the laminates 1, 3, 11 and 12 in which the lubricant after heat treatment is not gel-like. , a low coefficient of friction is maintained even when the number of revolutions increases, indicating that the wear resistance is further improved. Furthermore, it can be seen from FIG. 6 that the laminate 9 still has a lubricant layer on the surface even after 100 rotations, and maintains a low coefficient of friction.
  • the laminates 1, 3, and 6 obtained in Examples 1, 3, and 6 and the electropolished Al substrate obtained in Production Example 1 each contained 2 g/L of acetic acid and 10 g/L of sodium chloride. It was immersed in an aqueous solution having a pH of 3.
  • Ag/AgCl (saturated KCl aqueous solution) as the reference electrode, and platinum as the counter electrode scanning at a scanning speed of 1 mV/s, potentiodynamic polarization measurement was performed. and measured the corrosion current density. Photographs of the surface morphology of the laminates 1, 3 and 6 and the electropolished Al substrate after the potentiodynamic polarization measurement are shown in FIG.
  • the corrosion current density values of laminates 1, 3, and 6 were decreased by five orders of magnitude or more from the corrosion current density value of the electropolished Al substrate. From this, it can be seen that the laminates 1, 3, and 6 are superior in corrosion resistance to the electropolished Al substrate. Furthermore, it can be seen from FIG. 7 that no conspicuous pitting corrosion occurred on the surfaces of the laminates 1, 3, and 6, whereas a large number of pitting corrosion occurred on the surface of the electropolished Al substrate. .
  • Laminates 1, 3, and 6 obtained in Examples 1, 3, and 6 and the electropolished Al substrate obtained in Production Example 1 were placed on a Peltier element set at 20° C., and laminate 1 , 3, 6 and an O-ring were placed on the electropolished Al substrate, and these were placed in a constant temperature and humidity bath at a temperature of 20° C. and a humidity of 60%. Then, the temperature of the Peltier device was lowered to -20°C and left for 30 minutes. Thereafter, the O-ring was filled with ultrapure water produced by an ultrapure water production apparatus (Milli-Q), and further cooled at -20°C for 30 minutes to prepare an ice block. The ice adhesion force was then measured when removing the ice block created in the O-ring. Furthermore, the same procedure was repeated for laminates 1, 3, and 6, and the ice adhesion force was measured each time. Table 6 shows the results.
  • each atomic number concentration (atom%) in the porous portion the ratio of fluorine atoms to the sum of fluorine atoms and aluminum atoms in the porous portion F / (F + Al)
  • Table 8 also shows the number of revolutions when the coefficient of friction exceeds 0.3 or 0.6 in the wear resistance test (rotational speed 10 mm/s) using a ball-on-flat tribometer.
  • FIG. 11 shows electron micrographs of cross-sectional morphologies of the surfaces of the laminates 8, 9, and 13.
  • FIG. 12 shows the results of cross-sectional EDS analysis of the surfaces of the laminates 8, 9, and 13.
  • PSi mixtures 1 to 3 which are composed of PMHS and PDMS, are superior to the case of using PMHS or PDMS alone, with almost no change in static contact angle and water droplet falling angle. It can be seen that the water slipperiness is shown. From Table 8, FIGS. 11 and 12, it can be seen that PSi mixtures 1 to 3 penetrated more into the porous part (higher filling rate in the porous part) than when PMHS or PDMS was used alone. , it can be seen that the adhesiveness of the lubricant layer is high. From Table 8, PSi mixtures 1 to 3 had a friction coefficient exceeding 0.6 in a wear resistance test (10 mm/s) using a ball-on-flat tribometer. It can be seen that the wear resistance is extremely high compared to that of .
  • Example 15 [Synovial liquefaction of a stainless steel substrate having a porous portion on at least a part of its surface]
  • the stainless steel substrate prepared in Production Example 4 was immersed in polydimethylsiloxane (PDMS: KF-96-100CS manufactured by Shin-Etsu Chemical Co., Ltd.) to impregnate the porous portion with PDMS.
  • PDMS polydimethylsiloxane
  • the laminate was treated at 5,000 rpm for 60 seconds to remove excess PDMS, and then heat-treated at 300° C. for 2 hours in an electric furnace to solidify the PDMS to obtain a laminate 15 .
  • FIG. 14 shows an SEM photograph of the surface of the titanium base material thus produced. As shown in FIG. 14, a porous oxide film having a large number of cylindrical pores with a diameter of 30 nm to 50 nm is formed on the surface of the prepared titanium base material.
  • Example 16 [Synovial liquefaction of a titanium base material having a porous oxide film on at least a part of its surface] ⁇ Example 16> A laminate 16 was obtained in the same manner as in Example 15, except that the titanium base material produced in Production Example 5 was used.
  • a zinc substrate having FIG. 14 shows SEM photographs of the surface and cross section of the zinc base material thus produced.
  • Example 17 [Synovial liquefaction of a zinc substrate having a porous coating on at least a part of its surface]
  • the zinc surface prepared in Production Example 6 was impregnated with polymethylhydrogensiloxane (PMHS: KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.) and then heat-treated at 200° C. for 2 hours to obtain laminate 17 .
  • PMHS polymethylhydrogensiloxane
  • FIG. 15 shows an SEM photograph of the surface of the iron substrate thus produced.
  • Example 18 [Synovial liquefaction of an iron substrate having a porous coating on at least a part of its surface] ⁇ Example 18> A laminate 18 was obtained in the same manner as in Example 15, except that the iron base material produced in Production Example 7 was used.
  • PVA polyvinyl alcohol
  • 1M boehmite ( ⁇ -AlOOH) clear sol 20 mL of the PVA solution were mixed to obtain a 0.6M boehmite sol.
  • the 0.6 M boehmite sol was spin-cast on the ⁇ -alumina pellets at 3000 rpm/min for 20 seconds, dried at room temperature (25° C.) for 3 hours, and then annealed in air at 700° C. for 3 hours to obtain a thick film.
  • a mesoporous ⁇ -alumina layer having a thickness of 1.2 ⁇ m was deposited to prepare a mesoporous alumina porous material.
  • Example 19 [Synovial liquefaction of mesoporous alumina porous material] ⁇ Example 19> Amorphous fluororesin (CYTOP: manufactured by AGC, CTL-107MK) was added dropwise to the mesoporous alumina porous material produced in Production Example 8, and the entire surface of the mesoporous alumina porous material was covered with the amorphous fluororesin. After standing for one minute, heat treatment was performed at 80° C. for 30 minutes and then at 180° C. for 30 minutes to obtain a laminate 19 .
  • CYTOP manufactured by AGC, CTL-107MK
  • the lubricating solid surface prepared by injecting a lubricant and performing heat treatment has excellent lubricating properties against various liquids, and the adhesion between the lubricant and the substrate is enhanced by the porous part. It was found to improve and exhibit excellent mechanical durability.
  • the synovial solid surface prepared by impregnating with a lubricant and performing heat treatment exhibits water repellency with a static contact angle of water droplets of 95° or more. ° or less, it can be seen that it has excellent synovial properties against water.
  • the porous portion and at least a part of the porous portion were coated by impregnating the porous body with a lubricant and performing heat treatment.
  • a synovial solid surface having an organic layer formed from a lubricant filled inside the porous portion exhibits excellent water repellency with a static contact angle of water droplets of 110° or more. The drop falling angle is 20° or less, indicating that the liquid has synovial properties against water.

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Abstract

Le but de la présente invention est de fournir : un stratifié ayant de meilleures propriétés synoviales, résistance à l'usure, résistance aux taches, imperméabilité aux liquides, propriétés de glissement de neige/glace, propriétés déperlantes, résistance à la corrosion, durabilité, etc. ; et un procédé de production d'un tel stratifié.　Pour résoudre le problème, la présente invention concerne un stratifié comprenant : un substrat métallique ; une partie poreuse disposée dans au moins une partie du substrat métallique ; et une couche organique recouvrant au moins une partie de la partie poreuse et remplissant l'intérieur de la partie poreuse, la couche organique étant une couche composée de polysiloxane et/ou d'une résine fluorée amorphe.
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