Laminate and method for manufacturing laminate

Abstract

The purpose of the present invention is to provide: a laminate having improved synovial properties, wear resistance, stain resistance, liquid repellency, snow / ice sliding properties, droplet sliding properties, corrosion resistance, durability, etc.; and a method for producing same.　To solve the problem, the present invention provides a laminate comprising: 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 interior of the porous portion, wherein the organic layer is a layer formed from at least one of polysiloxane and / or amorphous fluororesin.

Description

[Technical Field]

[0001] The present invention relates to a laminate and a method for manufacturing the laminate, and more particularly to a laminate having one or more of synovial properties, stain resistance, liquid repellency, and snow / ice sliding properties, and a method for manufacturing the same. [Background technology]

[0002] Slippery liquid-infused porous surface (SLIPS), which mimics the insect-trapping function of pitcher plants found in nature, exhibits dynamic liquid repellency by injecting lubricants such as perfluoropolyether and silicone oil into its micro-nanostructure, thereby reducing the free energy of the surface. SLIPS has the ability to easily slide off various liquids such as water and oil, and also exhibits many noteworthy properties such as surface anti-fouling, prevention of snow and ice adhesion, and improved corrosion resistance. The following prior art is known as related to SLIPS:

[0003] Patent Document 1 describes an aluminum composite material for use in suppressing snow accumulation, which has an aluminum oxide film on the surface of an aluminum component having a hierarchical structure consisting of hierarchical etching pits and an aluminum oxide film having nanopores present on the surface of the etching pits, and the aluminum oxide film has a monomolecular layer of a fluorine-containing organic phosphoric acid compound, and further has a coating layer of fluorine-containing oil on top of this monomolecular layer.

[0004] Patent Document 2 describes an article including a liquid-impregnated surface, the surface including a plurality of micro- and / or nano-scale solid features spaced closely enough to stably contain an impregnating liquid therebetween, the impregnating liquid filling the spaces between the solid features and being held in place between the solid features despite movement of the surface. The article also describes that the solid features may be pores, and that the impregnating liquid may be silicone oil or a fluorocarbon.

[0005] Patent Document 3 describes an article for repelling biological material, which includes a lubricating fluid layer, the lubricating fluid being immiscible with biological material, the lubricating layer forming an ultra-smooth surface on a rough solid substrate, the lubricating fluid adhering to the substrate, the substrate being preferentially wetted by the lubricating fluid, and the solid substrate and the lubricating fluid forming an easy-to-slip surface configured and arranged to contact the biological material. It also describes that the lubricating fluid may be a liquid silicone elastomer or a perfluorofluid, and that the substrate may be a rough surface including a porous material.

[0006] Patent Document 4 describes an article having a slippery surface, which has at least one surface comprising a supramolecular polymer having the general formula PxSy (wherein P is a covalently crosslinked polymer, S is a supramolecular block within the polymer network, x+y is 1, and y is 0 to 1), and a lubricating liquid, wherein the lubricating liquid may comprise a silicone oil or a perfluorocarbon, and the supramolecular polymer and the lubricating liquid have an affinity for each other such that the lubricating liquid is absorbed into the polymer material in an amount sufficient to form a slippery lubricating layer on the surface of the liquid-swollen polymer.

[0007] Patent Document 5 describes a metal product having a fluoropolymer thin film formed on the metal surface, which is obtained by impregnating a surface treatment film, such as an anodized film having gaps such as pores and holes, on the surface of a metal with a fluorine-based monomer having a fluorocarbon chain, and then irradiating this surface treatment film with a low-energy electron beam to form a fluorine polymer thin film.

[0008] Patent Document 6 describes a water- and oil-repellent substrate having a substrate, a porous layer provided on the substrate, and a lubricating liquid impregnated inside the porous layer, wherein the porous layer is composed of a mixture containing at least inorganic oxide fine particles and an inorganic binder containing one or more types of alkoxysilane hydrolysates, and the lubricating liquid is a fluorine-based oil or a silicone oil.

[0009] Non-patent documents 1 to 4 describe the creation of a synovial solid surface that functions as a liquid-like surface by utilizing solid wax-like properties to overcome the durability issue that is a problem with SLIPS. This surface is created by covalently grafting organic molecules with chemical bonds (Si-C, Si-O, CH) such as polydimethylsiloxane (PDMS) or polymethylhydrosiloxane (PMHS). [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2019-85597 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-531989 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-140405 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-531005 [Patent Document 5] Japanese Patent Application Publication No. 11-342371 [Patent Document 6] Japanese Patent Application Publication No. 2019-14793 [Non-patent literature]

[0011] [Non-Patent Document 1] Langmuir, Vol.34, No.38, P.11405-11413 (2011). [Non-patent document 2] Journal of Materials Chemistry A, Vol.6, No.34, P.16355-16360 (2018). [Non-patent document 3] ACS Nano, Vol.11, No.2, P.2248-2256 (2017). [Non-patent document 4] Angewandte Chemie International Edition,Vol.51, No.12, P.2956-2959 (2012). Summary of the Invention [Problem to be solved by the invention]

[0012] Previously known SLIPS systems were less susceptible to physical damage due to the high fluidity of the lubricant, but the lubricant could be consumed through cleaning, evaporation, desorption, etc., posing durability issues. 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 were all unsatisfactory in terms of synovial properties (wettability; static contact angle, contact angle hysteresis, and droplet sliding angle) with respect to various solvents, abrasion resistance, durability, corrosion resistance, ice resistance, etc. The synovial solid surfaces described in Non-Patent Documents 1 to 4 have a graft layer thickness of only a few nm, and therefore the improvement in durability is limited.

[0013] The problem to be solved by the present invention is to provide a laminate having improved lubrication properties, abrasion resistance, stain resistance, liquid repellency, snow and ice sliding properties, droplet sliding properties, corrosion resistance, durability, etc., and a method for producing the same. [Means for solving the problem]

[0014] As a result of extensive research into solving the above-mentioned problems, the inventors have discovered that a laminate having a porous portion and an organic layer that covers at least a portion of the porous portion and is filled inside the porous portion, wherein the organic layer is a layer formed from one or more of an amorphous fluororesin and / or a polysiloxane, has excellent liquid-slip properties that allow various liquids such as water and oil to slide off easily, similar to SLIPS, and also exhibits many noteworthy properties such as abrasion resistance, stain resistance, liquid repellency, snow and ice sliding properties, droplet rolling properties, corrosion resistance, and durability, thereby completing the present invention. Furthermore, as a result of extensive research into solving the above-mentioned problems, the inventors have discovered that a laminate comprising 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 filled inside the porous portion, wherein the organic layer is a layer formed from one or more amorphous fluororesin and / or polysiloxane, has, like SLIPS, excellent liquid-slip properties that allow various liquids such as water and oil to slide off easily, and also exhibits many noteworthy properties such as abrasion resistance, stain resistance, liquid repellency, snow and ice sliding properties, droplet rolling properties, corrosion resistance, and durability, thereby completing the present invention.

[0015] That is, the present invention provides the following laminate and method for producing the laminate. Item 1: A porous portion and an organic layer that covers at least a portion of the porous portion and is filled inside 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: A metal substrate, a porous portion provided on at least a part of the metal substrate, and an organic layer covering at least a part 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 3: The polysiloxane is represented by the following formula (1); [ka] (In formula (1), R 1 , R 2 , X 1 and X 3 are each independently an alkyl group, an aromatic group, or 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. 3 and X 4 may be the same or different from each other.) Item 3. The laminate according to item 1 or 2, wherein the compound is a compound represented by the formula: Item 4: The laminate according to any one of Items 1 to 3, wherein the organic layer is in a gel state. Item 5: The laminate according to any one of Items 1 to 4, which has one or more of synovial properties, stain resistance, liquid repellency, and snow / ice sliding properties. Item 6: The laminate according to any one of Items 1 to 5, which is used as an electric wire, a steel tower, a metal structure, a utility pole, a transformer, an electric wire accessory, a power transmission-related device, a sign, a billboard, an antenna, a roof, a bag, a vehicle, an aircraft, a guardrail, a building material, or a food plant component. Item 7: A step of forming an organic layer on a metal substrate having a porous portion on at least a part of the surface, the organic layer covering at least a part of the porous portion and filling the inside of the porous portion; heating the organic layer; and 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 a step of forming a porous portion on at least a portion of the surface of the metal substrate. [Effects of the Invention]

[0016] The present invention provides a laminate having improved lubrication properties, abrasion resistance, stain resistance, liquid repellency, snow and ice sliding properties, droplet rolling off properties, corrosion resistance, durability, etc., and a method for producing the same. [Brief explanation of the drawings]

[0017] [Figure 1] 1 shows SEM images of the surface morphology of laminates 1, 3, and 6 (Examples) and metal substrate 1 (Comparative Example). [Figure 2] 1 is an SEM image of the cross-sectional morphology of the surface portion of laminates 1, 3, and 6 (Examples). [Figure 3] 1 shows cross-sectional EDS analysis images of the surface portions of laminates 1, 3, and 6 (Examples). [Figure 4] 10 is an SEM image of the cross-sectional morphology of the surface portion of laminates 15 to 17 (comparative examples). [Figure 5]1 shows an image of the surface morphology of laminate 6 (Example) and laminate 17 (Comparative Example) after a wear resistance test, an SEM image of the surface morphology, and a cross-sectional EDS analysis image of the surface portion. [Figure 6] 1 shows an image of the surface morphology of laminate 9 (Example) after a wear resistance test, an SEM image of the surface morphology, and a cross-sectional EDS analysis image of the surface portion. [Figure 7] 1 shows surface morphology images of laminates 1 to 3 (Examples) and an electrolytically polished Al substrate (Comparative Example) after potentiodynamic polarization measurement. [Figure 8] SEM images of the surface morphology of Metal Substrate 1 and Metal Substrate 2, which are different in anodization conditions. [Figure 9] 1 is an SEM image of the cross-sectional morphology of the surface portion of laminates 6 and 7 (Examples). [Figure 10] 10 shows cross-sectional EDS analysis images of the surface portions of laminates 6 and 7 (Examples). [Figure 11] 10 is an SEM image of the cross-sectional morphology of the surface portion of laminates 8, 9, and 13 (Examples). [Figure 12] 10 shows cross-sectional EDS analysis images of the surface portions of laminates 8, 9, and 13 (Examples). [Figure 13] 1 is an SEM image of the surface morphology of the surface portion of the stainless steel substrate produced in Production Example 4. [Figure 14] 1 is an SEM image of the surface morphology of the surface portion of the titanium substrate produced in Production Example 5. [Figure 15] 1 is an SEM image of the surface morphology and cross-sectional morphology of the surface portion of the zinc substrate produced in Production Example 6. [Figure 16] 10 is an SEM image of the surface morphology of the surface portion of the iron substrate produced in Production Example 7. [Explanation of symbols]

[0018] 1 Lubricant layer 2 Porous part 3 Metal base material DETAILED DESCRIPTION OF THE INVENTION

[0019] The laminate and the method for producing the laminate of the present invention will be described in detail below. Note that the present invention is not limited in any way to the embodiments exemplified below, as long as they do not deviate from the gist of the present invention.

[0020] [Laminate] A first aspect of the present invention is a laminate comprising a porous portion and an organic layer that covers at least a portion of the porous portion and fills the interior of the porous portion, the organic layer being a layer formed from one or more of polysiloxane and / or amorphous fluororesin. A second aspect of the present invention is a laminate comprising 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 interior of the porous portion, wherein the organic layer is a layer formed from one or more of polysiloxane and / or amorphous fluororesin.

[0021] <Porous part> In the first and second aspects of the present invention, the porous portion is not particularly limited as long as it has openings in the surface portion and can be filled with polysiloxane and / or amorphous fluororesin that form the organic layer. 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 does not easily separate. For example, it is 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 50 nm or more, and for example, 1 mm or less, preferably 100 μm or less, more preferably 10 μm or less, even more preferably 1 μm or less, and even more preferably 500 nm or less. If the average diameter of the pores forming the porous portion is less than 1 nm, problems such as difficulty in filling the polysiloxane and / or amorphous fluororesin forming the organic layer, time consuming processing, and the need for special techniques may arise. Furthermore, if the average diameter exceeds 1 mm, the amount of polysiloxane and / or amorphous fluororesin used to form the organic layer increases, which is cost-disadvantageous, and there is a risk that the pores will easily separate after filling.

[0022] The thickness of the porous portion is not particularly limited. For example, it is 100 nm or more, preferably 1 μm or more, more preferably 10 μm or more, and for example, 1 mm or less, preferably 500 μm or less, more preferably 100 μm or less. If the thickness of the porous portion is less than 100 nm, the amount of polysiloxane and / or amorphous fluororesin that form the organic layer will be reduced, and the laminate may not exhibit the desired effect.

[0023] The materials and components constituting 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 amorphous fluororesin. Examples include metals, oxides, carbon, ceramics, activated carbon, polymers, organic-inorganic composites, etc. In the present invention, those containing oxides, particularly metal oxides, are preferred. 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, etc. In particular, a porous portion formed by treating the surface layer of the metal substrate is preferred. In the first aspect of the present invention, the porous portion may be formed from one or more porous members. Alternatively, a porous member having a porous portion provided thereon may be used. Furthermore, the porous portion may be provided in at least a portion of the non-metallic substrate. In the second aspect of the present invention, a metal substrate can be used in which a porous portion, which is a porous anodic oxide film, is formed on at least a portion of the metal substrate by anodizing the metal substrate. Alternatively, a metal substrate can be used in which a porous portion is formed by reacting the metal substrate with a reagent capable of making the metal substrate porous (for example, various acids, various bases, etc.).

[0024] (anodic oxidation treatment) The anodic oxidation treatment is an electrochemical treatment in which the surface of a metal substrate is oxidized directly under an electric field in an aqueous solution or an organic electrolyte containing a small amount of water, using the metal substrate as the anode. The metal substrate used in the anodization treatment is not particularly limited, and those described in the above <Metal Substrate> can be used. In the present invention, a metal substrate containing Al, Ti, Fe, Cu, Zn, or an alloy containing one or more of these elements is preferably used. A metal substrate containing Al or an Al alloy is particularly preferred.

[0025] The conditions for the anodization treatment (electrolyte, anodization voltage, anodization current, anodization time, etc.) are not particularly limited as long as they are capable of forming a porous anodization film having pores. The conditions for the anodization treatment can be appropriately adjusted depending on the film thickness of the anodization film, the pore size, etc. For example, for aluminum, an acid aqueous solution can be used, such as an acid aqueous solution containing sulfuric acid, phosphoric acid, nitric acid, chromic acid, silicic acid, oxalic acid, malonic acid, citric acid, sulfamic acid, mixed acids thereof, or salts of these acids. A weakly alkaline borax aqueous solution can also be used. In the present invention, sulfuric acid, oxalic acid, or phosphoric acid is preferred. Furthermore, an aqueous base solution (for example, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide) or a solvent containing a salt (for example, a water-ethylene glycol mixed solution containing ammonium fluoride) can be used as the electrolyte. 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.

[0026] The anodization voltage is not particularly limited, and is, for example, 0.1 V or more, preferably 10 V or more, more preferably 20 V or more, and is, for example, 300 V or less, preferably 240 V or less, more preferably 200 V or less. The anodic oxidation current is not particularly limited, and may be, for example, 10 A / m 2 More than 50A / m 2 or more, for example, 1000A / m 2 Less than 500A / m, preferably 500A / m2 The following is the result. The time for the anodization treatment is not particularly limited, and is, for example, 1 second or more, preferably 1 minute or more, more preferably 10 minutes or more, and even more preferably 15 minutes or more, and is, for example, 100 minutes or less, preferably 60 minutes or less, and more preferably 45 minutes or less.

[0027] In the present invention, the pore size of the porous portion obtained by anodization 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 or less. In the present invention, the thickness of the porous portion obtained by anodization is, for example, 100 nm or more, preferably 500 nm or more, and, for example, 300 μm or less, more preferably 200 μm or less.

[0028] In the present invention, it is preferable to remove oil and fat components, a gas-phase oxide film, and the like present on the anodized surface by carrying out pretreatment such as cleaning, degreasing, etching, or electrolytic polishing, as necessary, before the anodized surface is subjected to anodized treatment.

[0029] In the present invention, after the anodization treatment, a pore widening treatment may be performed as necessary to further enlarge the diameter of the pores (nanopores) formed by the anodization treatment. The pore widening treatment can be performed by immersing the metal substrate after the anodization treatment in an aqueous solution of an acid such as sulfuric acid, phosphoric acid, nitric acid, chromic acid, silicic acid, oxalic acid, sulfamic acid, or a mixed acid thereof for a certain period of time. The conditions for the pore widening treatment in the present invention are, for example, a temperature of the aqueous acid solution in the range of 10°C to 40°C, a concentration of the aqueous acid solution in the range of 1% by mass to 15% by mass, and a treatment time in the range of 60 seconds to 7200 seconds. In the present invention, the pore widening treatment is preferably performed by immersion 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.

[0030] <Metal base material> The metal substrate is not particularly limited. Examples include Mg, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Pd, Ag, Sn, Ta, W, Pt, Au, Pb, alloys containing one or more of these, and laminates thereof. Among these, alloys containing one or more of Al, Ti, Fe, Cu, Zn, Cr, and Ni, and laminates thereof are preferred. Particularly preferred are Al, Al alloys, Ti, Ti alloys, iron, zinc, zinc alloys (e.g., zamak, brass, etc.), and iron-chromium alloys (e.g., stainless steel, etc.). Examples of stainless steel include austenitic stainless steel, austenitic-ferritic duplex stainless steel, ferritic stainless steel, and martensitic stainless steel. Austenitic stainless steel (e.g., SUS200 series, SUS300 series, etc., designated by JIS steel grades) is particularly preferred.

[0031] The shape of the metal substrate is not particularly limited. Any shape can be used depending on the application. Examples include plate, wire / rod (octagonal, hexagonal, flat, square, round, etc.), L-shaped, linear arrow pile, U-shaped arrow pile, groove (U-shaped), I-shaped, H-shaped, rail-shaped, tubular, and a combination of one or more of these shapes. When the metal substrate is in the form of a plate, the thickness 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. When the metal substrate is in the form of a wire / rod, the diameter 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.

[0032] The metal substrate is preferably subjected to a pretreatment such as cleaning, degreasing, etching, or electrolytic polishing to remove oil and fat components, vapor phase oxide film, and the like present on the surface of the metal substrate.

[0033] <Organic layer> In the present invention, the organic layer covers at least a part of the porous portion and fills the inside of the porous portion. In the present invention, the organic layer is a layer formed from one or more of polysiloxane and / or amorphous fluororesin. In the present invention, the organic layer may be, for example, (1) a coating film obtained by applying one or more of polysiloxane and / or amorphous fluororesin or a dried coating film thereof, or (2) a crosslinked coating film obtained by heat-treating the coating film or dried coating film of (1). In the present invention, the polysiloxane and / or amorphous fluororesin forming the organic layer may be dissolved in an appropriate organic solvent or the like. In the present invention, the organic layer is preferably in a gel state. When the organic layer is in a gel state, the droplet rolling angle is reduced and the synovial properties are improved. Here, the term "gel-like" refers to a state in which heat treatment of polysiloxane and / or amorphous fluororesin causes a portion of the polysiloxane and / or amorphous fluororesin to thermally decompose and form intermolecular crosslinks, resulting in an increase in viscosity and a decrease in fluidity. For example, when dimethylpolysiloxane, a type of polysiloxane, is heat-treated at a temperature above the thermal decomposition onset temperature (about 150°C), for example at 280°C, for 3 hours, a portion of the dimethylpolysiloxane is thermally decomposed and forms intermolecular crosslinks, resulting in an increase in viscosity and a decrease in fluidity.

[0034] (Polysiloxane) Polysiloxane is a resin having an -Si-O- bond in the molecule, and is not particularly limited as long as it can form a film. For example, R a 3SiO 0.5 Siloxane unit (M unit) represented by R b Siloxane unit (D unit) represented by 2SiO, R c SiO 1.5 and siloxane units (Q units) represented by SiO2. a , R b and R c are each independently an alkyl group, an aromatic group, or an unsaturated hydrocarbon group, and R a , R b and R c When there are a plurality of each of these, they may be the same or different. Examples include one or more resins selected from the group consisting of 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, MDTQ resins composed of M units, D units, T units and Q units, DT resins composed of D units and T units, MDT resins composed of M units, D units and T units, MTQ resins composed of M units, T units and Q units, and QDT resins composed of D units, T units and Q units. The structure of the polysiloxane is not particularly limited and may be any of linear, cyclic, three-dimensional network structure, etc. In the present invention, it is preferable to use a linear polysiloxane.

[0035] Specific examples of polysiloxanes include 1,1,3,3-tetramethyldisiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, dimethylsiloxane terminally blocked with trimethylsiloxy groups, methylhydrogenpolysiloxane terminally blocked with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer terminally blocked with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane-methylphenylsiloxane copolymer terminally blocked with trimethylsiloxy groups, dimethylpolysiloxane terminally blocked with dimethylhydrogensiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer terminally blocked with dimethylhydrogensiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer terminally blocked with dimethylhydrogensiloxy groups, dimethylsiloxane-methylphenylsiloxane copolymer terminally blocked with dimethylhydrogensiloxy groups, Examples of suitable dimethylsiloxanes include methylphenylpolysiloxanes capped with dimethylhydrogensiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups, methylvinylpolysiloxanes capped at both molecular chain terminals with trimethylsiloxy groups, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymers capped at both molecular chain terminals with trimethylsiloxy groups, dimethylpolysiloxanes capped at both molecular chain terminals with dimethylvinylsiloxy groups, methylvinylpolysiloxanes capped at both molecular chain terminals with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular chain terminals with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular chain terminals with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymers capped at both molecular chain terminals with dimethylvinylsiloxy groups, dimethylpolysiloxanes capped at both molecular chain terminals with trivinylsiloxy groups, and polysiloxanes obtained from methyltrialkoxysilanes.

[0036] The polysiloxane in the present invention is a compound represented by the following formula (1): [ka] (In formula (1), R 1 , R 2, X 1 and X 3 are each independently an alkyl group, an aromatic group, or 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. 3 and X 4 may be the same or different from each other.) Preferably, the polysiloxane is a linear polysiloxane represented by the formula:

[0037] The polysiloxane in the present invention is preferably a polysiloxane represented by the following formula (2): R 3 SiO 1.5 ···(2) (In formula (2), R 3 is an alkyl group, an aromatic group, or an unsaturated hydrocarbon group, and multiple R 3 may be the same or different from each other.) Preferably, the polysiloxane (polysilsesquioxane) has a three-dimensional network structure containing a repeating unit represented by the formula: 3 (OR 4 )2 or -SiR 3 (OR 4 )O 0.5 (In the formula, 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 multiple R 3 and multiple R 4 may be the same or different from each other.

[0038] R in formulas (1) and (2) 1 , R 2 , R 3 , X 1 , X 2 , X 3 and X 4Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, cyclohexyl, heptyl, dodecyl, and stearyl groups. These alkyl groups having 1 to 20 carbon atoms may have a substituent such as a halogen atom. R in formulas (1) and (2) 1 , R 2 , R 3 , X 1 , X 2 , X 3 and X 4 Examples of the aromatic group include aromatic groups having 6 to 30 carbon atoms. Examples include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group (or anthracene group), a phenanthrenyl group (or phenanthrene group), a biphenyl group, a terphenyl group, a pyrenyl group (or pyrene group), a perylenyl group (or perylene group), a benzyl group, and a phenethynyl group. These aromatic groups having 6 to 30 carbon atoms may have a substituent such as a halogen. R in formulas (1) and (2) 1 , R 2 , R 3 , X 1 , X 2 , X 3 and X 4 Examples of the unsaturated hydrocarbon group include unsaturated aliphatic hydrocarbon groups having 2 to 20 carbon atoms, such as ethenyl (vinyl), propenyl (allyl), butenyl, pentenyl, hexenyl, heptenyl, octenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, and octynyl groups.

[0039] In the polysiloxane of formula (1), the number of repeating units n is an integer of 1 or more, for example, 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 of, for example, 500 mm at 25°C. 2 / sec or more, preferably 10,000 mm 2 / sec or more, for example, 10,000,000 mm2 / sec or less, preferably 1,000,000mm 2 / second or less. In the polysiloxane (polysilsesquioxane) having a three-dimensional network structure containing the repeating unit represented by formula (2), the weight-average molecular weight is not particularly limited, and is, for example, 400 or more, preferably 500 or more, and for example, 5,000 or less, preferably 4,000 or less.

[0040] Commercially available polysiloxanes can be used, such as KF-96, KF-965, KF-968, KF-50, KF-54, and 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 X-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, X-40-9301, X-88-1004 and X-88-1007 (all manufactured by Shin-Etsu Silicones Co., Ltd.).

[0041] As the polysiloxane in the present invention, it is preferable to use at least one of polymethylhydrogensiloxane (PMHS) represented by the following formula (3), polydimethylsiloxane (PDMS) represented by the following formula (4), and polymethylsilsesquioxane composed of a structural unit represented by the following formula (5). The polysiloxane used in the present invention is preferably a mixture of PMHS represented by the following formula (3) and PDMS represented by the following formula (4): The blending ratio (volume ratio) of PMHS to PDMS is not particularly limited, but is, for example, PDMS / PMHS=30 / 70 to 85 / 15, preferably 45 / 55 to 80 / 20.

[0042] [ka] (In the formula, p and q represent the number of repeating units, p is 10 to 200, and q is 10 to 100.) [ka] (In the formula, r represents the number of repeating units and is 1 to 2500, preferably 4 to 2250.) CH3SiO 1.5 ···(5)

[0043] (amorphous fluororesin) The amorphous fluororesin is not particularly limited as long as it is an amorphous (non-crystalline) resin. Examples of amorphous fluororesins include one or more selected from the group consisting of perfluoro(4-vinyloxy-1-butene) cyclized polymer (BVE), tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD), tetrafluoroethylene-perfluoromethyl vinyl ether copolymer (TFE / MFA), tetrafluoroethylene-perfluoroethyl vinyl ether copolymer (TFE / EFA), tetrafluoroethylene-perfluoropropyl vinyl ether copolymer (TFE / PFA), and the like. Amorphous fluororesin may be a commercially available product, such as the AF series (manufactured by DuPont-Mitsui Fluorochemicals), the Algoflon series (manufactured by Solvay Special Polymers Japan), or the Cytop series (manufactured by AGC).

[0044] In the present invention, the amorphous fluororesin may be, for example, a fluororesin having the following repeating unit (6): [ka] (In the formula, s represents the number of repeating units.) It is preferable to use a perfluoro(4-vinyloxy-1-butene) cyclized polymer (BVE) having the formula: For example, CTX-809A, CTL-109AE, CTX-109AE, CTL-809M, CTL-107MK, CTX-809SP2, CT-SOLV180, CT-SOLV100E, CT-SOLV100K, etc., from the Cytop series can be used.

[0045] The average molecular weight of the amorphous fluororesin is not particularly limited and is, for example, 100,000 or more, preferably 120,000 or more, more preferably 150,000 or more, and is, for example, 500,000 or less, preferably 300,000 or less, more preferably 200,000 or less.

[0046] (Coating and Impregnation Methods) In the present invention, the organic layer formed from one or more of polysiloxane and / or amorphous fluororesin covers at least a part of the porous portion and fills the interior of the porous portion. The method for coating at least a portion of the porous portion with an organic layer and filling the interior of the porous portion with the organic layer is not particularly limited. For example, dip coating, bar coating, die coating, slit coating, roll coating, spray coating, spin coating, and other methods can be used. In the present invention, dip coating is preferred from the standpoint of production efficiency, etc. Furthermore, when using dip coating, ultrasonication can be used to promote filling of the interior of the porous portion. Furthermore, in the present invention, spray coating can be used to selectively coat and fill only desired portions of the porous portion with the organic layer. The amount of polysiloxane and / or amorphous fluororesin coated and filled is not particularly limited. For example, 10 μg / cm 2 or more, preferably 50 μg / cm 2 That's all.

[0047] (heat treatment) In the present invention, it is preferable that an organic layer formed from one or more of polysiloxane and / or amorphous fluororesin is used to cover at least a portion of the porous portion and fill the interior of the porous portion, and then, if necessary, dried (solvent removal) and then subjected to a heat treatment. The heat treatment conditions are not particularly limited. The temperature may be within a range in which the polysiloxane and / or amorphous fluororesin do not ignite or spontaneously combust. In the present invention, the heat treatment conditions are preferably such that at least a portion of the polysiloxane and / or amorphous fluororesin undergoes intermolecular crosslinking by heat treatment, the organic layer gels, the viscosity increases, and a gel-like substance having viscoelasticity is obtained. Heat treatment conditions include, for example, in air, a temperature above the thermal decomposition temperature, 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. Heating is preferably carried out in a heating furnace (oven).

[0048] By carrying out the heat treatment, the organic layer formed from one or more of polysiloxane and / or amorphous fluororesin can be firmly integrated with the porous portion. In the laminate of the present invention, an organic layer formed from one or more of polysiloxane and / or amorphous fluororesin is filled into the porous portion and exerts an anchoring effect, thereby enabling an organic layer with excellent abrasion resistance to be provided on at least a portion of the porous portion. Furthermore, in the present invention, by performing a heat treatment, an organic layer formed from one or more of polysiloxane and / or amorphous fluororesin can be intermolecularly crosslinked to form a three-dimensional network and gelled. This firmly integrates the organic layer with the porous portion and significantly suppresses the separation of the organic layer, making it possible to maintain one or more of synovial properties, antifouling properties, liquid repellency, and snow / ice sliding properties for a long period of time.

[0049] <Characteristics of laminate> The laminate of the present invention has one or more of synovial properties, stain resistance, 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. Furthermore, the laminate of the present invention preferably has a contact angle hysteresis, which is the difference between the advancing contact angle and the receding contact angle, of 15° or less, preferably 10° or less, for solvents having a surface tension of 20 mN / m or more and 80 mN / m or less (water, rapeseed oil, hexadecane, dodecane, ethylene glycol, ethanol, etc.). Furthermore, the laminate of the present invention preferably has a droplet sliding angle of 20° or less, preferably 16° or less, for solvents having a surface tension of 20 mN / m or more and 80 mN / m or less. When the static contact angle, contact angle hysteresis, and droplet sliding angle are within these ranges, the laminate can have one or more of synovial properties, antifouling properties, liquid repellency, and snow / ice sliding properties. Furthermore, the laminate of the present invention exhibits little change over time (deterioration over time) in the static contact angle, contact angle hysteresis, and droplet sliding angle, and can maintain one or more of synovial properties, antifouling properties, liquid repellency, and snow / ice sliding properties for a long period of time. This allows, for example, excellent anti-snow and anti-icing properties to be maintained for a long period of time.

[0050] <Applications of laminates> The laminate of the present invention exhibits little change over time (aging deterioration) in static contact angle, contact angle hysteresis, and droplet sliding angle, and can continuously exhibit one or more of the following properties for a long period of time: lubricity, abrasion resistance, stain resistance, liquid repellency, snow and ice sliding property, droplet sliding property, corrosion resistance, and durability. Utilizing these properties, the laminate can be used in a wide range of applications, including, for example, power transmission-related facilities, equipment, and instruments such as electric wires, utility poles, transformers, insulators, and electric wire accessories; buildings such as steel towers, radio towers, metal structures, buildings, houses, warehouses, guardrails, and protective fences; building materials such as roofing materials, exterior wall materials, window materials, and staircase materials; and surfaces such as traffic signs, convex mirrors, traffic lights, billboards, signboards, and outdoor displays. Examples of suitable materials include display equipment and devices; antennas for broadcasting, communications, radar, etc.; transportation machinery and equipment such as passenger cars, freight vehicles, motorcycles, all-terrain vehicles, snowmobiles, etc., construction, agricultural, and work vehicles such as snowplows, railway vehicles, aircraft, and ships; processing equipment and tools (including food-use equipment) such as heat exchangers, coolers, freezers and refrigerators, ovens, cutters, liquid dispensers, tanks, stirring, mixing, and reaction vessels, and discharge nozzles; sporting goods such as skis, sleds, skates, snowshoes, poles, outdoor activity equipment, and mountain climbing equipment; and articles requiring waterproofing, such as bags, shoes, fabrics, and nonwoven fabrics. In particular, the laminate of the present invention is suitable for use in applications where excellent snow and ice sliding properties (snow and ice adhesion resistance) are required for a long period of time.

[0051] [Method of manufacturing laminate] A method for producing a laminate according to a first aspect of the present invention includes the steps of preparing a porous member, forming an organic layer that covers at least a portion of the porous member and fills the porous portion, and heating the organic layer, wherein the organic layer is a layer formed from one or more of polysiloxane and / or amorphous fluororesin. The method may further include the step of forming a porous portion on the porous member. A method for producing a laminate according to a second aspect of the present invention includes the steps of: forming an organic layer on a metal substrate having a porous portion on at least a portion of its surface, the organic layer covering at least a portion of the porous portion and filling the porous portion; and heating the organic layer, wherein the organic layer is a layer formed from one or more of polysiloxane and / or amorphous fluororesin. The method may further include the step of forming a porous portion on at least a portion of the surface of the metal substrate.

[0052] In the method for producing a laminate of the present invention, the metal substrate, the porous portion (porous member), the organic layer, the polysiloxane, and the amorphous fluororesin are the same as those described in the sections <Metal substrate>, <Porous portion>, <Organic layer>, (Polysiloxane), and (Amorphous fluororesin) in the above [Laminate]. The process for forming the porous portion is the same as that described in the section (anodic oxidation treatment) in <Porous portion>. The step of forming the organic layer is the same as that described in the <Organic Layer> section, and the step of heating the organic layer is the same as that described in the <Organic Layer> section (Heat Treatment). [Example]

[0053] The present invention will be described in detail below with reference to specific examples. These specific examples are merely one embodiment of the present invention, and the present invention is not limited to these examples in any way. Unless otherwise specified, the compounds used in this example were commercially available products and were used as they were without purification.

[0054] [Preparation of electropolished Al substrate] <Production Example 1> An aluminum plate with a thickness of 0.3 mm and purity of 99.5% was washed with acetone and subjected to electrolytic polishing treatment in an ethanol solution containing 20% ​​by volume of 60% by mass perchloric acid at 20 V for 5 minutes using aluminum foil as the counter electrode to obtain an electrolytically polished Al substrate.

[0055] [Preparation of a metal substrate having a porous portion on at least a part of its surface] <Production Example 2> The electrolytically polished Al substrate obtained in Production Example 1 was subjected to anodization treatment in 0.3 M H2SO4 at 15°C with an applied voltage of 25 V for 30 minutes to form a porous alumina coating layer on the aluminum plate. Furthermore, a pore widening treatment was performed by immersing the substrate in a 5 mass % H3PO4 aqueous solution at 30°C for 15 minutes to adjust the pore diameter of the porous alumina coating layer to 30 nm to 50 nm, thereby obtaining a metal substrate 1 having a porous portion on at least a part of its surface.

[0056] <Production Example 3> The electrolytically polished Al substrate obtained in Production Example 1 was subjected to anodization treatment in 0.3 M H3PO4 at 20°C with an applied voltage of 100 V for 30 minutes to form a porous alumina coating layer on the aluminum plate. Furthermore, a pore widening treatment was performed by immersing the substrate in a 5 mass % H3PO4 aqueous solution at 30°C for 15 minutes to adjust the pore diameter of the porous alumina coating layer to 80 nm to 120 nm, thereby obtaining a metal substrate 2 having a porous portion on at least a part of its surface.

[0057] [Laminate fabrication] Example 1 Polymethylhydrogensiloxane (PMHS: KF-99, manufactured by Shin-Etsu Silicone Co., Ltd.) was used as the lubricant. The metal substrate 1 having porous portions on at least a part of the surface thereof obtained in Production Example 2 was immersed in PMHS for 10 minutes under ultrasonic waves to impregnate the porous portions with PMHS. The metal substrate 1 was taken out and left at a 45° incline at 25°C under atmospheric pressure to remove excess PMHS. Thereafter, the PMHS was solidified by heat treatment in an oven at 200° C. for 2 hours, and a laminate 1 was obtained.

[0058] <Example 2> Laminate 2 was obtained in the same manner as in Example 1, except that the heat treatment was carried out in an oven at 150° C. for 2 hours.

[0059] Example 3 Polydimethylsiloxane (PDMS: KF-96, manufactured by Shin-Etsu Silicones Co., Ltd.) was used as the lubricant. The metal substrate 1 having porous portions on at least a part of the surface thereof obtained in Production Example 2 was immersed in PDMS under ultrasonic waves for 10 minutes to impregnate the porous portions with PDMS. The metal substrate 1 was taken out and left at a 45° incline at 25°C under atmospheric pressure to remove excess PDMS. Thereafter, the PDMS was solidified by heat treatment in an oven at 300° C. for 2 hours, and a laminate 3 was obtained.

[0060] Example 4 Laminate 4 was obtained in the same manner as in Example 3, except that the heat treatment was carried out in an oven at 280° C. for 2 hours.

[0061] <Example 5> Laminate 5 was obtained in the same manner as in Example 3, except that the heat treatment was carried out in an oven at 250° C. for 2 hours.

[0062] Example 6 As a lubricant, amorphous fluororesin (CYTOP: manufactured by AGC Corporation, CTL-107MK) was used. The metal substrate 1 having porous portions on at least a part of its surface obtained in Production Example 2 was immersed in a 7 mass % solution of CYTOP under ultrasonic waves for 10 minutes to impregnate the porous portions with CYTOP. The metal substrate 1 was removed and left to dry at 25°C and atmospheric pressure for 10 minutes, after which it was heat-treated in an oven at 80°C for 30 minutes, and then at 180°C for 30 minutes to solidify the CYTOP, thereby obtaining a laminate 6.

[0063] Example 7 In Example 6, a laminate 7 was obtained in the same manner as in Example 3, except that the metal substrate 1 having a porous portion on at least a part of its surface obtained in Production Example 2 was replaced with the metal substrate 2 having a porous portion on at least a part of its surface obtained in Production Example 3.

[0064] Example 8 As a lubricant, PSi mixture 1 containing 2 parts polymethylhydrogensiloxane (PMHS: Shin-Etsu Silicone Co., Ltd., KF-99) and 1 part polydimethylsiloxane (PDMS: Shin-Etsu Silicone Co., Ltd., KF-96) was used. The metal substrate 1 having porous portions on at least a part of its surface obtained in Production Example 2 was immersed in the PSi mixture 1 under ultrasonic waves for 10 minutes, so that the porous portions were impregnated with the PSi mixture 1. The metal substrate 1 was taken out and left at a 45° incline at 25°C under atmospheric pressure to remove excess PSi mixture 1. Thereafter, the mixture was heated in an oven at 200° C. for 2 hours to solidify the PSi mixture 1, thereby obtaining a laminate 8.

[0065] Example 9 In Example 8, a laminate 9 was obtained in the same manner as in Example 8, except that a PSi mixture 2 containing 1 part polymethylhydrogensiloxane (PMHS: manufactured by Shin-Etsu Silicones Co., Ltd., KF-99) and 1 part polydimethylsiloxane (PDMS: manufactured by Shin-Etsu Silicones Co., Ltd., KF-96) was used as the lubricant.

[0066] Example 10 A laminate 10 was obtained in the same manner as in Example 9, except that the heat treatment was carried out in an oven at 180° C. for 2 hours.

[0067] Example 11 A laminate 11 was obtained in the same manner as in Example 9, except that the heat treatment was carried out in an oven at 220° C. for 2 hours.

[0068] Example 12 A laminate 12 was obtained in the same manner as in Example 9, except that the heat treatment was carried out in an oven at 250° C. for 2 hours.

[0069] Example 13 As the lubricant, PSi mixture 3 containing 1 part polymethylhydrogensiloxane (PMHS: Shin-Etsu Silicone Co., Ltd., KF-99) and 2 parts polydimethylsiloxane (PDMS: Shin-Etsu Silicone Co., Ltd., KF-96) was used. The metal substrate 1 having porous portions on at least a part of its surface obtained in Production Example 2 was immersed in the PSi mixture 3 for 10 minutes under ultrasonic waves, and the PSi mixture 3 was impregnated into the porous portions. The metal substrate 1 was taken out and left at a 45° inclination under atmospheric pressure at 25°C to remove excess PSi mixture 3. Thereafter, the mixture was heated in an oven at 220° C. for 2 hours to solidify the PSi mixture 3, thereby obtaining a laminate 13.

[0070] Example 14 As the lubricant, polymethylsilsesquioxane (PSQ: manufactured by Shin-Etsu Silicones Co., Ltd., KR-4000G (50% by mass isoparaffin solution)) 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 a 50% by mass isoparaffin solution of PSQ under ultrasonic waves for 10 minutes. Thereafter, it was dried at room temperature (25° C.) to form a dry film, and a laminate 14 was obtained.

[0071] <Comparative Example 1> Polymethylhydrogensiloxane (PMHS: KF-99, manufactured by Shin-Etsu Silicone Co., Ltd.) was used as the lubricant. The electrolytically polished Al substrate obtained in Production Example 1 was immersed in PMHS under ultrasonic waves for 10 minutes. The electropolished Al substrate was removed and left at a 45° incline at 25°C under atmospheric pressure to remove excess PMHS. Thereafter, the PMHS was solidified by heat treatment in an oven at 200° C. for 2 hours, and a laminate 15 was obtained.

[0072] <Comparative Example 2> A laminate 16 was obtained in the same manner as in Comparative Example 1, except that polydimethylsiloxane (PDMS: KF-96, manufactured by Shin-Etsu Silicones Co., Ltd.) was used as the lubricant.

[0073] <Comparative Example 3> A laminate 17 was obtained in the same manner as in Comparative Example 1, except that an amorphous fluororesin (CYTOP: manufactured by AGC Corporation, CTL-107MK) was used as the lubricant.

[0074] [evaluation] <Measurement method etc.>

[0075] (Method for measuring static contact angle) Using a contact angle meter (Kyowa Interface Science Co., Ltd., DM-CE1), a 4 μL droplet was dropped onto the sample surface from a microsyringe, and the droplet was observed and measured with a CCD camera attached to the device to determine the static contact angle.

[0076] (Method for measuring contact angle hysteresis) Using a contact angle meter (DM-CE1, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle when injecting a droplet of approximately 4 μL onto the sample surface from a microsyringe (advancing contact angle) and the contact angle when sucking up the droplet (receding contact angle) were observed and measured using a CCD camera attached to the device, and the difference between the advancing contact angle and the receding contact angle was calculated as the contact angle hysteresis.

[0077] (Method for measuring the droplet falling angle) A 10 μL droplet was placed on the sample on a motorized tilting stage, and the stage was tilted at a speed of 0.1° / s. The angle at which the droplet began to roll was determined as the droplet rolling angle.

[0078] (Surface SEM) Observation of the surface morphology using an electron microscope (surface SEM) was carried out by the following method. To prevent charging during observation, a tungsten film of approximately 10 nm was formed on the synovial solid surface using a sputtering device (Vacuum Devices, MSP-20TK).Then, the surface was observed using a field emission scanning electron microscope (ZEISS, Sigma-500) at an accelerating voltage of 2 kV or less.

[0079] (Cross-sectional SEM and cross-sectional EDS analysis) The cross-sections were observed and analyzed as follows. Cross-section samples were prepared using a cross-section polisher (JEOL, SM-09010), and then observed and analyzed using a field emission scanning electron microscope (ZEISS, Sigma-500) equipped with an EDS (Bruker, XFlash6-30) at an accelerating voltage of 2 kV or less.

[0080] (wear test) A ball-on-flat tribometer (manufactured by CSM Instruments) was used, and the test was carried out using an SUJ2 steel ball under the conditions of 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.

[0081] (Method for measuring ice adhesion) The ice adhesion force was measured by the shear adhesion strength test described below. A cylindrical polyester container wrapped with wire was placed on a sample fixed on a water-cooled cooling unit (VICS, WLVPU-30), and the sample was cooled to -20°C for 30 minutes using a Peltier controller (VICS, VPE-20). The container was then filled with pure water and cooled again at -20°C for 30 minutes to freeze the pure water in the container and form an ice block on the surface of the sample. After the ice block was formed, the sample was placed on a water-cooled cooling unit maintained at -20°C, and the tip of a stress measuring device (Imada Co., Ltd., ZTS-50N) was attached to the wire wrapped around the container, and the measuring device was manually pulled horizontally to determine the shear stress when the ice block peeled off from the sample surface, which was taken as the ice adhesion force.

[0082] <Wettability> For the laminates 1, 3, and 6 obtained in Examples 1, 3, and 6, the static contact angle (°), contact angle hysteresis (°), which is the difference between the advancing contact angle and the receding contact angle, and the droplet sliding angle (°) for a 10 μL droplet were measured for the liquids (water (solvent 1), ethylene glycol (solvent 2), rapeseed oil (solvent 3), hexadecane (solvent 4), and ethanol (solvent 5)) having the surface tensions shown in Table 1. The results are shown in Table 1.

[0083] [Table 1]

[0084] Table 1 shows that the static contact angles of laminates 1, 3, and 6 with respect to the solvent (water: surface tension 72.8 mN / m) are 100 to 120°, and the static contact angles with respect to organic solvents other than water are 90° or less. This indicates that the surfaces of laminates 1, 3, and 6 are water-repellent and lipophilic. Judging from the static contact angles, the liquid-repellency with respect to solvents 2 to 5 is not high, but they exhibit excellent liquid-synthetic properties. Furthermore, the contact angle hysteresis (the difference between the advancing contact angle and the receding contact angle) is approximately 10° or less with respect to solvents 1 to 5 for all laminates 1, 3, and 6, indicating that the effect of the surface tension of the solvent is small. Furthermore, with regard to the droplet sliding angle for 10 μL of solvent, the droplet sliding angles for solvents 1 to 5 in laminate 1 were all 11° or less, the droplet sliding angles for solvents 1 to 3 in laminate 3 were all 5° or less, and the droplet sliding angles for solvents 1 to 5 in laminate 6 were all 13° or less, indicating that they have excellent synovial properties.

[0085] The sliding angles of water droplets of 10 μL and 30 μL were measured for the laminates 1, 3, 6, and 14 obtained in Examples 1, 3, 6, and 14 and the polytetrafluoroethylene plate (PTFE plate). The results are shown in Table 2. [Table 2]

[0086] From Table 2, it can be seen that the water sliding angles of Laminates 1, 3, 6 and 14 at a water droplet volume of 30 μL and the water sliding angles of Laminates 1, 3 and 6 at a water droplet volume of 10 μL are smaller than the water contact angle of the PTFE plate, indicating that they have excellent water sliding properties. In particular, the water droplet sliding angle indicates that Laminates 1, 3 and 6 have excellent water sliding properties.

[0087] <Effect of heat treatment temperature on wettability> The static contact angle (°) of water and the water droplet sliding angle (°) of a 10 μL water droplet were measured for the laminates 1 to 5 and 9 to 12 obtained in Examples 1 to 5 and 9 to 12. The results are shown in Table 3. [Table 3]

[0088] When PMHS is heat-treated, it is in a gel state at 150°C and in a solid (powder) state at 200°C. When PDMS is heat-treated, it is in a liquid state at 250°C, a gel state at 280°C, and a solid state (powder state) at 300°C. When PSi mixture 2 was heat treated at 180°C, 200°C, 220°C and 250°C, it was in a gel state. As can be seen from Table 3, laminates 2 and 4, which were obtained by adjusting the heat treatment temperature so that the lubricant would become gel-like after heat treatment, have smaller water sliding angles than laminates 1 and 3, which were obtained by adjusting the heat treatment temperature so that the lubricant would become solid after heat treatment. This shows that the lubrication properties (water sliding properties) of the laminate, such as the water sliding angle, can be controlled by adjusting the heat treatment temperature of the lubricant.

[0089] <Surface form> The surface morphologies of the laminates 1, 3 and 6 obtained in Examples 1, 3 and 6 and the metal substrate 1 obtained in Production Example 2 were observed under an electron microscope. The results are shown in FIG. 1, it can be seen that the surface of the metal substrate 1 has a porous portion with pores having a diameter of 30 to 50 nm present on the surface. On the other hand, it can be seen that the surfaces of the laminates 1, 3, and 6 are all smooth. Furthermore, the occurrence of wrinkles due to thermal shrinkage was confirmed on the surface of the laminate 3.

[0090] <Surface section form> The cross-sectional morphology of the surface portion of the laminates 1, 3, and 6 obtained in Examples 1, 3, and 6 was observed by an electron microscope. A cross-sectional SEM image of the surface portion is shown in Figure 2. An SEM image of the porous portion is also shown in Figure 2. FIG. 3 shows the results of EDS analysis of the cross sections of the surface portions of the laminates 1, 3, and 6 obtained in Examples 1, 3, and 6. The cross-sectional morphology of the surface portion of each of the laminates 15 to 17 obtained in Comparative Examples 1 to 3 was observed by an electron microscope. FIG. 4 shows a cross-sectional SEM image of the surface portion. 2, it can be seen that in the surface portions of the laminates 1, 3, and 6, the lubricant has penetrated into the porous portion 2 provided on the metal layer 3, and a lubricant layer 1 has been formed on the porous portion 2. Furthermore, it can be seen from the SEM image of the porous portion in FIG. 2 and FIG. 3 that the porous portions of the laminates 1, 3, and 6 are filled with the lubricant, and that the filling rate of the lubricant is particularly high in the laminates 1 and 3. 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.

[0091] <Wear resistance> A wear test was carried out at a rotational speed of 1 mm / s for the laminates 1, 3, and 6 obtained in Examples 1, 3, and 6 and the laminates 15 to 17 obtained in Comparative Examples 1 to 3. Table 4 shows the results, including the rotational speed at which the friction coefficient (dynamic friction coefficient) exceeded 0.6 (the rotational speed at which the friction coefficient exceeded 0.6) and the initial friction coefficient. FIG. 5 shows a photograph of the surface morphology, an electron microscope photograph of the surface morphology, and a surface image resulting from cross-sectional EDS analysis of the surface portion for Laminate 6 and Laminate 17 after 200 rotations.

[0092] [Table 4]

[0093] Table 4 shows that there is no significant difference in the initial friction coefficient between laminates 1, 3, and 6 and laminates 15 to 17. However, while laminates 15 to 17 have a friction coefficient (dynamic friction coefficient) exceeding 0.6 at low rotation speeds, laminates 1, 3, and 6 maintain a low friction coefficient even as the rotation speed increases, indicating a significant improvement in wear resistance. It is believed that the wear resistance of laminates 1, 3, and 6 was improved because the lubricant penetrated into the porous portions and the adhesiveness of the liquid phase was improved. This shows that the laminates 1, 3 and 6 have significantly improved durability compared to the laminates 15-17. Furthermore, from Figure 5, it can be seen that the lubricant layer remains on the surface of laminate 6 even after 200 rotations, whereas the lubricant layer has peeled off from laminate 17, exposing the aluminum substrate.

[0094] <Heat treatment temperature dependence of wear resistance> A wear test was carried out on the laminates 1 to 12 obtained in Examples 1 to 4 and 9 to 12 at a rotational speed of 10 mm / s, and the rotational speed at which the friction coefficient exceeded 0.6 (the rotational speed at which the friction coefficient exceeded 0.6) was measured. The results are shown in Table 5. FIG. 6 shows a photograph of the surface morphology of the laminate 9 after 100 rotations, an electron microscope photograph of the surface morphology, and a surface image resulting from cross-sectional EDS analysis of the surface portion.

[0095] [Table 5]

[0096] Table 5 shows that laminates 2, 4, 9 and 10, in which the lubricant after heat treatment is in a gel state, maintain a low friction coefficient even when the rotation speed increases, and have improved wear resistance, compared to laminates 1, 3, 11 and 12, in which the lubricant after heat treatment is not in a gel state. Furthermore, it can be seen from FIG. 6 that the lubricant layer remains on the surface of the laminate 9 even after 100 rotations, and the laminate 9 maintains a low coefficient of friction.

[0097] <Corrosion resistance> The laminates 1, 3, and 6 obtained in Examples 1, 3, and 6 and the electropolished Al substrate obtained in Production Example 1 were each immersed in an aqueous solution containing 2 g / L of acetic acid and 10 g / L of sodium chloride and having a pH of 3. Potentiodynamic polarization measurements were performed using the laminates 1, 3, and 6 and the electropolished Al substrate as working electrodes, Ag / AgCl (saturated KCl aqueous solution) as a reference electrode, and platinum as a counter electrode, scanning at a scan rate of 1 mV / s, to measure the corrosion current density. FIG. 7 shows photographs of the surface morphology of the laminates 1, 3, and 6 and the electrolytically polished Al substrate after the potentiodynamic polarization measurement.

[0098] The corrosion current density values ​​of the laminates 1, 3, and 6 were five orders of magnitude lower than the corrosion current density value of the electrolytically polished Al substrate, which indicates that the laminates 1, 3, and 6 have superior corrosion resistance to the electrolytically polished Al substrate. Furthermore, it can be seen from FIG. 7 that no noticeable pitting corrosion occurred on the surfaces of the laminates 1, 3, and 6, whereas many pitting corrosion occurred on the surface of the electrolytically polished Al substrate.

[0099] <Ice resistance> The 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 to 20°C. O-rings were then placed on the laminates 1, 3, and 6 and the electropolished Al substrate, and these were then placed in a thermo-hygrostat chamber at a temperature of 20°C and a humidity of 60%. The temperature of the Peltier element was then lowered to -20°C and left for 30 minutes. Thereafter, the O-ring was filled with ultrapure water produced in an ultrapure water production system (Milli-Q), and the O-ring was further cooled to -20°C for 30 minutes to produce an ice block. Next, the ice adhesion force was measured when removing the ice blocks that had formed inside the O-ring. Furthermore, the same procedure was repeated for Laminates 1, 3, and 6, and the ice adhesion force was measured each time. The results are shown in Table 6.

[0100] [Table 6]

[0101] Table 6 shows that the ice adhesion force (shear adhesion strength of ice blocks) at -20°C was a large value of over 700 kPa for the electropolished Al substrate, while laminates 1, 3, and 6 showed low values ​​of approximately 50 to 120 kPa, demonstrating excellent ice resistance.

[0102] <Effect of anodizing conditions> For the laminate 6 obtained in Example 6 and the laminate 7 obtained in Example 7, the atomic number concentrations (atom%) in the porous part, the ratio of fluorine atoms to the sum of fluorine and aluminum atoms in the porous part F / (F + Al), and the number of rotations when the friction coefficient exceeds 0.3 or 0.6 in the abrasion resistance test (rotation speed 1 mm / s) using a ball-on-flat tribometer are shown in Table 7, respectively. Electron micrographs of the surface morphologies of the metal substrate 1 and the metal substrate 2 are shown in FIG. 8. Electron micrographs of the cross-sectional morphologies of the surface parts of the laminate 3 and the laminate 4 are shown in FIG. 9. Results of cross-sectional EDS analysis of the surface parts of the laminate 3 and the laminate 4 are shown in FIG. 10.

[0103] [Table 7]

[0104] From Table 7 and FIGS. 8 to 10, it can be seen that by adjusting the anodic oxidation conditions when forming the porous part on the electrolytically polished Al plate, the pore diameter of the porous part can be adjusted, and by increasing the pore diameter of the porous part, it becomes possible to improve the filling rate of the lubricant in the porous part. Also, from the results of the abrasion resistance test (rotation speed 1 mm / s) using a ball-on-flat tribometer in Table 7, it can be seen that the laminate 4 containing more lubricant in the porous part has improved abrasion resistance compared to the laminate 3.

[0105] <Various evaluations of the PSi mixture> For the laminates 1, 3, 8, 9, and 13 obtained in Examples 1, 3, 8, 9, and 13, the static contact angle (°) with respect to water, the contact angle hysteresis (°) which is the difference between the advancing contact angle and the receding contact angle with respect to water, and the water droplet falling angle (°) at 30 μL of water were measured. The results are shown in Table 8. Furthermore, for laminates 1, 3, 8, 9 and 13, the atomic 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)), and the rotation speed at which the friction coefficient exceeded 0.3 or 0.6 in a wear resistance test using a ball-on-flat tribometer (rotation speed 10 mm / s) are also shown in Table 8. FIG. 11 shows electron microscope photographs of the cross-sectional morphology of the surface portions of the laminates 8, 9, and 13. The results of cross-sectional EDS analysis of the surface portions of the laminates 8, 9, and 13 are shown in FIG.

[0106] [Table 8]

[0107] Table 8 shows that PSi mixtures 1 to 3 composed of PMHS and PDMS have almost no change in static contact angle and water droplet sliding angle compared to when PMHS or PDMS is used alone, demonstrating excellent water-repellent properties. From Table 8 and Figures 11 and 12, it can be seen that PSi mixtures 1 to 3 penetrate more into the porous area (higher filling rate in the porous area) compared to when PMHS or PDMS was used alone, and that the adhesion of the lubricant layer was improved. Table 8 shows that PSi mixtures 1 to 3 exhibit excellent wear resistance, as the rotation speed at which the friction coefficient exceeded 0.6 in a wear resistance test (10 mm / s) using a ball-on-flat tribometer was significantly higher than when PMHS or PDMS was used alone.

[0108] [Preparation of a stainless steel substrate having a porous portion on at least a portion of its surface] <Production Example 4> SUS304 stainless steel was wet-polished with #1500 SiC paper, degreased with acetone, dried, and then immersed in an aqueous solution of 2.67 M sodium hydroxide and 0.133 M ammonium peroxodisulfate at room temperature (25°C) for 18 hours to produce a stainless steel substrate with a porous layer on at least a portion of its surface. An SEM image of the surface of the produced stainless steel substrate is shown in Figure 13.

[0109] Example 15 [Synopsis of a stainless steel substrate having a porous portion on at least a portion 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. After removing excess PDMS using a spin coater at 5,000 rpm for 60 seconds, the substrate was heat-treated in an electric furnace at 300°C for 2 hours to solidify the PDMS, thereby obtaining laminate 15.

[0110] [Preparation of titanium substrate having a porous oxide film on at least part of its surface] <Production Example 5> A JIS type 2 titanium plate was electropolished in an ethylene glycol solution containing 1.0 M sodium chloride at 20°C for 10 minutes at 30 V and then for 10 minutes at 10 V to obtain a smooth surface. The electropolished titanium plate was anodized at 40 V for 5 minutes in an ethylene glycol electrolyte containing 0.1 M ammonium fluoride and 1.0 M water at 20°C to produce a titanium substrate with a porous oxide film on at least the surface. Because this film also contains fluoride ions, it was washed with ethylene glycol and then heat-treated at 350°C for 3 hours to convert it to an amorphous oxide. An SEM photograph of the surface of the produced titanium substrate is shown in Figure 14. As shown in Figure 14, a porous oxide film with numerous cylindrical pores with diameters of 30 nm to 50 nm was formed on the surface of the produced titanium substrate.

[0111] [Synovation of titanium substrates having porous oxide coatings on at least part of their surfaces] 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.

[0112] [Preparation of zinc substrate having a porous coating on at least a portion of its surface] <Production Example 6> A 1 mm thick, 99.99% pure Zn plate was subjected to pre-electropolishing by ultrasonic cleaning in acetone for 5 minutes and then in ethanol for 5 minutes using an ultrasonic cleaner (W-113). It was then electropolished by applying a voltage of 20 V for 10 minutes in 1 L of a 3:7 volumetric mixture of phosphoric acid and 99.5% ethanol, cooled to below 5°C, and vigorously stirring. A 12 cm x 17 cm SUS304 stainless steel plate was used as the counter electrode for electropolishing. After electropolishing, it was washed with deionized water and dried with compressed air. The electropolished Zn plate was then resuspended in 0.1 mol dm -3 The zinc substrate was subjected to constant-voltage anodization at a voltage of 4 V for 1800 seconds at room temperature (25°C) in an aqueous potassium hydroxide solution, to produce a zinc substrate having a porous coating on at least a portion of its surface. SEM photographs of the surface and cross section of the produced zinc substrate are shown in Figure 14.

[0113] [Synovation of zinc substrate having a porous coating on at least a portion of its surface] Example 17 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 a laminate 17.

[0114] [Preparation of iron substrate having a porous coating on at least a portion of its surface] <Production Example 7> A 0.3 mm thick iron plate with 99.99% purity was ultrasonically cleaned in acetone for 5 minutes. The sample was then anodized in 0.1 mol dm acetone without stirring. -3 of ammonium fluoride and 1.5 mol dm -3The iron substrate was anodized at a constant voltage of 80 V for 5 minutes without stirring in an ethylene glycol solution containing 1000 μL of ultrapure water. The temperature was then increased at a rate of 5 K / min, and heat treatment was performed in air at 400°C for 30 minutes. This converted the anodic oxide film, which contained a large amount of fluoride, into a porous oxide film, producing an iron substrate with a porous film on at least a portion of its surface. An SEM photograph of the surface of the produced iron substrate is shown in Figure 15.

[0115] [Synovation of iron substrate having a porous coating on at least a portion 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.

[0116] [Preparation of mesoporous alumina] <Production Example 8> α-Alumina powder (Baikowski, "BAIKALOX 1.0CR") was uniaxially pressed at 20 MPa and calcined in air at 1200°C for 12 hours to obtain macroporous α-alumina pellets (diameter 12 mm, thickness 1.0 mm). 8.4 parts of aluminum tri-sec-butoxide was mixed with 50 mL of hot water at 90°C and stirred to obtain a white sol. The resulting white sol was treated with 1 mL of 0.1 M aqueous nitric acid solution to obtain a 1 M boehmite (γ-AlOOH) clear sol. 1.05 parts of polyvinyl alcohol (PVA) (manufactured by PolyScience, weight average molecular weight Mw=78,000) was mixed with 50 mL of boiling water with stirring to obtain a PVA solution. 30 mL of the 1 M boehmite (γ-AlOOH) clear sol and 20 mL of the PVA solution were mixed to obtain a 0.6 M boehmite sol. The 0.6 M boehmite sol was spin-cast onto the α-alumina pellets at 3000 rmp / min for 20 seconds, then dried at room temperature (25°C) for 3 hours and annealed in air at 700°C for 3 hours to precipitate a 1.2 μm-thick mesoporous γ-alumina layer, producing a mesoporous alumina body.

[0117] [Synopsis of mesoporous alumina] Example 19 Amorphous fluororesin (CYTOP: manufactured by AGC Corporation, CTL-107MK) was added dropwise to the mesoporous alumina porous body prepared in Example 8, and the mesoporous alumina porous body was left to stand for approximately 10 minutes so that the entire surface was covered with the amorphous fluororesin.Then, the mesoporous alumina porous body was heat-treated at 80°C for 30 minutes and then at 180°C for 30 minutes to obtain laminate 19.

[0118] [Synovial surface properties of laminates 15 to 19] The static contact angle (°) of a 4 μL water droplet and the droplet sliding angle (°) of 10 μL water were measured for Laminates 15 to 19. The results are shown in Table 9.

[0119] [Table 9]

[0120] From Manufacturing Examples 1 to 3, Examples 1 to 14, Comparative Examples 1 to 3, and Tables 1 to 8 and FIGS. 1 to 12 relating to the evaluation results thereof, it was found that the synovial solid surface produced by injecting a lubricant into a porous portion formed by electrolytic oxidation (anodic oxidation) and then performing a heat treatment has excellent synovial properties with respect to various liquids, and the porous portion improves the adhesion between the lubricant and the substrate, thereby exhibiting excellent mechanical durability. From Manufacturing Examples 4 to 7, Examples 15 to 18, and Table 9 and Figures 13 to 16 relating to the evaluation results thereof, it can be seen that the synovial solid surfaces prepared by impregnating a lubricant into the porous portions formed on the surfaces of a stainless steel (SUS304) substrate, titanium, zinc, or iron and then performing a heat treatment have a static contact angle of a water droplet of 95° or more, indicating water repellency, and the droplet sliding angle for a 10 μL water droplet is all 5° or less, indicating excellent synovial properties with water. From Production Example 8, Example 19 and Table 9 relating to the evaluation results thereof, it can be seen that the synovial solid surface, which was produced by impregnating a porous body with a lubricant and then heat-treating it, and which has a porous portion and an organic layer formed from the lubricant that covers at least a portion of the porous portion and is filled inside the porous portion, has a static contact angle of a water droplet of 110° or more, exhibits excellent water repellency, and has a droplet sliding angle of 20° or less for a 10 μL water droplet, exhibits synovial properties against water.

Claims

1. The porous portion has an organic layer that covers at least a portion of the porous portion and fills the porous portion, the porous portion is an anodic oxide film of a metal material, the organic layer is a layer formed from one or more of polysiloxane and / or amorphous fluororesin, The polysiloxane is represented by the following formula (1): 【Chemistry 1】 (In formula (1), R 1 , R 2 , X 1 and X 3 each independently represent an alkyl group, an aromatic group or an unsaturated hydrocarbon group; X 2 and X 4 each independently represent an alkyl group, an aromatic group, an unsaturated hydrocarbon group or hydrogen; and n is an integer of 2 or greater. The n X 3 s and n X 4 s may be the same or different from one another.) is a compound represented by the organic layer is partially intermolecularly crosslinked; Laminate.

2. The electrochemical cell comprises a metal substrate, a porous portion provided on at least a portion of the metal substrate, and an organic layer that covers at least a portion of the porous portion and fills the interior of the porous portion, the porous portion is an anodic oxide film of a metal material, the organic layer is a layer formed from one or more of polysiloxane and / or amorphous fluororesin, The polysiloxane is represented by the following formula (1): 【Chemistry 1】 (In formula (1), R 1 , R 2 , X 1 and X 3 each independently represent an alkyl group, an aromatic group or an unsaturated hydrocarbon group; X 2 and X 4 each independently represent an alkyl group, an aromatic group, an unsaturated hydrocarbon group or hydrogen; and n is an integer of 2 or greater. The n X 3 s and n X 4 s may be the same or different from one another.) is a compound represented by the organic layer is partially intermolecularly crosslinked; Laminate.

3. The laminate according to claim 1 or 2, which has one or more of synovial properties, stain resistance, liquid repellency, and snow and ice sliding properties.

4. 3. The laminate according to claim 1 or 2, which is used as an electric wire, a steel tower, a metal structure, a utility pole, a transformer, an electric wire accessory, a power transmission-related device, a sign, a billboard, an antenna, a roof, a bag, a vehicle, an aircraft, a guardrail, a building material, or a food plant component.

5. A step of forming an organic layer on a metal substrate having a porous portion on at least a part of its surface, the organic layer covering at least a part of the porous portion and filling the interior of the porous portion; heating the organic layer; and the porous portion is an anodic oxide film of a metal material, the organic layer is a layer formed from one or more of polysiloxane and / or amorphous fluororesin, the organic layer is partially intermolecularly crosslinked; A method for manufacturing a laminate.

6. The method according to claim 5 , further comprising the step of forming a porous portion on at least a portion of the surface of the metal substrate.

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