WO2023032926A1 - Laminate and method for producing laminate - Google Patents

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

LAMINATED PRODUCT AND METHOD FOR MANUFACTURING LAMINATED BODY

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.

Slippery liquid infused porous surface (SLIPS), which mimics the trapping function of Nepenthes that exists in nature, is made by injecting lubricants such as perfluoropolyether and silicone oil into the micronanostructure to lower the free energy of the surface. Demonstrates dynamic liquid repellency.
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.

In Patent Document 1, 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.

In 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.

JP 2019-85597 A JP 2014-531989 A JP 2017-140405 A Japanese Patent Application Laid-Open No. 2015-531005 JP-A-11-342371 JP 2019-14793 A

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.
In the synovial solid surfaces described in Non-Patent Documents 1 to 4, 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.
In addition, as a result of extensive studies to solve the above problems, the present inventors have found that 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. Similar to , it has excellent synovial properties that allow various liquids such as water and oil to slide down easily, and also has abrasion resistance, stain resistance, liquid repellency, snow and ice sliding properties, droplet falling properties, The inventors have found that it exhibits many notable properties such as corrosion resistance and durability, and have completed the present invention.

That is, 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.

INDUSTRIAL APPLICABILITY 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. .

SEM images of the surface morphology of laminates 1, 3, 6 (examples) and metal substrate 1 (comparative example). SEM images of cross-sectional forms of surface portions of laminates 1, 3, and 6 (Examples). Cross-sectional EDS analysis images of the surface portions of laminates 1, 3, and 6 (Examples). SEM images of cross-sectional morphologies of surface portions of laminates 15 to 17 (comparative examples). An image of the surface morphology, an SEM image of the surface morphology, and a cross-sectional EDS analysis image of the surface portion after the abrasion resistance test was performed on the laminate 6 (Example) and the laminate 17 (Comparative Example). An image of the surface morphology, an SEM image of the surface morphology, and a cross-sectional EDS analysis image of the surface portion after the abrasion resistance test was performed on the laminate 9 (Example). Surface morphology images after potentiodynamic polarization measurement of laminates 1 to 3 (Examples) and an electropolished Al substrate (Comparative Example). SEM images of the surface morphology of Metal Substrate 1 and Metal Substrate 2 with different anodizing conditions. SEM images of the cross-sectional morphology of the surfaces of laminates 6 and 7 (Example). Cross-sectional EDS analysis images of the surface portions of laminates 6 and 7 (Example). SEM images of cross-sectional forms of surface portions of laminates 8, 9, and 13 (Examples). Cross-sectional EDS analysis images of surface portions of laminates 8, 9, and 13 (Example). 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. SEM images of the surface morphology and cross-sectional morphology of the surface portion of the zinc base material produced in Production Example 6. FIG. 4 is a SEM image of the surface morphology of the iron substrate surface portion produced in Production Example 7. FIG.

1 Lubricant layer 2 Porous portion 3 Metal substrate

The laminate and the method for producing the laminate of the present invention will be described in detail below. It should be noted that the present invention is not limited at all by the embodiments exemplified below within the scope of the invention.

[Laminate]
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.

<Porous part>
In the first and second aspects of the present invention, 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. For example, 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 μm or less, more preferably 10 μm or less, even more preferably 1 μm or less, still more preferably 500 nm or less. is. When 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. In addition, if 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 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 filling amount of polysiloxane and/or amorphous fluororesin forming the organic layer is reduced, and the laminate may not exhibit the desired effects.

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.
In the first aspect of the present invention, 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.
In the second aspect of the present invention, it is possible to use 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. In addition, it is also possible to use 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. In the present invention, 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 (electrolytic solution, anodizing voltage, anodizing current, anodizing time, etc.) 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.
As 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. In the present invention, sulfuric acid, oxalic acid or phosphoric acid are preferred.
In addition, 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.) can be used as the electrolytic solution. .
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.

In the present invention, 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.
In the present invention, 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 μm or less, more preferably 200 μm or less.

In the present invention, 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.

In the present invention, after the anodizing treatment, if necessary, 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. or lower, 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. In the present invention, 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.

<Metal substrate>
The metal substrate is not particularly limited. For example, Mg, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Nb, Pd, Ag, Sn, Ta, W, Pt, Au, Pb, one or more of these alloys containing these, laminates thereof, and the like. Among these, 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.). Examples of stainless steel include austenitic stainless steel, austenitic ferritic duplex stainless steel, ferritic stainless steel, and martensitic stainless steel. In particular, 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.

<Organic layer>
In the present invention, the organic layer covers at least a portion of the porous portion and fills the inside of the porous portion.
Moreover, 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 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.
In the present invention, the polysiloxane and/or amorphous fluororesin forming the organic layer may be dissolved in a suitable organic solvent or the like. In the present invention, the organic layer is preferably gel-like. When the organic layer is a gel-like material, the drop falling angle is reduced and the synovial properties are improved.
The term "gel-like" as used herein 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. For example, when dimethylpolysiloxane, which is a type of polysiloxane, is heat-treated at a thermal decomposition initiation temperature (about 150° C.) or higher, for example, at 280° C. for 3 hours, part of the dimethylpolysiloxane is thermally decomposed and intermolecularly crosslinked. Viscosity increases and a gel-like substance is formed.

(Polysiloxane)
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. For example, 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. In the formula, 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.
For example, 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 One or more selected from the group consisting of 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.

Specific examples of polysiloxane include 1,1,3,3-tetramethyldisiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, and trimethylsiloxy group-blocked at both ends of the molecular chain. Dimethylsiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both molecular chain ends, dimethylsiloxane/methylhydrogensiloxane copolymer blocked at both molecular chain ends with trimethylsiloxy groups, dimethylsiloxane/methylhydrogen at both molecular chain ends blocked with trimethylsiloxy groups Siloxane-methylphenylsiloxane copolymer, dimethylpolysiloxane with dimethylhydrogensiloxy group-blocked at both molecular chain ends, dimethylsiloxane-methylhydrogensiloxane copolymer with dimethylhydrogensiloxy group-blocked at both molecular chain ends, dimethylhydrogensiloxane at both molecular chain ends Gensiloxy group-blocked dimethylsiloxane/methylphenylsiloxane copolymer, both molecular chain ends dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane, both molecular chain ends trimethylsiloxy group-blocked dimethylsiloxane/methylvinylsiloxane copolymer, molecular chain both ends Trimethylsiloxy-terminated methylvinylpolysiloxane, both molecular chain ends trimethylsiloxy-terminated dimethylsiloxane/methylvinylsiloxane/methylphenylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy-terminated dimethylpolysiloxane, molecular chain both ends dimethyl Vinylsiloxy group-blocked methylvinylpolysiloxane, both molecular chain ends dimethylvinylsiloxy group-blocked dimethylsiloxane/methylvinylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane/methylvinylsiloxane/methylphenylsiloxane copolymer , trivinylsiloxy group-blocked dimethylpolysiloxane at both ends of the molecular chain, polysiloxane obtained from methyltrialkoxysilane, and the like.

As the polysiloxane in the present invention, 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.)
It is preferably a linear polysiloxane represented by.

Further, as the 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.).

Examples of 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 aromatic groups for R ¹ , R ² , R ³ , X ¹ , X ² , X ³ and X ⁴ in formulas (1) and (2) include aromatic groups having 6 to 30 carbon atoms. For example, phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group (or anthracene group), phenanthrenyl group (or phenanthrene group), biphenyl group, terphenyl group, pyrenyl group (or pyrene group), perylenyl group (or perylene group), benzyl group, phenethinyl group, and the like. These aromatic groups having 6 to 30 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. For example, 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.

In the polysiloxane of formula (1), 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, X-40-9301, X-88-1004 and X-88-1007 (all manufactured by Shin-Etsu Silicone Co., Ltd.).

As the 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).
As 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 mixing ratio (volume ratio) of PMHS and PDMS is not particularly limited, but is, for example, PDMS/PMHS=30/70 to 85/15, preferably 45/55 to 80/20.

(In the formula, p and q represent the number of repeating units, p is 10 to 200 and q is 10 to 100.)

(Wherein, r represents the number of repeating units, 1 to 2500, preferably 4 to 2250.)
CH ₃ SiO _1.5 (5)

(Amorphous fluororesin)
The amorphous fluororesin is not particularly limited as long as it is an amorphous (amorphous) resin.
Examples of 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. One or more selected types can be mentioned.
Commercially available amorphous fluororesins may be used as they are. For example, the AF series (manufactured by DuPont Fluorochemicals, Mitsui), the Algoflon series (manufactured by Solvay Special Polymers Japan), and the Cytop series (manufactured by AGC) can be mentioned.

In the present invention, 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.

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.

(Coating and impregnation method)
In the present invention, 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. For example, 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. In the present invention, it is preferable to use the dip coating method from the viewpoint of production efficiency and the like. In addition, when using the dip coating method, it is possible to promote the filling into the inside of the porous portion by performing it under ultrasonic waves. In addition, in the present invention, by using 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 μg/cm ² or more, preferably 50 μg/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. In the present invention, at least a portion of the polysiloxane and/or the amorphous fluororesin undergoes intermolecular cross-linking by heat treatment, the organic layer is gelled, the viscosity is increased, and the heat treatment conditions are such that a gel-like substance having viscoelasticity can be obtained. Preferably.
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. As a heating means, it is preferable to use a heating furnace (oven).

By performing 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 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.
Further, in the present invention, 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.

<Laminate characteristics>
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. In addition, 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.
If the static contact angle, contact angle hysteresis, and drop falling angle are within these ranges, 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.

<Use of laminate>
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. For example, 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. Articles, etc. that require waterproofness, etc.; In particular, 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.

[Laminate production method]
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.
In the method for producing a laminate according to the second aspect of the present invention, 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.

Hereinafter, the present invention will be described in detail based on specific examples. These specific examples are merely one aspect of the present invention. The present invention is in no way limited by these examples.
Unless otherwise specified, the compounds used in these specific examples were commercially available products and used as they were without purification.

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

[Preparation of a metal substrate having a porous portion on at least part of the surface]
<Production Example 2>
Using the electropolished Al substrate obtained in Production Example 1, anodization was performed at 15° C. in 0.3 M H ₂ SO ₄ at an applied voltage of 25 V for 30 minutes to form a porous alumina coating layer on the aluminum plate. formed.
Furthermore, a pore widening treatment is performed by immersing the porous alumina coating layer in a 5% by mass H ₃ PO ₄ 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, and at least part of the surface is porous. A metal substrate 1 having a mass was obtained.

<Production Example 3>
Using the electropolished Al substrate obtained in Production Example 1, anodization treatment was performed at 20° C. in 0.3 M H ₃ PO ₄ at an applied voltage of 100 V for 30 minutes to form a porous alumina coating layer on the aluminum plate. formed.
Furthermore, a pore widening treatment is performed by immersing the porous alumina coating layer in a 5% by mass H ₃ PO ₄ 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, and at least part of the surface is porous. A metal substrate 2 having a mass was obtained.

[Preparation of laminate]
<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.

<Example 5>
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.

<Example 6>
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.

<Example 8>
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.

<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.

<Example 13>
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.
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.

<Comparative Example 1>
Polymethylhydrogensiloxane (PMHS: KF-99, manufactured by Shin-Etsu Silicone Co., Ltd.) was used as the lubricant.
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.

<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 Silicone Co., Ltd.) was used as the lubricant.

<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, CTL-107MK) was used as the lubricant.

[evaluation]
<Measurement method, etc.>

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

(Measurement method of contact angle hysteresis) Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DM-CE1), the contact angle when injecting a droplet from a microsyringe into a droplet of about 4 μL on the sample surface (Advancing contact angle) and the contact angle (receding contact angle) when the droplet is sucked are observed and measured with a CCD camera attached to the device, and the difference between the advancing contact angle and the receding contact angle is defined as the contact angle hysteresis. asked.

(Method for measuring droplet falling angle)
A droplet of 10 μL 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.

(Surface SEM)
The surface morphology was observed with an electron microscope (surface SEM) by the following method.
In order to suppress charge-up during observation of the synovial solid surface, a tungsten film of about 10 nm was formed using a sputtering apparatus (manufactured by Vacuum Device Co., Ltd., MSP-20TK). After that, observation was performed using a field emission scanning electron microscope (Sigma-500 manufactured by ZEISS) at an acceleration voltage of 2 kV or less.

(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.

(Abrasion test)
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.

(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 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. After ice block formation, while the sample was placed on a water-cooled cooling unit maintained at -20°C, the tip of a stress measuring device (Imada ZTS-50N) was bitten by a wire wrapped around the container, and the measuring device was operated. The sample was pulled horizontally by hand, and the shear stress at which the ice block separated from the surface of the sample was determined as the ice adhesion force.

<Wettability>
For laminates 1, 3 and 6 obtained in Examples 1, 3 and 6, liquids having surface tensions shown in Table 1 (water (solvent 1), ethylene glycol (solvent 2), rapeseed oil (solvent 3), hexadecane (solvent 4) and ethanol (solvent 5)), the static contact angle (°), the contact angle hysteresis (°) which is the difference between the advancing contact angle and the receding contact angle, and the droplet falling angle (°) at a droplet volume of 10 μL ) was measured. Table 1 shows the results.

From Table 1, 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. These results show that the surfaces of the laminates 1, 3 and 6 are water-repellent and oleophilic. In terms of static contact angle, the liquid repellency for solvents 2 to 5 is not high, but exhibits excellent synovial properties. 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 μL 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 μL and 30 μL. Table 2 shows the results.

From Table 2, the water tumble angle at a water droplet amount of 30 μL for the laminates 1, 3, 6 and 14 and the water tumble angle at a water droplet amount of 10 μL 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.

<Effect of heat treatment temperature on wettability>
For the laminates 1 to 5 and 9 to 12 obtained in Examples 1 to 5 and 9 to 12, the static contact angle (°) of water and the falling angle (°) of water droplets at a water droplet volume of 10 μL were measured. Table 3 shows the results.

When PMHS is heat-treated, it becomes a gel at 150°C and a solid (powder) at 200°C.
When PDMS is heat-treated, it is liquid at 250°C, gel at 280°C, and solid (powder) at 300°C.
When the PSi mixture 2 is heat-treated, it turns into a gel at 180°C, 200°C, 220°C and 250°C.
From Table 3, the heat treatment temperature is adjusted so that the lubricant becomes solid after the heat treatment for the laminates 2 and 4 obtained by adjusting the heat treatment temperature so that the lubricant becomes a gel after the heat treatment. As compared with the laminates 1 and 3 obtained by the above, the water tumble angle is small. From this, it can be seen that by adjusting the heat treatment temperature of the lubricant, it is possible to control the lubricating property (water lubricating property) of the laminate, such as the water sliding angle.

<Surface morphology>
The surface morphology of the laminates 1, 3 and 6 obtained in Examples 1, 3 and 6 and the metal substrate 1 obtained in Production Example 2 was observed with an electron microscope. The results are shown in FIG.
From FIG. 1, it can be seen that the surface of the metal substrate 1 has a porous portion in which pores having a pore diameter of 30 to 50 nm are 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. In addition, the generation of wrinkles due to heat shrinkage was confirmed on the surface of the laminate 3 .

<Cross-sectional shape of the surface>
The cross-sectional morphologies of the surface portions of the laminates 1, 3 and 6 obtained in Examples 1, 3 and 6 were observed with an electron microscope. A cross-sectional SEM image of the surface portion is shown in FIG. SEM images of the porous portion are also shown in FIG.
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.
The cross-sectional morphologies of the surface portions of the laminates 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. It can be seen that 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.

<Abrasion resistance>
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 were subjected to an abrasion test at a rotational speed of 1 mm/s. Table 4 shows the results of the number of revolutions when the coefficient of friction (coefficient of dynamic friction) exceeds 0.6 (the number of revolutions when the coefficient of friction exceeds 0.6) and the initial coefficient of friction.
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.

From Table 4, it can be seen that the laminates 1, 3 and 6 and the laminates 15 to 17 do not have a large difference in the initial coefficient of friction. However, although 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. , it can be seen that the wear resistance is greatly improved.
It is considered that 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.
Further, from FIG. 5, 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.

<Heat treatment temperature dependence of wear resistance>
The laminates 1 to 4 to 12 obtained in Examples 1 to 4 and 9 to 12 were subjected to an abrasion test at a rotation speed of 10 mm / s, and the number of rotations when the coefficient of friction exceeded 0.6 (friction The number of rotations when the coefficient exceeds 0.6) was measured. Table 5 shows the results.
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.

From Table 5, 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.

<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 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. Using the laminates 1, 3, and 6 and the electropolished Al substrate as the working electrode, 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. .

<Ice resistance>
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.

From Table 6, the ice adhesion (shear adhesion strength of ice blocks) at −20° C. showed a large value exceeding 700 kPa for the electropolished Al substrate, but the laminates 1, 3, and 6 showed a value of about 50 to 120 kPa. A low value is shown, and it turns out that it has the anti-icing property excellent.

<Effect of anodic oxidation conditions>
Regarding the laminate 6 obtained in Example 6 and the laminate 7 obtained in Example 7, each atom concentration (atom%) in the porous portion, fluorine atoms with respect to the sum of fluorine atoms and aluminum atoms in the porous portion Table 7 shows the ratio F / (F + Al) and the number of rotations when the friction coefficient exceeds 0.3 or 0.6 in the wear resistance test (rotation speed 1 mm / s) by a ball-on-flat tribometer. .
FIG. 8 shows electron micrographs of the surface morphology of the metal substrate 1 and the metal substrate 2 .
FIG. 9 shows electron micrographs of the cross-sectional forms of the surface portions of the laminates 3 and 4. As shown in FIG.
FIG. 10 shows the results of cross-sectional EDS analysis of the surface portions of the laminates 3 and 4. FIG.

From Table 7 and FIGS. 8 to 10, it is possible to adjust the pore size of the porous portion by adjusting the anodic oxidation conditions when forming the porous portion on the electropolished Al plate. It can be seen that it is possible to improve the filling rate of the lubricant in the porous portion by increasing the .
In addition, from the results of the wear resistance test (rotational speed 1 mm / s) by a ball-on-flat tribometer in Table 7, the laminate 4, which contains more lubricant in the porous portion than the laminate 3, has better wear resistance. You can see that it is improving.

<Various evaluations of PSi mixture>
For the laminates 1, 3, 8, 9 and 13 obtained in Examples 1, 3, 8, 9 and 13, the static contact angle (°) to water and the difference between the advancing and receding contact angles to water A certain contact angle hysteresis (°) and water drop falling angle (°) in 30 μL of water were measured. Table 8 shows the results.
Furthermore, for the laminates 1, 3, 8, 9 and 13, 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. As shown in FIG.
FIG. 12 shows the results of cross-sectional EDS analysis of the surfaces of the laminates 8, 9, and 13. FIG.

From Table 8, 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 .

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

<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. Using a spin coater, 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 .

[Preparation of Titanium Base Material Having Porous Oxide Film on at least Part of Surface]
<Production Example 5>
A JIS class 2 titanium plate was electropolished in an ethylene glycol solution containing 1.0 M sodium chloride at 20° C. at 30 V for 10 minutes and then at 10 V for 10 minutes 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., resulting in porous oxidation of the surface at least to the sun. A titanium substrate having a coating was produced. Since this film also contains fluoride ions, it was changed to an amorphous oxide by heat treatment at 350° C. for 3 hours after washing with ethylene glycol. 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.

[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.

[Preparation of zinc substrate having porous coating on at least part of surface]
<Production Example 6>
A Zn plate with a thickness of 1 mm and a purity of 99.99% was subjected to ultrasonic cleaning for 5 minutes in acetone and 5 minutes in ethanol using an ultrasonic cleaning machine (W-113) to perform electropolishing pretreatment. rice field. Next, electropolishing was performed by applying a voltage of 20 V for 10 minutes while cooling to 5° C. or less in 1 L of a phosphoric acid:99.5% ethanol solution mixed at a volume ratio of 3:7 and vigorously stirring. A SUS304 stainless steel plate of 12 cm×17 cm was used as the counter electrode for electropolishing. After electropolishing, it was washed with deionized water and dried with compressed air. Next, the electrolytically polished Zn plate is subjected to constant voltage anodization at room temperature (25 ° C.) in a 0.1 mol dm ^-3 potassium hydroxide aqueous solution at a voltage of 4 V for 1800 seconds to form a porous coating on at least part of the surface. A zinc substrate having FIG. 14 shows SEM photographs of the surface and cross section of the zinc base material thus produced.

[Synovial liquefaction of a zinc substrate having a porous coating on at least a part 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 laminate 17 .

[Preparation of iron substrate having porous coating on at least part of surface]
<Production Example 7>
A Fe plate with a thickness of 0.3 mm and a purity of 99.99% was ultrasonically cleaned in acetone for 5 minutes. Then, the sample was anodized in an ethylene glycol solution containing 0.1 mol·dm ⁻³ of ammonium fluoride and 1.5 mol·dm ⁻³ of ultrapure water without stirring at a constant voltage of 80 V. It was anodized by applying voltage for 5 minutes. Next, the temperature is raised at a temperature elevation rate of 5 K/min, and heat treatment is performed in the atmosphere at 400 ° C. for 30 minutes to change the fluoride-rich anodic oxide film into a porous oxide film, thereby forming at least a portion of the surface. An iron substrate with a porous coating was produced. FIG. 15 shows an SEM photograph of the surface of the iron substrate thus produced.

[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.

[Preparation of mesoporous alumina porous material]
<Production Example 8>
α-Alumina powder (manufactured by Baikowski, "BAIKALOX 1.0CR") was uniaxially pressurized at 20 MPa and fired at 1200 ° C. in air 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 obtained white sol was treated by adding 1 mL of 0.1 M nitric acid aqueous solution to obtain 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 while stirring to obtain a PVA solution.
30 mL of the 1M boehmite (γ-AlOOH) clear sol and 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 α-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 γ-alumina layer having a thickness of 1.2 μm was deposited to prepare a mesoporous alumina porous material.

[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 .

[Synovial surface characteristics of laminates 15 to 19]
For laminates 15 to 19, the static contact angle (°) with a 4 μL water droplet and the drop falling angle (°) with 10 μL water were measured. The results are shown in Table 9

From Production Examples 1 to 3, Examples 1 to 14, Comparative Examples 1 to 3, Tables 1 to 8 and FIGS. 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.
From Production Examples 4 to 7, Examples 15 to 18, and Table 9 and FIGS. 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.
From Production Examples 8 and 19 and Table 9 relating to the evaluation results thereof, 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.

Claims (8)

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.
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,
   A laminate, wherein the organic layer is a layer formed from one or more of polysiloxane and/or amorphous fluororesin.
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.)
   The laminate according to claim 1 or 2, which is a compound represented by.
4. The laminate according to claim 1 or 2, wherein the organic layer is gel.
5. The laminate according to claim 1 or 2, which has one or more of synovial properties, antifouling properties, liquid repellency, and snow/ice sliding properties.
6. Used as electric wires, steel towers, metal structures, electric poles, transformers, electric wire accessories, equipment related to power transmission, signs, signboards, antennas, roofs, bags, vehicles, aircraft, guardrails, building materials, and food plant members. 3. Or the laminated body of 2.
7. forming an organic layer covering at least a portion of the porous portion and filling the interior of the porous portion on a metal substrate having a porous portion on at least a portion of the surface;
   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.
8. The method according to claim 7, comprising the step of forming a porous portion on at least part of the surface of the metal substrate.

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